Heat-storage warm-keeping composite fabric and preparation method thereof

Abstract

The invention relates to the technical field of layered materials, and discloses a heat-storage and warm-keeping composite fabric and a preparation method thereof. The preparation method of the heat-storage and warm-keeping composite fabric comprises the following steps: preparing the modified acrylic fibers loaded with the modified phase-change microcapsules; the preparation method comprises the following steps: blending Cs0. 33WO3 nanoparticles and a PA6 / 66 copolymer, extruding, slicing, and carrying out melt spinning with the PA6 / 66 copolymer to obtain modified PA6 / 66 hollow fibers; preparing a polyurethane finishing liquid containing the modified nano carbon black and chitosan; preparing the modified acrylic fibers and the cotton fibers into an outer fabric; the modified PA6 / 66 hollow fiber is made into a middle layer fabric; fitting the inner-layer fabric, the middle-layer fabric and the outer-layer fabric to obtain a composite fabric; and finishing the composite fabric with a polyurethane finishing liquid to obtain the heat-storage and warm-keeping composite fabric. The heat-storage and warm-keeping composite fabric has excellent antistatic performance, heat-storage and warm-keeping performance, anti-pilling performance, moisture absorption and air permeability.

Description

Technical Field

[0001] The present invention relates to the technical field of layered materials, and particularly to a heat storage and warmth - retaining composite fabric and a preparation method thereof. Background Art

[0002] When doing outdoor sports in a cold environment, the sharp change in skin surface temperature will affect the exercise effect, experience, and even physical health. Winter sports clothing not only needs to have the function of moisture absorption and sweat discharge to keep the body skin dry, but also needs to be able to store heat and keep warm to help the human body resist the cold.

[0003] Acrylic fiber has the characteristics of good warmth retention, not easy to mildew and moth - eat, fluffy and soft, etc., and is widely used in winter warm - keeping clothing fabrics. For example, Chinese patent application CN107354529A discloses a preparation method of acrylic fiber, acrylic fiber and fabric; wherein, the preparation method includes: respectively providing a ceramic powder composition and modified graphene; dispersing the ceramic powder composition in deionized water, then adding a coupling agent, after stirring, adding a polyacrylonitrile solution and uniformly mixing to obtain a cortical material; dispersing the modified graphene in deionized water, stirring and then adding a polyacrylonitrile solution and uniformly mixing to obtain a core - layer material; through composite spinning, coating the cortical material outside the core - layer material to form a core - shell composite structure acrylic fiber; thus, on the premise of ensuring antistatic performance, it can effectively reduce the cost by reducing the usage amount of graphene, and make the acrylic fiber have the characteristics of warmth retention, easy dyeing and durability, etc.

[0004] However, acrylic fiber fabrics have problems such as poor moisture absorption and air permeability, easy pilling, especially in a dry winter environment, the static electricity phenomenon is more significant, which will exacerbate the pilling phenomenon of the fabric. Summary of the Invention

[0005] In order to solve the above - mentioned technical problems, the present invention provides a preparation method of a heat storage and warmth - retaining composite fabric, including the following steps: Step (1), the acrylic fiber is pretreated with an aqueous sodium hydroxide solution, then grafted with sorbitol, and finally loaded with modified phase - change microcapsules to obtain modified acrylic fiber; Among them, the preparation method of the modified phase - change microcapsules includes the following steps: Step S1, graphene oxide is successively modified with phthalic anhydride, functionalized with zinc ions, and treated with a silane coupling agent KH - 570 to obtain composite - modified graphene oxide; Step S2, prepare phase - change microcapsules with n - butyl stearate and n - octadecane binary phase - change material as the core material, and methyl methacrylate, pentaerythritol triacrylate, and composite - modified graphene oxide as the shell; Step S3, nano - silver is surface - treated by amination and then grafted onto the phase - change microcapsules to obtain modified phase - change microcapsules; Step (2): Using cesium carbonate and tungsten oxide as raw materials to prepare Cs 0.33 WO3 nanoparticles; Cs 0.33 WO3 nanoparticles are blended with PA6 / 66 copolymer, extruded and sliced, and then melt-spun with PA6 / 66 copolymer to obtain modified PA6 / 66 hollow fibers; The modified acrylic fibers and cotton fibers are made into the outer fabric; the modified PA6 / 66 hollow fibers are made into the middle fabric; the inner fabric, the middle fabric, and the outer fabric are laminated to obtain the composite fabric; Step (3): Modifying nano-carbon black with polydopamine to obtain modified nano-carbon black; preparing a polyurethane finishing solution containing modified nano-carbon black and chitosan through a reaction; The composite fabric is padded twice with the polyurethane finishing solution, and then baked to obtain the heat storage and warmth retention composite fabric.

[0006] Preferably, in the step (1), the preparation method of the modified acrylic fibers specifically includes the following steps: Heat an aqueous sodium hydroxide solution with a mass fraction of 3-5% to 70-90°C, add acrylic fibers, with a solid-liquid ratio of 20:(175-195), react at 70-90°C for 4-8 minutes, then take out, wash, and dry to obtain pretreated acrylic fibers; Immerse the pretreated acrylic fibers in an aqueous sorbitol solution with a mass fraction of 8-10% for 10-30 minutes, extrude and control the wet weight to be 180-200 wt%, first heat at 75-80°C for 3-5 minutes, then heat at 178-182°C for 4-6 minutes, take out, wash, and dry to obtain functionalized acrylic fibers; Immerse the functionalized acrylic fibers in a modified phase change microcapsule / water dispersion with a concentration of 40-50 g / L for 3-5 minutes, then dry at 55-60°C for 10-15 minutes, and then immerse in an aqueous ethylene glycol diglycidyl ether solution with a concentration of 40-50 g / L for 5-10 minutes, take out, and cure at 103-108°C for 50-70 minutes to obtain modified acrylic fibers; In the above process, the acrylic fibers are pretreated with an aqueous sodium hydroxide solution and undergo a hydrolysis reaction in the alkali solution, and the cyano groups in the acrylic fibers are converted into carboxyl groups to obtain pretreated acrylic fibers; then the carboxyl groups on the surface of the pretreated acrylic fibers react with the hydroxyl groups of sorbitol to obtain functionalized acrylic fibers with rich hydrophilic hydroxyl groups on the surface; further, using ethylene glycol diglycidyl ether as a crosslinking agent, the epoxy groups of ethylene glycol diglycidyl ether react with the hydroxyl groups on the functionalized acrylic fibers and the modified phase change microcapsules to graft the modified phase change microcapsules onto the acrylic fibers to obtain modified acrylic fibers.

[0007] Further, in the step (1), the preparation method of the modified phase change microcapsules specifically includes the following steps: Step S1: Mix graphene oxide, phthalic anhydride, benzene, and p-toluenesulfonic acid in a mass ratio of 1:(1.5 - 2.5):(9 - 10):0.04, reflux and react at 97 - 103 °C for 2.5 - 3.5 h, and purify to obtain modified graphene oxide; Mix the modified graphene oxide and an aqueous zinc nitrate solution with a concentration of 1 mol / L in a mass ratio of (2 - 4):(30 - 50), and under the condition of 40 - 45 KHz, ultrasonically treat at room temperature for 20 - 30 h, and purify to obtain zinc ion-functionalized graphene oxide; Add the zinc ion-functionalized graphene oxide into ethanol, ultrasonically treat, adjust the pH of the mixed system to 2.9 - 3.1 with an aqueous hydrochloric acid solution, then add a 3.6% silane coupling agent KH-570 / ethanol solution under stirring, heat to 58 - 62 °C and stir and react for 20 - 30 h, and purify to obtain composite modified graphene oxide; wherein, the mass ratio of the zinc ion-functionalized graphene oxide, ethanol, and the silane coupling agent KH-570 / ethanol solution is (0.1 - 0.2):(80 - 100):(8 - 12); In the above process, the surface of graphene oxide has abundant hydroxyl and carboxyl groups. The acid anhydride ring opening of phthalic anhydride reacts with some hydroxyl groups on the surface of graphene oxide to generate carboxyl groups, introducing more carboxyl groups on the surface of graphene oxide, and then further combining with the metal zinc ions in zinc nitrate to uniformly fix the zinc ions on graphene oxide, obtaining zinc ion-functionalized graphene oxide; then, the zinc ion-functionalized graphene oxide is treated with silanol after hydrolysis of the silane coupling agent KH-570 to introduce carbon-carbon double bonds, obtaining composite modified graphene oxide; As is well known, graphene oxide has excellent mechanical properties, electrical conductivity, thermal conductivity, and photothermal conversion effect. The fixation of zinc ions can improve the electrical conductivity of graphene oxide, enhance the light absorption efficiency of graphene oxide, and reduce the infrared emissivity, effectively inhibiting thermal radiation and reducing the heat transfer radiated to the surrounding environment to achieve a better heat pipe effect.

[0008] Step S2: Mix n-butyl stearate and n-octadecane at a mass ratio of (1.6 - 3.2):(2.4 - 4.8), melt them at 40 - 44 °C, stir for 10 - 20 min, and cool to room temperature to obtain a binary phase change material; mix the binary phase change material, methyl methacrylate, pentaerythritol triacrylate, and composite modified graphene oxide at a mass ratio of (4 - 8):(8 - 16):(0.8 - 1.6):(0.003 - 0.005), and ultrasonicate for 30 - 60 min to obtain an oil phase; mix alkyl vinyl sulfonate and deionized water at a mass ratio of (0.5 - 0.9):(58.6 - 117.2), stir for 20 - 30 min, then add the above oil phase and emulsify to obtain an O / W pre-emulsion; add an aqueous solution of ammonium persulfate with a mass fraction of 10% to the above O / W pre-emulsion within 60 - 120 min, stir and react at 70 - 80 °C for 4.5 - 5.5 h, filter, wash, and dry to obtain phase change microcapsules; wherein, the mass ratio of the aqueous ammonium persulfate solution to the O / W pre-emulsion is (15 - 30):(71.9 - 143.8); In the above process, n-octadecane and n-butyl stearate are used as the binary phase change core material, and methyl methacrylate, pentaerythritol triacrylate, and composite modified graphene oxide are free-radically copolymerized to obtain the shell of the phase change microcapsule. The phase change temperatures of n-octadecane and n-butyl stearate are both within the human comfort temperature range. The polymer shell that confines the phase change material in the nanocapsule has a relatively low thermal conductivity, which is not conducive to accelerating the thermal response of heat storage and release and improving the energy utilization efficiency. Doping the composite modified graphene oxide into the shell of the phase change microcapsule in the form of chemical bonds solves this problem; the introduction of pentaerythritol triacrylate containing hydroxyl groups and three vinyl groups in the shell of the phase change microcapsule increases the structural stability and reactivity of the phase change microcapsule (providing reactive groups of hydroxyl groups); Step S3: Add nano-silver to an ethanol aqueous solution with a volume fraction of 80%, add silane coupling agent KH-550 in a nitrogen atmosphere, react at 40 - 45 °C for 8 - 10 h, and purify to obtain amino-functionalized nano-silver; wherein, the mass ratio of nano-silver, ethanol aqueous solution, and silane coupling agent KH-550 is (0.5 - 3):(80 - 120):(0.5 - 1); The amino-functionalized silver nanoparticles are ultrasonically dispersed in ultrapure water for 20 - 40 min to obtain mixture A; the phase change microcapsules are ultrasonically dispersed in ultrapure water for 1 - 2 h to obtain mixture B; mixture A and mixture B are mixed, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide are added under stirring conditions, and the reaction is carried out at room temperature for 40 - 50 h, followed by purification to obtain modified phase change microcapsules; wherein, the mass ratio of amino-functionalized silver nanoparticles, phase change microcapsules, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N-hydroxysuccinimide is (0.4 - 0.8):(10 - 15):(1 - 1.5):(1 - 1.5); In the above process, the silver nanoparticles are modified with the silane coupling agent KH-550 to introduce amino groups on their surfaces, and then through the amidation reaction between the amino groups and the carboxyl groups on the surface of the composite modified graphene oxide in the phase change microcapsule shell, modified phase change microcapsules with silver nanoparticles deposited on the surface are obtained; the deposition of silver nanoparticles improves the electrical conductivity and thermal conductivity of the phase change microcapsules. As a thermal conductive material, silver nanoparticles exhibit local surface plasmon resonance (LSPR), thereby enhancing the light absorption capacity of the phase change microcapsules, converting light energy into heat energy, and quickly transferring it to the phase change material; further, the amino-functionalized silver nanoparticles are deposited on the phase change microcapsules, introducing hydrophilic amino groups, and increasing the surface roughness and light absorption specific surface area of the phase change microcapsules.

[0009] Preferably, in the step (2), the preparation method of the modified PA6 / 66 hollow fiber specifically includes the following steps: Cesium carbonate and tungsten oxide are ball-milled and mixed at a molar ratio of 1:3, and then heat-treated in a reducing gas atmosphere at 590 - 610 °C for 4 - 6 h to obtain Cs 0.33 WO3 nanoparticles; wherein, the reducing gas is obtained by mixing hydrogen and nitrogen at a volume ratio of 5:95; Cs 0.33 WO3 nanoparticles and PA6 / 66 copolymer are mixed at a mass ratio of (0.15 - 0.25):1, extruded at 230 - 240 °C, and sliced to obtain modified PA6 / 66 slices; The modified PA6 / 66 slices and PA6 / 66 copolymer are mixed at a mass ratio of 1:(8 - 10), melt-spun at 280 - 300 °C, and the spun fibers are air-cooled, wound, and stretched with a draw ratio of 1.5 - 1.7 to obtain modified PA6 / 66 hollow fibers; In the above process, Cs 0.33 WO3 nanoparticles are prepared from cesium carbonate and tungsten oxide, and then mixed with PA6 / 66 copolymer and subjected to subsequent treatment to obtain modified PA6 / 66 hollow fibers, Cs 0.33WO3 nanoparticles can absorb near-infrared radiation and generate heat, making the fabric warmer, while the hollow fibers can reduce heat loss, thereby achieving the purpose of heating and keeping warm.

[0010] Preferably, in step (2), the outer fabric is obtained by blending modified acrylic fiber and cotton fiber in a mass ratio of 1:1 into an outer yarn with a count of 30-40S (English count), and then knitting; the outer fabric has a gram weight of 100-120g / m 2 .

[0011] Preferably, in step (2), the middle layer fabric is obtained by spinning and knitting modified PA6 / 66 hollow fibers; the weight of the middle layer fabric is 80-100 g / m 2 .

[0012] Preferably, in step (2), the inner layer fabric is made of pure cotton yarn spun by knitting technology and has a gram weight of 100-120 g / m 2 Pure cotton fiber fabric.

[0013] Preferably, in step (3), the method for preparing the polyurethane finishing liquid specifically comprises the following steps: Mix nano carbon black, dopamine hydrochloride, and a Tris-HCl buffer solution having a pH of 8.5 in a dosage ratio of (0.4-0.6) g:(0.1-0.2) g:(100-120) mL, stir at 23-28° C. for 20-30 h, and purify to obtain modified nano carbon black; In a nitrogen atmosphere, polyethylene glycol, dimethylol propionic acid and toluene diisocyanate were mixed and stirred, and then dibutyltin dilaurate was added, heated to 85-90°C and stirred for reaction for 40-50 minutes, and then modified nano carbon black was added, and the temperature was lowered to 70-80°C, and the reaction was continued for 100-150 minutes. Acetone was added during the reaction, and then the temperature was lowered to 50-55°C, triethylamine was added and reacted for 40-50 minutes, and then chitosan was added and reacted at 34-36°C for 20- 40min, then add distilled water to obtain a polyurethane finishing liquid with a concentration of 20-40g / L; wherein the mass ratio of polyethylene glycol, dimethylolpropionic acid, toluene diisocyanate, dibutyltin dilaurate, modified nano carbon black, acetone, triethylamine, and chitosan is (6-12):(1.3-2.6):(5.2-10.4):(0.2-0.3):(0.1-0.3):(10-15):(1-2):(0.04-0.1); In the above process, under alkaline conditions, dopamine is polymerized on the surface of nano carbon black to form polydopamine, thereby obtaining modified nano carbon black having phenolic hydroxyl groups and amino groups on the surface; then the modified nano carbon black and chitosan are introduced into the polyurethane structure as modifiers to prepare a polyurethane finishing liquid; As a conductive material and carbon-based light absorption material, nano-carbon black has excellent electrical conductivity and high absorption efficiency in a wide range of sunlight wavelengths; due to the large number of conjugated double bonds in its own aromatic structure, polydopamine can significantly enhance the absorption of ultraviolet light, visible light, and the short-wave near-infrared region. Modifying nano-carbon black with polydopamine can, on the one hand, improve the light absorption efficiency and the photothermal conversion effect, and on the other hand, enable nano-carbon black to be introduced into polyurethane in the form of chemical bonds, improving its dispersibility and the hydrophilicity of nano-carbon black; introducing chitosan into polyurethane can improve the hydrophilicity, antistatic property, and crosslinking density of the polyurethane system; in addition, the functional groups such as hydroxyl and amino groups in polydopamine and chitosan interact with the hydroxyl groups in cotton fibers and modified acrylic fibers, improving the bonding strength between the polyurethane finishing solution and the composite fabric.

[0014] Preferably, in the step (3), the liquor pickup rate of the composite fabric impregnated and padded in the polyurethane finishing solution is 70-80%; baking conditions: baking at 145-155 °C for 2-4 min.

[0015] A heat storage and warmth retention composite fabric prepared by using the preparation method of the heat storage and warmth retention composite fabric described above.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: The heat storage and warmth retention composite fabric of the present invention is obtained by laminating the inner fabric, the middle fabric, and the outer fabric and then finishing with a polyurethane finishing solution. It not only has excellent heat storage and warmth retention performance, but also has excellent antistatic performance, anti-pilling performance, and moisture absorption and air permeability. Specifically, it is manifested in: 1. The inner fabric is a pure cotton fiber fabric. Cotton fibers have the characteristics of warmth retention, moisture absorption and air permeability, good antistatic property, and anti-pilling property, and the pure cotton fiber fabric has good skin-friendly performance, which can improve the wearing comfort of the fabric; 2. The middle fabric is obtained by spinning and knitting modified PA6 / 66 hollow fibers; the Cs 0.33 WO3 nanoparticles contained in the modified PA6 / 66 hollow fibers can absorb near-infrared radiation and generate heat, warming the fabric, while the hollow fibers can reduce heat loss, thus achieving the purpose of heating and keeping warm; 3. The outer fabric is obtained by blending and knitting modified acrylic fibers and cotton fibers. Among them: (1) Cotton fibers have a large cohesion force, and the fibers are not easily slipped out of the fabric surface. When blended with acrylic fibers, it can improve the anti-pilling performance of the fabric. (2) The modified acrylic fiber is obtained by pretreating acrylic fibers with an aqueous sodium hydroxide solution, then grafting sorbitol, and finally loading modified phase change microcapsules. The grafting of sorbitol improves the moisture absorption performance and antistatic performance of acrylic fibers. The combined action of the binary phase change material, composite modified graphene oxide, and amino-functionalized silver nanoparticles in the modified phase change microcapsules improves the heat storage and warmth retention performance, antistatic performance, wear resistance, and anti-pilling performance of the outer fabric. Further, loading the modified phase change microcapsules on the surface of acrylic fibers increases the surface roughness of the fibers, resulting in an increase in the cohesion force between the fibers and an increase in the anti-pilling performance.

[0017] 4. The polyurethane finishing solution of the present invention forms a polymer layer coating on the surface of the composite fabric. The interaction between polar groups in the polyurethane polymer effectively entangles the protruding filaments on the fabric surface through hydrogen bonding, and by tightly bonding the yarns together, a smooth, complete, durable, and tough polymer network is generated on the fabric surface, thereby improving the anti-pilling performance of the composite fabric. At the same time, the presence of modified nano-carbon black and chitosan in the polyurethane system further improves the moisture absorption and air permeability, antistatic performance, and anti-pilling performance of the fabric. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a test comparison chart of the heat storage and warmth retention rate of the heat storage and warmth retention composite fabric of Examples 2-4 and Comparative Examples 4-8 of the present invention; Figure 2 It is a test comparison chart of the charge surface density of the heat storage and warmth retention composite fabric of Examples 2-4 and Comparative Examples 4-8 of the present invention; Figure 3 It is a test comparison chart of the water absorption rate of the heat storage and warmth retention composite fabric of Examples 2-4 and Comparative Examples 4-8 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0019] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0020] Example 1

[0021] This example discloses a preparation method of modified phase change microcapsules, including the following steps: Step S1: Graphene oxide, phthalic anhydride, benzene, and p-toluenesulfonic acid are mixed in a mass ratio of 1:2:9.5:0.04. Then, glass beads are added, and the mixture is refluxed at 100 °C for 3 h. After the reaction, centrifugation is performed, and the centrifuged product is washed with ethanol and dried to obtain modified graphene oxide; 3 g of modified graphene oxide is added to 40 g of an aqueous zinc nitrate solution with a concentration of 1 mol / L. At room temperature, the mixture is ultrasonically treated for 24 h under the condition of 45 KHz. Then, filtration is carried out, and the filter residue is washed with distilled water and dried in vacuo to obtain zinc ion-functionalized graphene oxide; 0.15 g of zinc ion-functionalized graphene oxide is added to 90 g of ethanol, and the mixture is ultrasonically treated for 1.5 h. The pH of the mixed system is adjusted to 3 with a 1 mol / L hydrochloric acid aqueous solution. Then, 10 g of a 3.6% silane coupling agent KH-570 / ethanol solution is added under stirring, and the mixture is heated to 60 °C and stirred for 24 h. After the reaction, filtration is carried out, and the obtained filter residue is washed with deionized water and ethanol and dried in vacuo to obtain composite modified graphene oxide; Step S2: 2.4 g of n-butyl stearate and 3.6 g of n-octadecane are melted at 42 °C and stirred for 15 min, and then cooled to room temperature to obtain a binary phase change material. 6 g of the binary phase change material, 12 g of methyl methacrylate, 1.2 g of pentaerythritol triacrylate, and 0.004 g of composite modified graphene oxide are mixed and ultrasonically treated for 50 min to obtain an oil phase. 0.7 g of alkyl vinyl sulfonate is added to 87.9 g of deionized water, stirred for 25 min, and then the above oil phase is added and emulsified to obtain an O / W pre-emulsion. 22.5 g of a 10% aqueous ammonium persulfate solution is added to the above O / W pre-emulsion within 90 min, and the mixture is stirred at 75 °C for 5 h. After filtration, the obtained filter residue is washed with deionized water and dried in vacuo to obtain phase change microcapsules; Step S3: 1.8 g of silver nanoparticles is added to 100 g of an ethanol aqueous solution with a volume fraction of 80%, and the mixture is ultrasonically treated for 30 min. Then, 0.8 g of silane coupling agent KH-550 is added under a nitrogen atmosphere, and the reaction is carried out at 42 °C for 9 h. After centrifugation, washing, and drying, amino-functionalized silver nanoparticles are obtained; 0.6 g of amino-functionalized silver nanoparticles is ultrasonically dispersed in 70 g of ultrapure water for 30 min to obtain a mixed solution A. 12.5 g of phase change microcapsules is ultrasonically dispersed in 135 g of ultrapure water for 1.5 h to obtain a mixed solution B. The mixed solution A and the mixed solution B are mixed, and under stirring conditions, 1.2 g of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 1.2 g of N-hydroxysuccinimide are added, and the reaction is carried out at room temperature for 45 h. After the reaction, filtration is carried out, and the obtained filter residue is washed with ultrapure water and dried in vacuo to obtain modified phase change microcapsules.

[0022] Example 2 This embodiment discloses a preparation method of a heat storage and warm-keeping composite fabric, comprising the following steps: Step (1): Heat an aqueous sodium hydroxide solution with a mass fraction of 3% to 70 °C, add acrylic fibers, with a solid-liquid ratio of 20:175, react at 70 °C for 8 min, then take out, wash with deionized water 3 times, and then dry in vacuum at 50 °C to obtain pretreated acrylic fibers; Immerse the pretreated acrylic fibers in an aqueous sorbitol solution with a mass fraction of 8% for 10 min, extrude and control the wet weight to be 180 wt%, first heat at 75 °C for 5 min, then heat at 178 °C for 6 min, take out, wash with distilled water and then dry at 100 °C for 50 min to obtain functionalized acrylic fibers; Immerse the functionalized acrylic fibers in a modified phase change microcapsule / water dispersion with a concentration of 40 g / L for 3 min and then dry at 55 °C for 15 min, then immerse in an aqueous ethylene glycol diglycidyl ether solution with a concentration of 40 g / L for 5 min, take out, and cure at 103 °C for 70 min to obtain modified acrylic fibers; Step (2): Ball-mill and mix cesium carbonate and tungsten oxide in a molar ratio of 1:3, and then heat-treat at 590 °C for 6 h in a reducing gas atmosphere to obtain Cs 0.33 WO3 nanoparticles; wherein, the reducing gas is obtained by mixing hydrogen and nitrogen in a volume ratio of 5:95; Mix the Cs 0.33 WO3 nanoparticles and PA6 / 66 copolymer in a mass ratio of 0.15:1, extrude at 230 °C, and slice to obtain modified PA6 / 66 slices; Mix the modified PA6 / 66 slices and PA6 / 66 copolymer in a mass ratio of 1:8, melt-spin at 280 °C, and after the spun fibers are air-cooled, wind and stretch with a draw ratio of 1.5 to obtain modified PA6 / 66 hollow fibers; Blend the modified acrylic fibers and cotton fibers in a mass ratio of 1:1 into an outer layer yarn with a count of 30S (English count), and knit to obtain an outer layer fabric with a gram weight of 100 g / m 2 ; The modified PA6 / 66 hollow fibers are spun and knitted to obtain an intermediate layer fabric with a gram weight of 80 g / m 2 ; Bond, cut the inner layer fabric, the intermediate layer fabric, and the outer layer fabric to obtain a composite fabric; wherein, the inner layer fabric is a pure cotton fiber fabric with a gram weight of 100 g / m spun by a knitting process from pure cotton yarns 2 ; Step (3): Add 0.4 g of nano carbon black and 0.1 g of dopamine hydrochloride into 100 mL of Tris-HCl buffer solution with a pH of 8.5, stir at 23 °C for 20 h, centrifuge, wash the obtained precipitate with water and ethanol, and dry at 60 °C for 15 h to obtain modified nano carbon black; In a nitrogen atmosphere, mix 6 g of polyethylene glycol, 1.3 g of dimethylolpropionic acid, and 5.2 g of toluene diisocyanate, stir, then add 0.2 g of dibutyltin dilaurate, heat to 85 °C and stir for 50 min, then add 0.1 g of modified nano carbon black, cool to 70 °C, and continue to react for 150 min. Add 10 g of acetone during the reaction to reduce the viscosity of the reaction system, then cool to 50 °C, add 1 g of triethylamine and react for 40 min, then add 0.04 g of chitosan, carry out chain extension reaction at 34 °C for 40 min, and then add distilled water to obtain a polyurethane finishing solution with a concentration of 20 g / L; Dip the composite fabric into the polyurethane finishing solution for two dips and two rolls, with a liquor pickup rate of 70%, and then bake at 145 °C for 4 min to obtain a heat storage and warm-keeping composite fabric.

[0023] Example 3 This example discloses a preparation method of a heat storage and warm-keeping composite fabric, including the following steps: Step (1): Heat the sodium hydroxide aqueous solution with a mass fraction of 5% to 90 °C, add acrylic fibers, with a solid-liquid ratio of 20:195, react at 90 °C for 4 min, take out, wash 5 times with deionized water, and then dry in vacuum at 60 °C to obtain pretreated acrylic fibers; Immerse the pretreated acrylic fibers in a sorbitol aqueous solution with a mass fraction of 10% for 30 min, extrude and control the wet weight to be 200 wt%, first heat at 80 °C for 3 min, then heat at 182 °C for 4 min, take out, wash with distilled water and dry at 100 °C for 70 min to obtain functionalized acrylic fibers; Immerse the functionalized acrylic fibers in a modified phase change microcapsule / water dispersion with a concentration of 50 g / L for 5 min and then dry at 60 °C for 10 min, then immerse in an ethylene glycol diglycidyl ether aqueous solution with a concentration of 50 g / L for 10 min, take out, and cure at 108 °C for 50 min to obtain modified acrylic fibers; Step (2): Ball-mill and mix cesium carbonate and tungsten oxide in a molar ratio of 1:3, and then heat-treat at 610 °C for 4 h in a reducing gas atmosphere to obtain Cs 0.33 WO3 nanoparticles; wherein, the reducing gas is obtained by mixing hydrogen and nitrogen in a volume ratio of 5:95; Cs 0.33WO3 nanoparticles and PA6 / 66 copolymer are mixed at a mass ratio of 0.25:1, extruded at 240 °C, and sliced to obtain modified PA6 / 66 slices; The modified PA6 / 66 slices and PA6 / 66 copolymer are mixed at a mass ratio of 1:10, melt-spun at 300 °C. After the spun fibers are cooled by air, they are wound and stretched with a draw ratio of 1.7 to obtain modified PA6 / 66 hollow fibers; The modified acrylic fibers and cotton fibers are blended at a mass ratio of 1:1 into an outer layer yarn with a count of 40S (English count), and knitted to obtain an outer layer fabric with a weight of 120 g / m 2 ; The modified PA6 / 66 hollow fibers are spun and knitted to obtain an intermediate layer fabric with a weight of 100 g / m 2 ; The inner layer fabric, intermediate layer fabric, and outer layer fabric are laminated and cut to obtain a composite fabric; wherein, the inner layer fabric is a pure cotton fiber fabric with a weight of 120 g / m spun from pure cotton yarn through a knitting process 2 ; Step (3): Add 0.6 g of nano carbon black and 0.2 g of dopamine hydrochloride to 120 mL of Tris-HCl buffer solution with a pH of 8.5, stir at 28 °C for 20 h, centrifuge, wash the obtained precipitate with water and ethanol, and dry at 70 °C for 10 h to obtain modified nano carbon black; In a nitrogen atmosphere, mix 12 g of polyethylene glycol, 2.6 g of dimethylolpropionic acid, and 10.4 g of toluene diisocyanate, stir, then add 0.3 g of dibutyltin dilaurate, heat to 90 °C and stir for 40 min, then add 0.3 g of modified nano carbon black, cool to 80 °C, and continue to react for 100 min. Add 15 g of acetone during the reaction to reduce the viscosity of the reaction system, then cool to 55 °C, add 2 g of triethylamine and react for 50 min, then add 0.1 g of chitosan, carry out a chain extension reaction at 36 °C for 20 min, and then add distilled water to obtain a polyurethane finishing solution with a concentration of 40 g / L; The composite fabric is dip-rolled twice in the polyurethane finishing solution with a liquor pickup rate of 80%, and then baked at 155 °C for 2 min to obtain a heat storage and warm-keeping composite fabric.

[0024] Example 4 This example discloses a preparation method of a heat storage and warm-keeping composite fabric, including the following steps: Step (1): Heat an aqueous sodium hydroxide solution with a mass fraction of 4% to 80 °C, add acrylic fibers with a solid-liquid ratio of 20:185, react at 80 °C for 6 min, take out, wash 4 times with deionized water, and then vacuum dry at 55 °C to obtain pretreated acrylic fibers; The pretreated acrylic fibers are impregnated in an aqueous solution of sorbitol with a mass fraction of 9% for 20 min, extruded and the wet weight is controlled to be 190 wt%. First, it is heated at 78 °C for 4 min, then heated at 180 °C for 5 min, taken out, washed with distilled water and dried at 100 °C for 60 min to obtain functionalized acrylic fibers; The functionalized acrylic fibers are impregnated in a modified phase change microcapsule / water dispersion with a concentration of 45 g / L for 4 min and then dried at 58 °C for 12 min. Then, they are impregnated in an aqueous solution of ethylene glycol diglycidyl ether with a concentration of 45 g / L for 8 min, taken out and cured at 105 °C for 60 min to obtain modified acrylic fibers; Step (2): Cesium carbonate and tungsten oxide are ball-milled and mixed at a molar ratio of 1:3, and then heat-treated at 600 °C for 5 h in a reducing gas atmosphere to obtain Cs 0.33 WO3 nanoparticles; wherein, the reducing gas is obtained by mixing hydrogen and nitrogen at a volume ratio of 5:95; Cs 0.33 WO3 nanoparticles and PA6 / 66 copolymer are mixed at a mass ratio of 0.2:1, extruded at 235 °C and sliced to obtain modified PA6 / 66 slices; The modified PA6 / 66 slices and PA6 / 66 copolymer are mixed at a mass ratio of 1:9, melt-spun at 290 °C. After the spun fibers are air-cooled, they are wound and stretched with a draw ratio of 1.6 to obtain modified PA6 / 66 hollow fibers; The modified acrylic fibers and cotton fibers are blended at a mass ratio of 1:1 into an outer layer yarn with a count of 35S (English count) and knitted to obtain an outer layer fabric with a gram weight of 110 g / m 2 ; The modified PA6 / 66 hollow fibers are spun and knitted to obtain an intermediate layer fabric with a gram weight of 90 g / m 2 ; The inner layer fabric, the intermediate layer fabric and the outer layer fabric are laminated and cut to obtain a composite fabric; wherein, the inner layer fabric is a pure cotton fiber fabric with a gram weight of 110 g / m spun from pure cotton yarns through a knitting process 2 ; Step (3): 0.5 g of nano carbon black and 0.15 g of hydrochloric acid dopamine are added to 110 mL of Tris-HCl buffer solution with a pH of 8.5, stirred at 25 °C for 25 h, centrifuged, and the obtained precipitate is washed with water and ethanol and dried at 65 °C for 12 h to obtain modified nano carbon black; In a nitrogen atmosphere, 9 g of polyethylene glycol, 1.9 g of dimethylolpropionic acid, and 7.8 g of toluene diisocyanate were mixed and stirred. Then, 0.3 g of dibutyltin dilaurate was added, and the mixture was heated to 87.5 °C and stirred for reaction for 45 min. Then, 0.2 g of modified nano carbon black was added, and the temperature was lowered to 75 °C, and the reaction was continued for 120 min. During the reaction process, 12.5 g of acetone was added to reduce the viscosity of the reaction system. Then, the temperature was lowered to 53 °C, 1.5 g of triethylamine was added and reacted for 45 min. Then, 0.07 g of chitosan was added, and chain extension reaction was carried out at 35 °C for 30 min. Then, distilled water was added to obtain a polyurethane finishing solution with a concentration of 30 g / L. The composite fabric was dip-dyed and padded twice in the polyurethane finishing solution, and the liquor pickup rate of padding was 75%. Then, it was baked at 150 °C for 3 min to obtain a heat storage and warming composite fabric.

[0025] The modified phase change microcapsules in Examples 2-4 above were the modified phase change microcapsules prepared in Example 1.

[0026] Comparative Example 1 This comparative example discloses a preparation method of phase change microcapsules, which includes the following steps: Step S1: 0.15 g of graphene oxide was added to 90 g of ethanol, and ultrasonic treatment was carried out for 1.5 h. The pH of the mixed system was adjusted to 3 by a hydrochloric acid aqueous solution with a concentration of 1 mol / L. Then, 10 g of a silane coupling agent KH-570 / ethanol solution with a mass fraction of 3.6% was added under stirring, and the mixture was heated to 60 °C and stirred for reaction for 24 h. After the reaction ended, filtration was carried out, and the obtained filter residue was washed with deionized water and ethanol and dried in vacuum to obtain composite modified graphene oxide. Step S2: 2.4 g of n-butyl stearate and 3.6 g of n-octadecane were melted at 42 °C and stirred for 15 min, and then cooled to room temperature to obtain a binary phase change material; 6 g of the binary phase change material, 12 g of methyl methacrylate, 1.2 g of pentaerythritol triacrylate, and 0.004 g of composite modified graphene oxide were mixed and ultrasonicated for 50 min to obtain an oil phase; 0.7 g of alkyl vinyl sulfonate was added to 87.9 g of deionized water, stirred for 25 min, and then the above oil phase was added and emulsified to obtain an O / W pre-emulsion; 22.5 g of an aqueous solution of ammonium persulfate with a mass fraction of 10% was added to the above O / W pre-emulsion within 90 min, and the mixture was stirred and reacted at 75 °C for 5 h. Filtration was carried out, and the obtained filter residue was washed with deionized water and dried in vacuum to obtain phase change microcapsules. Step S3: 1.8 g of nano silver was added to 100 g of an ethanol aqueous solution with a volume fraction of 80%, and ultrasonic treatment was carried out for 30 min. Then, 0.8 g of a silane coupling agent KH-550 was added in a nitrogen atmosphere, and the reaction was carried out at 42 °C for 9 h. Centrifugation, washing, and drying were carried out to obtain amino-functionalized nano silver. Disperse 0.6 g of amino-functionalized silver nanoparticles in 70 g of ultrapure water by ultrasonic treatment for 30 min to obtain mixture A; disperse 12.5 g of phase change microcapsules in 135 g of ultrapure water by ultrasonic treatment for 1.5 h to obtain mixture B; mix mixture A and mixture B, and under stirring conditions, add 1.2 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 1.2 g of N-hydroxysuccinimide, react at room temperature for 45 h, after the reaction is completed, filter, wash the obtained filter residue with ultrapure water, and dry it under vacuum to obtain modified phase change microcapsules.

[0027] Comparative Example 2 This comparative example discloses a preparation method of modified phase change microcapsules, which includes the following steps: Step S1: Melt 2.4 g of n-butyl stearate and 3.6 g of n-octadecane at 42 °C, stir for 15 min, and cool to room temperature to obtain a binary phase change material; ultrasonically treat 6 g of the binary phase change material, 12 g of methyl methacrylate, and 1.2 g of pentaerythritol triacrylate for 50 min to obtain an oil phase; add 0.7 g of alkyl vinyl sulfonate to 87.9 g of deionized water, stir for 25 min, and then add the above oil phase to emulsify to obtain an O / W pre-emulsion; add 22.5 g of an aqueous solution of ammonium persulfate with a mass fraction of 10% to the above O / W pre-emulsion within 90 min, stir and react at 75 °C for 5 h, filter, wash the obtained filter residue with deionized water, and dry it under vacuum to obtain phase change microcapsules; Step S2: Add 1.8 g of silver nanoparticles to 100 g of an ethanol aqueous solution with a volume fraction of 80%, ultrasonically treat for 30 min, then add 0.8 g of silane coupling agent KH-550 in a nitrogen atmosphere, react at 42 °C for 9 h, centrifuge, wash, and dry to obtain amino-functionalized silver nanoparticles; Disperse 0.6 g of amino-functionalized silver nanoparticles in 70 g of ultrapure water by ultrasonic treatment for 30 min to obtain mixture A; disperse 12.5 g of phase change microcapsules in 135 g of ultrapure water by ultrasonic treatment for 1.5 h to obtain mixture B; mix mixture A and mixture B, and under stirring conditions, add 1.2 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 1.2 g of N-hydroxysuccinimide, react at room temperature for 45 h, after the reaction is completed, filter, wash the obtained filter residue with ultrapure water, and dry it under vacuum to obtain modified phase change microcapsules.

[0028] Comparative Example 3 This comparative example discloses a preparation method of modified phase change microcapsules, which includes the following steps: Step S1: Mix graphene oxide, phthalic anhydride, benzene, and p-toluenesulfonic acid in a mass ratio of 1:2:9.5:0.04, add glass beads, reflux and react at 100 °C for 3 h, after the reaction is completed, centrifuge, and wash the centrifuged product with ethanol, and dry to obtain modified graphene oxide; 3 g of modified graphene oxide was added to 40 g of an aqueous solution of zinc nitrate with a concentration of 1 mol / L. At room temperature, ultrasonic treatment was carried out for 24 h under the condition of 45 KHz, followed by filtration. The filter residue was washed with distilled water and then dried in vacuo to obtain zinc ion-functionalized graphene oxide; 0.15 g of zinc ion-functionalized graphene oxide was added to 90 g of ethanol, and ultrasonic treatment was carried out for 1.5 h. The pH of the mixed system was adjusted to 3 with an aqueous solution of hydrochloric acid with a concentration of 1 mol / L. Then, 10 g of a silane coupling agent KH-570 / ethanol solution with a mass fraction of 3.6% was added under stirring, and the mixture was heated to 60 °C and stirred for reaction for 24 h. After the reaction, filtration was carried out, and the obtained filter residue was washed with deionized water and ethanol and then dried in vacuo to obtain composite-modified graphene oxide; Step S2: 2.4 g of n-butyl stearate and 3.6 g of n-octadecane were melted at 42 °C and stirred for 15 min, and then cooled to room temperature to obtain a binary phase change material; 6 g of the binary phase change material, 12 g of methyl methacrylate, 1.2 g of pentaerythritol triacrylate, and 0.004 g of composite-modified graphene oxide were mixed and ultrasonicated for 50 min to obtain an oil phase; 0.7 g of alkyl vinyl sulfonate was added to 87.9 g of deionized water, stirred for 25 min, and then the above oil phase was added and emulsified to obtain an O / W pre-emulsion; 22.5 g of an aqueous solution of ammonium persulfate with a mass fraction of 10% was added to the above O / W pre-emulsion within 90 min, and the mixture was stirred and reacted at 75 °C for 5 h. After filtration, the obtained filter residue was washed with deionized water and dried in vacuo to obtain modified phase change microcapsules; Comparative Example 4 Compared with Example 4, in the process of preparing modified acrylic fibers in Comparative Example 4, the modified phase change microcapsules prepared in Comparative Example 1 were used, and other conditions remained unchanged.

[0029] Comparative Example 5 Compared with Example 4, in the process of preparing modified acrylic fibers in Comparative Example 5, the modified phase change microcapsules prepared in Comparative Example 2 were used, and other conditions remained unchanged.

[0030] Comparative Example 6 Compared with Example 4, in the process of preparing modified acrylic fibers in Comparative Example 6, the modified phase change microcapsules prepared in Comparative Example 3 were used, and other conditions remained unchanged.

[0031] Comparative Example 7 Compared with Example 4, in the process of preparing polyurethane finishing liquor in Comparative Example 7, modified nano-carbon black was not added, and other conditions remained unchanged.

[0032] Comparative Example 8 Compared with Example 4, in the process of preparing polyurethane finishing liquor in Comparative Example 8, chitosan was not added, and other conditions remained unchanged.

[0033] In the above examples and comparative examples, graphene oxide has a thickness of 0.55 - 1.2 nm and a diameter of 0.5 - 3 μm, and is from Zhongke Leiming (Beijing) Technology Co., Ltd.; nano silver has a particle size of 20 nm, model number ML-Ag-N20, and a spherical microscopic morphology, and is from Zhejiang Manli Nano Technology Co., Ltd.; PA6 / 66 copolymer, brand: BASF, product number: C3309, density: 1.12 g / cm3, melting point: 195 - 197 °C; purchased from Shanghai Juying Plasticization Technology Co., Ltd.; nano carbon black has an average particle size of 30 nm, brand Cabot, model number BLACKPEARLS2000, product number 13165, and is from Guangzhou Jingyi New Materials Co., Ltd.; polyethylene glycol (PEG), Mn = 600 g / mol), and is from Jinan Qihang Chemical Technology Co., Ltd.; chitosan, viscosity of 200 - 400 mPas, degree of deacetylation of 95%), and is from Shanghai Aladdin Biochemical Technology Co., Ltd. (Shanghai, China).

[0034] Experimental Example Perform performance tests on the heat storage and warm-keeping composite fabrics of Examples 2 - 4 and Comparative Examples 4 - 8.

[0035] I. Antistatic property test: Conduct the test in accordance with GB / T12703.2 - 2009 "Textiles - Test methods for electrostatic properties - Part 2: Charge surface density".

[0036] II. Warmth retention property test: Conduct the test in accordance with the flat plate method of GB / T35762 - 2017.

[0037] III. Pilling resistance property test: Conduct the test in accordance with the circular track method of GB / T4802.1 - 2008 for pilling test of textile fabrics.

[0038] IV. Moisture absorption test: Conduct the test in accordance with GB / T21655.1 - 2008 "Textiles - Evaluation of moisture absorption and quick drying - Part 1: Single item combined test method".

[0039] The test results are shown in Table 1: Table 1 <![CDATA[Surface charge density / μC·m 2 > Heat preservation rate / % Pilling resistance grade Water absorption rate / % Example 2 0.61 50.4 Grade 5 280 Example 3 0.53 51.6 Grade 5 293 Example 4 0.57 50.9 Grade 5 286 Comparative Example 4 0.69 49.7 Grade 5 279 Comparative Example 5 1.27 45.3 Grade 5 266 Comparative Example 6 0.88 48.2 Grade 4 258 Comparative Example 7 1.01 46.8 Grade 4 233 Comparative Example 8 0.76 50.8 Grade 3 212 It can be seen from the test results in Table 1 that the heat storage and warm-keeping composite fabrics prepared in Examples 2-4 of the present invention have excellent antistatic performance, heat storage and warm-keeping performance, anti-pilling performance and moisture absorption and air permeability. From the comparison between Comparative Example 4 and Example 4, it can be seen that phthalic anhydride reacts with graphene oxide to introduce more hydrophilic carboxyl groups on the surface of graphene oxide, and then zinc ions are uniformly fixed on graphene oxide, improving the hydrophilicity and conductivity of graphene oxide, enhancing the light absorption efficiency of graphene oxide, and reducing the infrared emissivity. Furthermore, the modified phase change microcapsules containing zinc ion-functionalized graphene oxide are attached to the outer fabric, which can improve the antistatic performance, heat storage and warm-keeping performance and moisture absorption and air permeability of the fabric. From the comparison between Comparative Examples 5-6 and Example 4, it can be seen that the composite modified graphene oxide in the modified phase change microcapsules improves the antistatic performance, heat storage and warm-keeping performance and moisture absorption and air permeability of the composite fabric by improving the conductivity, thermal conductivity, hydrophilicity and photothermal conversion ability of the phase change microcapsules. The amino-functionalized silver nanoparticles on the modified phase change microcapsules further improve the above properties, and at the same time, due to increasing the surface roughness of the phase change microcapsules, the surface roughness of the acrylic fibers is increased, the bonding force between the fibers is increased, and the anti-pilling performance of the fabric is improved. From the comparison between Comparative Example 7 and Example 4, The modified nano-carbon black treated with polydopamine in the polyurethane finishing solution has excellent conductivity, photothermal conversion efficiency and hydrophilicity, thus endowing the composite fabric with better antistatic performance, heat storage and warm-keeping performance and moisture absorption and air permeability. In addition, the organic functional groups on the surface of the modified nano-carbon black enhance the bonding strength between the polyurethane finishing solution and the composite fabric, and also have a positive impact on the anti-pilling performance of the composite fabric; from the comparison between Comparative Example 8 and Example 4, it can be seen that introducing chitosan into polyurethane improves the hydrophilicity, antistatic property and crosslinking density of the polyurethane system, and forms a durable and tough polymer network on the surface of the composite fabric, thus endowing the composite fabric with excellent antistatic performance, anti-pilling performance and moisture absorption and air permeability.

[0040] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of a heat storage and warmth retention composite fabric, characterized in that, It includes the following steps: Step (1): The acrylic fiber is pretreated with an aqueous sodium hydroxide solution, then grafted with sorbitol, and finally loaded with modified phase change microcapsules to obtain modified acrylic fibers. Among them, the preparation method of the modified phase change microcapsules includes the following steps: Step S1: Graphene oxide is successively modified with phthalic anhydride, functionalized with zinc ions, and treated with silane coupling agent KH-570 to obtain composite modified graphene oxide. Step S2: Prepare phase change microcapsules with n-butyl stearate and n-octadecane binary phase change material as the core material and methyl methacrylate, pentaerythritol triacrylate, and composite modified graphene oxide as the shell. Step S3: Nano silver is surface-treated with amino groups and then attached to the phase change microcapsules to obtain modified phase change microcapsules. Step (2): Prepare Cs 0.33 WO3 nanoparticles using cesium carbonate and tungsten oxide as raw materials; Cs 0.33 WO3 nanoparticles are blended with PA6 / 66 copolymer, extruded and sliced, and then melt-spun with PA6 / 66 copolymer to obtain modified PA6 / 66 hollow fibers; The modified acrylic fibers and cotton fibers are made into the outer fabric; the modified PA6 / 66 hollow fibers are made into the middle fabric; the inner fabric, middle fabric, and outer fabric are laminated to obtain a composite fabric. Step (3): Modify nano carbon black with polydopamine to obtain modified nano carbon black; prepare a polyurethane finishing solution containing modified nano carbon black and chitosan through reaction. The composite fabric is padded and dried in the polyurethane finishing solution to obtain a heat storage and warmth retention composite fabric.

2. The preparation method of the heat storage and heat preservation composite fabric according to claim 1, characterized in that, In the said step (1), the preparation method of the modified acrylic fibers specifically includes the following steps: Heat an aqueous sodium hydroxide solution with a mass fraction of 3-5% to 70-90 °C, add acrylic fibers, with a solid-liquid ratio of 20:(175-195), react at 70-90 °C for 4-8 min, then take out, wash, and dry to obtain pretreated acrylic fibers. Immerse the pretreated acrylic fibers in an aqueous sorbitol solution with a mass fraction of 8-10% for 10-30 min, extrude and control the wet weight to be 180-200 wt%, first heat at 75-80 °C for 3-5 min, then heat at 178-182 °C for 4-6 min, take out, wash, and dry to obtain functionalized acrylic fibers. Immerse the functionalized acrylic fibers in a modified phase change microcapsule / water dispersion with a concentration of 40-50 g / L for 3-5 min, dry at 55-60 °C for 10-15 min, then immerse in an aqueous ethylene glycol diglycidyl ether solution with a concentration of 40-50 g / L for 5-10 min, take out, and cure at 103-108 °C for 50-70 min to obtain modified acrylic fibers.

3. The preparation method of the heat storage and heat preservation composite fabric according to claim 1, characterized in that, In the said step (1), the preparation method of the modified phase change microcapsules specifically includes the following steps: Step S1: Mix graphene oxide, phthalic anhydride, benzene, and p-toluenesulfonic acid in a mass ratio of 1:(1.5-2.5):(9-10):0.04, reflux and react at 97-103 °C for 2.5-3.5 h, and purify to obtain modified graphene oxide. Mix the modified graphene oxide and an aqueous zinc nitrate solution with a concentration of 1 mol / L in a mass ratio of (2-4):(30-50), and under the condition of 40-45 KHz at room temperature, ultrasonically treat for 20-30 h, and purify to obtain zinc ion-functionalized graphene oxide. Add zinc ion-functionalized graphene oxide into ethanol, and perform ultrasonic treatment. Adjust the pH of the mixed system to 2.9 - 3.1 with hydrochloric acid aqueous solution. Then, add a 3.6% silane coupling agent KH-570 / ethanol solution under stirring, heat to 58 - 62 °C, and stir and react for 20 - 30 h. After purification, composite modified graphene oxide is obtained; wherein, the mass ratio of zinc ion-functionalized graphene oxide, ethanol, and silane coupling agent KH-570 / ethanol solution is (0.1 - 0.2):(80 - 100):(8 - 12); Step S2: Mix n-butyl stearate and n-octadecane in a mass ratio of (1.6 - 3.2):(2.4 - 4.8), melt at 40 - 44 °C, stir for 10 - 20 min, and cool to room temperature to obtain a binary phase change material; mix the binary phase change material, methyl methacrylate, pentaerythritol triacrylate, and composite modified graphene oxide in a mass ratio of (4 - 8):(8 - 16):(0.8 - 1.6):(0.003 - 0.005), and perform ultrasonic treatment for 30 - 60 min to obtain an oil phase; mix alkyl vinyl sulfonate and deionized water in a mass ratio of (0.5 - 0.9):(58.6 - 117.2), stir for 20 - 30 min, then add the above oil phase and emulsify to obtain an O / W pre-emulsion; add a 10% ammonium persulfate aqueous solution to the above O / W pre-emulsion within 60 - 120 min, stir and react at 70 - 80 °C for 4.5 - 5.5 h, filter, wash, and dry to obtain phase change microcapsules; wherein, the mass ratio of ammonium persulfate aqueous solution and O / W pre-emulsion is (15 - 30):(71.9 - 143.8); Step S3: Add nano silver into an ethanol aqueous solution with a volume fraction of 80%, add silane coupling agent KH-550 in a nitrogen atmosphere, react at 40 - 45 °C for 8 - 10 h, and purify to obtain amino-functionalized nano silver; wherein, the mass ratio of nano silver, ethanol aqueous solution, and silane coupling agent KH-550 is (0.5 - 3):(80 - 120):(0.5 - 1); Disperse the amino-functionalized nano silver in ultrapure water by ultrasonic treatment for 20 - 40 min to obtain mixture A; disperse the phase change microcapsules in ultrapure water by ultrasonic treatment for 1 - 2 h to obtain mixture B; mix mixture A and mixture B, add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide under stirring conditions, and react at room temperature for 40 - 50 h. After purification, modified phase change microcapsules are obtained; wherein, the mass ratio of amino-functionalized nano silver, phase change microcapsules, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N-hydroxysuccinimide is (0.4 - 0.8):(10 - 15):(1 - 1.5):(1 - 1.5).

4. The preparation method of the heat storage and warmth retention composite fabric according to claim 1, characterized in that, In the step (2), the preparation method of the modified PA6 / 66 hollow fiber specifically includes the following steps: After ball-milling and mixing cesium carbonate and tungsten oxide in a molar ratio of 1:3, heat-treat them at 590 - 610 °C for 4 - 6 h in a reducing gas atmosphere to obtain Cs 0.33 WO3 nanoparticles; wherein, the reducing gas is obtained by mixing hydrogen and nitrogen in a volume ratio of 5:95; Mix Cs 0.33 WO3 nanoparticles and PA6 / 66 copolymer in a mass ratio of (0.15 - 0.25):1, extrude at 230 - 240 °C, slice to obtain modified PA6 / 66 slices; Mix the modified PA6 / 66 chips and the PA6 / 66 copolymer in a mass ratio of 1:(8 - 10), and perform melt spinning at 280 - 300 °C. After the spun fibers are air-cooled, wind them up and stretch them with a draw ratio of 1.5 - 1.7 to obtain the modified PA6 / 66 hollow fibers.

5. The preparation method of the heat storage and warmth retention composite fabric according to claim 1, characterized in that In the step (2), the outer fabric is obtained by knitting the outer layer yarn which is spun from modified acrylic fiber and cotton fiber in a mass ratio of 1:1 and has an English count of 30 - 40S; the gram weight of the outer fabric is 100 - 120 g / m 2 .

6. The preparation method of the heat storage and warm-keeping composite fabric according to claim 1, characterized in that, In the step (2), the middle layer fabric is obtained by spinning and knitting modified PA6 / 66 hollow fibers; the gram weight of the middle layer fabric is 80-100 g / m 2 .

7. The preparation method of the heat storage and warmth retention composite fabric according to claim 1, characterized in that, In the step (2), the inner fabric is a pure cotton fiber fabric with a gram weight of 100-120 g / m spun from pure cotton yarns through a knitting process. 2 ​ 8. The preparation method of the heat storage and warming composite fabric according to claim 1, characterized in that In the step (3), the preparation method of the polyurethane finishing solution specifically includes the following steps: Mix nano carbon black, dopamine hydrochloride, and Tris-HCl buffer solution with a pH of 8.5 in a dosage ratio of (0.4 - 0.6) g:(0.1 - 0.2) g:(100 - 120) mL, stir at 23 - 28 °C for 20 - 30 h, and purify to obtain the modified nano carbon black; In a nitrogen atmosphere, mix polyethylene glycol, dimethylolpropionic acid, and toluene diisocyanate, stir, then add dibutyltin dilaurate, heat to 85 - 90 °C and stir for reaction for 40 - 50 min, then add the modified nano carbon black, cool to 70 - 80 °C, and continue the reaction for 100 - 150 min. Add acetone during the reaction process, then cool to 50 - 55 °C, add triethylamine and react for 40 - 50 min, then add chitosan, react at 34 - 36 °C for 20 - 40 min, and then add distilled water to obtain a polyurethane finishing solution with a concentration of 20 - 40 g / L; wherein, the mass ratio of polyethylene glycol, dimethylolpropionic acid, toluene diisocyanate, dibutyltin dilaurate, modified nano carbon black, acetone, triethylamine, and chitosan is (6 - 12):(1.3 - 2.6):(5.2 - 10.4):(0.2 - 0.3):(0.1 - 0.3):(10 - 15):(1 - 2):(0.04 - 0.1).

9. The preparation method of the heat storage and warming composite fabric according to claim 1, characterized in that, In the step (3), the liquor pickup rate of the composite fabric impregnated in the polyurethane finishing solution is 70 - 80%; baking conditions: bake at 145 - 155 °C for 2 - 4 min.

10. A heat storage and warm-keeping composite fabric prepared by using the preparation method of the heat storage and warm-keeping composite fabric according to any one of claims 1 - 9.

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