Heat-storage and warmth-retaining composite fabric and preparation method thereof

Abstract

The present invention relates to the technical field of layered materials, and discloses a heat storage and warmth-keeping composite fabric and a preparation method thereof. The preparation method of the heat storage and warmth-keeping composite fabric comprises the following steps: preparing modified acrylic fiber loaded with modified phase change microcapsules; 0.33 WO3 nanoparticles are blended with a PA6 / 66 copolymer, extruded and sliced, and then melt-spun with the PA6 / 66 copolymer to obtain modified PA6 / 66 hollow fibers; a polyurethane finishing solution containing modified nano-carbon black and chitosan is prepared; an outer layer fabric is made from modified acrylic fiber and cotton fiber; an intermediate layer fabric is made from the modified PA6 / 66 hollow fibers; the inner layer fabric, the intermediate layer fabric, and the outer layer fabric are laminated to obtain a composite fabric; and the composite fabric is finished with the polyurethane finishing solution to obtain a heat-storage and heat-insulating composite fabric. The heat-storage and heat-insulating composite fabric of the present invention has excellent antistatic properties, heat-storage and heat-insulating properties, anti-pilling properties, and moisture absorption and breathability.

Description

Technical Field

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

[0002] When exercising outdoors in a cold environment, the sudden change in skin surface temperature will affect the exercise effect, experience and even physical health. Winter sportswear not only needs to have moisture absorption and perspiration function to keep the skin dry, but also needs to be able to store heat and keep warm to help the body resist the cold.

[0003] Acrylic fibers are widely used in winter clothing fabrics due to their excellent warmth retention, resistance to mold and mildew, and fluffiness and softness. For example, Chinese patent application CN107354529A discloses a method for preparing acrylic fibers, acrylic fibers, and fabrics. The method comprises: separately providing a ceramic powder composition and modified graphene; dispersing the ceramic powder composition in deionized water, adding a coupling agent, stirring, and then adding a polyacrylonitrile solution to uniformly mix to obtain a skin material; dispersing the modified graphene in deionized water, stirring, and then adding a polyacrylonitrile solution to uniformly mix to obtain a core material; and coating the skin material over the core material through composite spinning to form an acrylic fiber with a skin-core composite structure. This method effectively reduces the cost of graphene usage while ensuring antistatic properties, and imparts to the acrylic fiber characteristics of warmth retention, ease of dyeing, and durability.

[0004] However, acrylic fabrics have the problems of poor moisture absorption and breathability and easy pilling. Especially in the dry winter environment, the static electricity phenomenon is more significant, which will aggravate the pilling phenomenon of the fabric. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a method for preparing a heat-storage and heat-retaining composite fabric, comprising the following steps:

[0006] Step (1), acrylic fiber is pretreated with a sodium hydroxide aqueous solution, then grafted with sorbitol, and finally loaded with modified phase change microcapsules to obtain modified acrylic fiber;

[0007] The preparation method of the modified phase-change microcapsules comprises the following steps:

[0008] Step S1, modifying graphene oxide with phthalic anhydride, functionalizing with zinc ions, and treating with a silane coupling agent KH-570 in sequence to obtain a composite modified graphene oxide;

[0009] Step S2, preparing a phase change microcapsule with n-butyl stearate and n-octadecane as the core material and methyl methacrylate, pentaerythritol triacrylate, and composite modified graphene oxide as the shell;

[0010] Step S3, nanosilver is surface-treated by amino group and then connected to the phase change microcapsules to obtain modified phase change microcapsules;

[0011] Step (2): Prepare Cs using cesium carbonate and tungsten oxide as raw materials. 0.33 WO3 nanoparticles; Cs 0.33 WO3 nanoparticles are blended with PA6 / 66 copolymer, extruded, sliced, and then melt-spun with PA6 / 66 copolymer to obtain modified PA6 / 66 hollow fibers;

[0012] The outer layer fabric is made of modified acrylic fiber and cotton fiber; the middle layer fabric is made of modified PA6 / 66 hollow fiber; the inner layer fabric, the middle layer fabric and the outer layer fabric are laminated to obtain a composite fabric;

[0013] Step (3), modifying nano carbon black with polydopamine to obtain modified nano carbon black; preparing a polyurethane finishing liquid containing modified nano carbon black and chitosan by reaction;

[0014] The composite fabric is twice dipped and twice rolled in a polyurethane finishing liquid, and baked to obtain a heat storage and warmth retaining composite fabric.

[0015] Preferably, in step (1), the method for preparing the modified acrylic fiber specifically comprises the following steps:

[0016] Heat a 3-5% mass fraction sodium hydroxide aqueous solution to 70-90° C., add acrylic fiber at a solid-liquid ratio of 20:(175-195), react at 70-90° C. for 4-8 minutes, remove, wash, and dry to obtain pretreated acrylic fiber;

[0017] The pretreated acrylic fiber is immersed in an aqueous solution of sorbitol with a mass fraction of 8-10% for 10-30 minutes, squeezed and the wet weight is controlled to be 180-200wt%, first heated at 75-80°C for 3-5 minutes, then heated at 178-182°C for 4-6 minutes, taken out, washed, and dried to obtain a functionalized acrylic fiber;

[0018] The functionalized acrylic fiber is immersed in a modified phase change microcapsule / water dispersion having a concentration of 40-50 g / L for 3-5 minutes, dried at 55-60° C. for 10-15 minutes, and then immersed in an aqueous solution of ethylene glycol diglycidyl ether having a concentration of 40-50 g / L for 5-10 minutes, removed, and cured at 103-108° C. for 50-70 minutes to obtain a modified acrylic fiber;

[0019] In the above process, the acrylic fiber is pretreated with an aqueous sodium hydroxide solution and undergoes a hydrolysis reaction in an alkaline solution, whereby the cyano groups in the acrylic fiber are converted into carboxyl groups to obtain a pretreated acrylic fiber; then, the carboxyl groups on the surface of the pretreated acrylic fiber undergo an esterification reaction with the hydroxyl groups of sorbitol to obtain a functionalized acrylic fiber having a surface rich in hydrophilic hydroxyl groups; further, ethylene glycol diglycidyl ether is used as a cross-linking agent, and the epoxy groups of ethylene glycol diglycidyl ether react with the hydroxyl groups on the functionalized acrylic fiber and the modified phase change microcapsules, and the modified phase change microcapsules are grafted onto the acrylic fiber to obtain a modified acrylic fiber.

[0020] Furthermore, in step (1), the method for preparing the modified phase-change microcapsules specifically comprises the following steps:

[0021] Step S1, mixing graphene oxide, phthalic anhydride, benzene, and p-toluenesulfonic acid in a mass ratio of 1:(1.5-2.5):(9-10):0.04, reflux reaction at 97-103° C. for 2.5-3.5 hours, and purifying to obtain modified graphene oxide;

[0022] Modified graphene oxide and a 1 mol / L zinc nitrate aqueous solution were mixed in a mass ratio of (2-4):(30-50), and ultrasonically treated at room temperature under 40-45 kHz for 20-30 h for purification to obtain zinc ion functionalized graphene oxide;

[0023] The zinc ion functionalized graphene oxide was added to ethanol, ultrasonicated, and the pH of the mixture was adjusted to 2.9-3.1 by aqueous hydrochloric acid solution. Then, a 3.6% by mass fraction of a silane coupling agent KH-570 / ethanol solution was added under stirring, and the mixture was heated to 58-62° C. and stirred for 20-30 hours, and purified to obtain a 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);

[0024] In the above process, the surface of graphene oxide is rich in hydroxyl and carboxyl groups. The anhydride of phthalic anhydride reacts with some hydroxyl groups on the surface of graphene oxide through ring opening to generate carboxyl groups, introducing more carboxyl groups on the surface of graphene oxide. The carboxyl groups then combine with the metallic zinc ions in zinc nitrate to uniformly fix the zinc ions on the graphene oxide, thereby obtaining zinc ion-functionalized graphene oxide. The zinc ion-functionalized graphene oxide is then treated with silanols obtained by hydrolysis of the silane coupling agent KH-570 to introduce carbon-carbon double bonds, thereby obtaining a composite modified graphene oxide.

[0025] As we all know, graphene oxide has excellent mechanical properties, electrical conductivity, thermal conductivity, and photothermal conversion effects. The fixation of zinc ions can improve the conductivity of graphene oxide, enhance the light absorption efficiency of graphene oxide, and reduce infrared emissivity, effectively inhibiting thermal radiation and achieving a better heat pipe effect by reducing heat transfer radiated to the surrounding environment.

[0026] Step S2, mixing n-butyl stearate and n-octadecane in a mass ratio of (1.6-3.2): (2.4-4.8), melting at 40-44 ° C, stirring for 10-20 minutes, and cooling to room temperature to obtain a binary phase change material; mixing 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), ultrasonicating for 30-60 minutes to obtain an oil phase; and mixing alkyl vinyl sulfonate. and deionized water in a mass ratio of (0.5-0.9):(58.6-117.2), stirred for 20-30 minutes, and then added with the above oil phase, emulsified to obtain an O / W pre-emulsion; adding a 10% by mass fraction of ammonium persulfate aqueous solution to the above O / W pre-emulsion within 60-120 minutes, stirring at 70-80°C for 4.5-5.5 hours, filtering, washing, and drying to obtain phase change microcapsules; wherein the mass ratio of the ammonium persulfate aqueous solution to the O / W pre-emulsion is (15-30):(71.9-143.8);

[0027] 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 radical 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 body's comfortable temperature range. The polymer shell of the phase-change material confined in the nanocapsule has a relatively low thermal conductivity, which is not conducive to accelerating the thermal response of thermal energy storage and release and improving energy utilization efficiency. The composite modified graphene oxide is doped into the shell of the phase-change microcapsule in the form of chemical bonds to solve this problem. The introduction of pentaerythritol triacrylate containing hydroxyl groups and three vinyl groups into the phase-change microcapsule shell increases the structural stability and reactivity of the phase-change microcapsule (providing reactive hydroxyl groups).

[0028] Step S3, adding nanosilver to an 80% by volume ethanol aqueous solution, adding a silane coupling agent KH-550 in a nitrogen atmosphere, reacting at 40-45° C. for 8-10 hours, and purifying to obtain amino nanosilver; wherein the mass ratio of nanosilver, ethanol aqueous solution, and silane coupling agent KH-550 is (0.5-3):(80-120):(0.5-1);

[0029] Ultrasonic dispersion of amination-modified nanosilver in ultrapure water for 20-40 minutes to obtain a mixture A; ultrasonic dispersion of phase-change microcapsules in ultrapure water for 1-2 hours to obtain a mixture B; the mixture A and the mixture B are mixed, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide are added under stirring, and the mixture is reacted at room temperature for 40-50 hours, and purified to obtain modified phase-change microcapsules; wherein the mass ratio of amination-modified nanosilver, 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);

[0030] In the above process, nanosilver is modified with a silane coupling agent KH-550, amino groups are introduced on its surface, and then, through an 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 nanosilver deposited on the surface are obtained; the deposition of nanosilver improves the electrical conductivity and thermal conductivity of the phase change microcapsules. As a thermal conductive material, nanosilver exhibits localized surface plasmon resonance (LSPR), thereby enhancing the light absorption ability of the phase change microcapsules, converting light energy into heat energy, and quickly transferring it to the phase change material; further, amino nanosilver is 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.

[0031] Preferably, in step (2), the method for preparing the modified PA6 / 66 hollow fiber specifically comprises the following steps:

[0032] Cesium carbonate and tungsten oxide were mixed by ball milling at a molar ratio of 1:3, and then heat treated 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;

[0033] Cs 0.33 WO3 nanoparticles and PA6 / 66 copolymer are mixed in a mass ratio of (0.15-0.25):1, extruded at 230-240°C, and sliced to obtain modified PA6 / 66 slices;

[0034] Modified PA6 / 66 chips and PA6 / 66 copolymer are mixed at a mass ratio of 1:(8-10), melt-spinned at 280-300°C, and the spun fibers are air-cooled, wound, and stretched at a stretch ratio of 1.5-1.7 to obtain modified PA6 / 66 hollow fibers;

[0035] In the above process, Cs was prepared using cesium carbonate and tungsten oxide as raw materials. 0.33WO3 nanoparticles are then mixed with PA6 / 66 copolymer and subsequently treated to obtain modified PA6 / 66 hollow fibers. 0.33 WO3 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.

[0036] Preferably, in step (2), the outer fabric is obtained by knitting an outer yarn having a count of 30-40S (English count) by blending modified acrylic fiber and cotton fiber in a mass ratio of 1:1; the outer fabric has a gram weight of 100-120 g / m 2 .

[0037] 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 .

[0038] Preferably, in step (2), the inner layer fabric is made of pure cotton yarn spun through a knitting process and has a gram weight of 100-120 g / m 2 Pure cotton fiber fabric.

[0039] Preferably, in step (3), the method for preparing the polyurethane finishing liquid specifically comprises the following steps:

[0040] Nanocarbon black, dopamine hydrochloride, and a Tris-HCl buffer solution having a pH of 8.5 were mixed in a ratio of (0.4-0.6) g: (0.1-0.2) g: (100-120) mL, stirred at 23-28° C. for 20-30 h, and purified to obtain modified nanocarbon black;

[0041] In a nitrogen atmosphere, polyethylene glycol, dihydroxymethylpropionic acid, and toluene diisocyanate were mixed and stirred, and then dibutyltin dilaurate was added. The mixture was heated to 85-90°C and stirred for reaction for 40-50 minutes. Then, modified nano carbon black was added, and the temperature was lowered to 70-80°C. The reaction was continued for 100-150 minutes. Acetone was added during the reaction, and the temperature was lowered to 50-55°C. Triethylamine was added and the reaction was continued for 40-50 minutes. Chitosan was added and the reaction was continued at 34-36°C for 20- 40min, and then adding 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);

[0042] In the above process, under alkaline conditions, dopamine polymerizes on the surface of nanocarbon black to form polydopamine, obtaining modified nanocarbon black containing phenolic hydroxyl groups and amino groups on the surface; then the modified nanocarbon black and chitosan are introduced as modifiers into the polyurethane structure to prepare a polyurethane finishing liquid;

[0043] Nanocarbon black, as a conductive material and carbon-based light-absorbing material, has excellent conductivity and high absorption efficiency in a wide range of solar wavelengths. Due to the large number of conjugated double bonds in the aromatic structure of polydopamine itself, it can significantly enhance the absorption of ultraviolet light, visible light, and near-infrared short-wave regions. Modifying nanocarbon black with polydopamine can, on the one hand, improve light absorption efficiency and photothermal conversion effect, and on the other hand, enable nanocarbon black to be introduced into polyurethane in the form of chemical bonds, thereby improving its dispersibility and improving the hydrophilicity of nanocarbon black. Introducing chitosan into polyurethane improves the hydrophilicity, antistatic property and cross-linking density of the polyurethane system. In addition, functional groups such as hydroxyl and amino groups in polydopamine and chitosan interact with hydroxyl groups in cotton fibers and modified acrylic fibers, thereby improving the bonding strength between the polyurethane finishing liquid and the composite fabric.

[0044] Preferably, in step (3), the liquid carrying rate of the composite fabric in the polyurethane finishing liquid is 70-80%; the baking conditions are: baking at 145-155°C for 2-4 minutes.

[0045] The heat-storage and heat-insulating composite fabric is prepared by adopting the preparation method of the heat-storage and heat-insulating composite fabric.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] The heat-storage and warmth-retaining composite fabric of the present invention is obtained by laminating an inner layer fabric, an intermediate layer fabric, and an outer layer fabric and then finishing with a polyurethane finishing liquid. It not only has excellent heat-storage and warmth-retaining properties, but also has excellent antistatic properties, anti-pilling properties, and moisture absorption and breathability. Specifically, it is embodied in:

[0048] 1. The inner layer is made of pure cotton fiber. Cotton fiber has the characteristics of warmth retention, moisture absorption and breathability, anti-static properties, and good anti-pilling properties. In addition, pure cotton fiber fabric has good skin-friendly properties and can improve the wearing comfort of the fabric.

[0049] 2. The middle layer fabric is made of modified PA6 / 66 hollow fiber through spinning and knitting; the Cs contained in the modified PA6 / 66 hollow fiber 0.33 WO3 nanoparticles can absorb near-infrared radiation and generate heat, making the fabric warmer, while the hollow fibers can reduce heat loss, thus achieving the purpose of heating and keeping warm;

[0050] 3. The outer fabric is obtained by blending and knitting modified acrylic fiber and cotton fiber, wherein: (1) cotton fiber has a strong cohesive force and is not easy to slide out of the fabric surface. Blending with acrylic fiber can improve the anti-pilling performance of the fabric; (2) modified acrylic fiber is obtained by pre-treating acrylic fiber with sodium hydroxide aqueous solution, grafting sorbitol, and finally loading modified phase change microcapsules. Sorbitol grafting improves the hygroscopicity and antistatic properties of acrylic fiber; the combined effect of binary phase change material and composite modified graphene oxide and amino-treated nanosilver in the modified phase change microcapsules improves the heat storage and warmth retention, antistatic performance, wear resistance and anti-pilling performance of the outer fabric; further, loading modified phase change microcapsules on the surface of acrylic fiber increases the surface roughness of the fiber, thereby increasing the cohesive force between fibers and improving the anti-pilling performance.

[0051] 4. The polyurethane finishing liquid of the present invention forms a polymer layer coating on the surface of the composite fabric. The interaction between the polar groups in the polyurethane polymer effectively entangles the protruding filaments on the fabric surface through hydrogen bonding. By tightly bonding the yarns together, a smooth, complete, durable and tough polymer network is produced 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 breathability, antistatic properties and anti-pilling properties of the fabric. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 This is a comparison chart of the thermal insulation rate test of the heat storage and warmth retaining composite fabrics of Examples 2-4 of the present invention and Comparative Examples 4-8;

[0053] Figure 2 3. This is a comparison chart of the charge surface density test of the heat storage and warmth retaining composite fabrics of Examples 2-4 of the present invention and Comparative Examples 4-8;

[0054] Figure 3 It is a comparison chart of water absorption test of heat storage and warmth retaining composite fabrics of Examples 2-4 of the present invention and Comparative Examples 4-8. DETAILED DESCRIPTION

[0055] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only 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 ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0056] Example 1

[0057] This embodiment discloses a method for preparing modified phase change microcapsules, comprising the following steps:

[0058] Step S1, graphene oxide, phthalic anhydride, benzene, and p-toluenesulfonic acid are mixed in a mass ratio of 1:2:9.5:0.04, and then glass beads are added. The mixture is refluxed at 100° C. for 3 hours. After the reaction is completed, the mixture is centrifuged, and the centrifuged product is washed with ethanol and dried to obtain modified graphene oxide;

[0059] 3 g of modified graphene oxide was added to 40 g of a 1 mol / L zinc nitrate aqueous solution, and ultrasonicated at 45 kHz for 24 h at room temperature. The mixture was filtered, and the residue was washed with distilled water and then vacuum-dried to obtain zinc ion functionalized graphene oxide.

[0060] 0.15 g of zinc ion functionalized graphene oxide was added to 90 g of ethanol and ultrasonically treated for 1.5 h. The pH of the mixture was adjusted to 3 with a 1 mol / L hydrochloric acid aqueous solution. Then, 10 g of a 3.6% mass fraction silane coupling agent KH-570 / ethanol solution was added under stirring. The mixture was heated to 60° C. and stirred for 24 h. After the reaction was completed, the mixture was filtered, and the resulting residue was washed with deionized water and ethanol and dried in vacuo to obtain a composite modified graphene oxide.

[0061] Step S2, 2.4g of n-butyl stearate and 3.6g of n-octadecane were melted at 42°C, stirred for 15min, and cooled to room temperature to obtain a binary phase change material; 6g of the binary phase change material, 12g of methyl methacrylate, 1.2g of pentaerythritol triacrylate, and 0.004g of composite modified graphene oxide were mixed and ultrasonicated for 50min to obtain an oil phase; 0.7g of alkyl vinyl sulfonate was added to 87.9g of deionized water, stirred for 25min, and then the above oil phase was added and emulsified to obtain an O / W pre-emulsion; 22.5g of a 10% mass fraction of ammonium persulfate aqueous solution was added to the above O / W pre-emulsion within 90min, stirred at 75°C for 5h, filtered, and the obtained filter residue was washed with deionized water and vacuum dried to obtain phase change microcapsules;

[0062] Step S3, adding 1.8 g of nanosilver to 100 g of 80% by volume ethanol aqueous solution, ultrasonicating for 30 min, then adding 0.8 g of silane coupling agent KH-550 in a nitrogen atmosphere, reacting at 42° C. for 9 h, centrifuging, washing, and drying to obtain amino nanosilver;

[0063] 0.6 g of amino-modified nanosilver was ultrasonically dispersed in 70 g of ultrapure water for 30 minutes to obtain a mixed solution A; 12.5 g of phase change microcapsules were ultrasonically dispersed in 135 g of ultrapure water for 1.5 hours to obtain a mixed solution B; the mixed solutions A and B were mixed, and 1.2 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 1.2 g of N-hydroxysuccinimide were added under stirring conditions, and the mixture was reacted at room temperature for 45 hours. After the reaction was completed, the mixture was filtered, and the resulting filter residue was washed with ultrapure water and vacuum dried to obtain modified phase change microcapsules.

[0064] Example 2

[0065] This embodiment discloses a method for preparing a heat-storage and heat-retaining composite fabric, comprising the following steps:

[0066] Step (1), heating a 3% mass fraction sodium hydroxide aqueous solution to 70°C, adding acrylic fiber, with a solid-liquid ratio of 20:175, reacting at 70°C for 8 minutes, taking out, washing with deionized water 3 times, and then vacuum drying at 50°C to obtain pretreated acrylic fiber;

[0067] The pretreated acrylic fiber was immersed in an 8% by mass sorbitol aqueous solution for 10 minutes, squeezed and the wet weight was controlled to 180wt%, first heated at 75°C for 5 minutes, then heated at 178°C for 6 minutes, taken out, washed with distilled water, and dried at 100°C for 50 minutes to obtain functionalized acrylic fiber;

[0068] The functionalized acrylic fiber was immersed in a modified phase change microcapsule / water dispersion at a concentration of 40 g / L for 3 minutes, dried at 55°C for 15 minutes, and then immersed in a 40 g / L aqueous solution of ethylene glycol diglycidyl ether for 5 minutes. The fiber was removed and cured at 103°C for 70 minutes to obtain a modified acrylic fiber.

[0069] Step (2): Cesium carbonate and tungsten oxide were mixed by ball milling at a molar ratio of 1:3, and then heat-treated at 590°C for 6 hours 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;

[0070] Cs 0.33 WO3 nanoparticles and PA6 / 66 copolymer were mixed at a mass ratio of 0.15:1, extruded at 230°C, and sliced to obtain modified PA6 / 66 slices;

[0071] Modified PA6 / 66 chips and PA6 / 66 copolymer were mixed at a mass ratio of 1:8 and melt-spun at 280°C. The spun fibers were air-cooled, wound, and stretched at a stretch ratio of 1.5 to obtain modified PA6 / 66 hollow fibers.

[0072] Modified acrylic fiber and cotton fiber were blended in a mass ratio of 1:1 to form an outer yarn with a count of 30S (English count), and knitted to obtain a weight of 100g / m 2 Outer fabric;

[0073] The modified PA6 / 66 hollow fiber was spun and knitted to obtain a gram weight of 80g / m 2 The middle layer fabric;

[0074] The inner layer fabric, the middle layer fabric and the outer layer fabric are laminated and cut to obtain a composite fabric; wherein the inner layer fabric is made of pure cotton yarn spun by a knitting process with a gram weight of 100g / m 2 Pure cotton fiber fabric;

[0075] Step (3), adding 0.4 g of nano-carbon black and 0.1 g of dopamine hydrochloride to 100 mL of Tris-HCl buffer solution with a pH of 8.5, stirring at 23° C. for 20 h, centrifuging, washing the resulting precipitate with water and ethanol, and drying at 60° C. for 15 h to obtain modified nano-carbon black;

[0076] In a nitrogen atmosphere, 6 g of polyethylene glycol, 1.3 g of dimethylol propionic acid, and 5.2 g of toluene diisocyanate were mixed and stirred, and then 0.2 g of dibutyltin dilaurate was added. The mixture was heated to 85 ° C and stirred for 50 min. Then 0.1 g of modified nano carbon black was added, and the temperature was lowered to 70 ° C. The reaction was continued for 150 min. During the reaction, 10 g of acetone was added to reduce the viscosity of the reaction system. The temperature was lowered to 50 ° C, 1 g of triethylamine was added and reacted for 40 min, and then 0.04 g of chitosan was added. The chain extension reaction was carried out at 34 ° C for 40 min, and then distilled water was added to obtain a polyurethane finishing liquid with a concentration of 20 g / L;

[0077] The composite fabric was twice dipped and twice rolled in a polyurethane finishing liquid, with the liquid carrying rate of the padding being 70%, and then baked at 145°C for 4 minutes to obtain a heat storage and warmth retaining composite fabric.

[0078] Example 3

[0079] This embodiment discloses a method for preparing a heat-storage and heat-retaining composite fabric, comprising the following steps:

[0080] Step (1), heating a 5% sodium hydroxide aqueous solution to 90°C, adding acrylic fiber with a solid-liquid ratio of 20:195, reacting at 90°C for 4 minutes, taking out, washing with deionized water 5 times, and then vacuum drying at 60°C to obtain pretreated acrylic fiber;

[0081] The pretreated acrylic fiber was immersed in a 10% by mass sorbitol aqueous solution for 30 minutes, squeezed and the wet weight was controlled to 200 wt%, first heated at 80°C for 3 minutes, then heated at 182°C for 4 minutes, taken out, washed with distilled water, and dried at 100°C for 70 minutes to obtain functionalized acrylic fiber;

[0082] The functionalized acrylic fiber was immersed in a modified phase change microcapsule / water dispersion at a concentration of 50 g / L for 5 minutes, dried at 60°C for 10 minutes, and then immersed in a 50 g / L aqueous solution of ethylene glycol diglycidyl ether for 10 minutes. The fiber was removed and cured at 108°C for 50 minutes to obtain a modified acrylic fiber.

[0083] Step (2): Cesium carbonate and tungsten oxide were mixed by ball milling at a molar ratio of 1:3, and then heat-treated at 610°C for 4 hours 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;

[0084] Cs 0.33 WO3 nanoparticles and PA6 / 66 copolymer were mixed at a mass ratio of 0.25:1, extruded at 240°C, and sliced to obtain modified PA6 / 66 slices;

[0085] Modified PA6 / 66 chips and PA6 / 66 copolymer were mixed at a mass ratio of 1:10 and melt-spun at 300°C. The spun fibers were air-cooled, wound, and stretched at a stretch ratio of 1.7 to obtain modified PA6 / 66 hollow fibers.

[0086] Modified acrylic fiber and cotton fiber were blended in a mass ratio of 1:1 to form an outer yarn with a count of 40S (English count), and knitted to obtain a weight of 120g / m 2 Outer fabric;

[0087] The modified PA6 / 66 hollow fiber was spun and knitted to obtain a gram weight of 100g / m 2 The middle layer fabric;

[0088] The inner layer fabric, the middle layer fabric and the outer layer fabric are laminated and cut to obtain a composite fabric; wherein the inner layer fabric is made of pure cotton yarn spun by a knitting process with a gram weight of 120g / m 2 Pure cotton fiber fabric;

[0089] Step (3), adding 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, stirring at 28° C. for 20 h, centrifuging, washing the resulting precipitate with water and ethanol, and drying at 70° C. for 10 h to obtain modified nano-carbon black;

[0090] In a nitrogen atmosphere, 12 g of polyethylene glycol, 2.6 g of dimethylol propionic acid, and 10.4 g of toluene diisocyanate were mixed and stirred, and then 0.3 g of dibutyltin dilaurate was added. The mixture was heated to 90 ° C and stirred for 40 min. Then 0.3 g of modified nano carbon black was added, and the temperature was lowered to 80 ° C. The reaction was continued for 100 min. During the reaction, 15 g of acetone was added to reduce the viscosity of the reaction system. The temperature was then lowered to 55 ° C. 2 g of triethylamine was added and reacted for 50 min. Then 0.1 g of chitosan was added and the chain extension reaction was carried out at 36 ° C for 20 min. Then distilled water was added to obtain a polyurethane finishing liquid with a concentration of 40 g / L;

[0091] The composite fabric was twice dipped and twice rolled in a polyurethane finishing liquid, with the liquid carrying rate of the padding being 80%, and then baked at 155° C. for 2 minutes to obtain a heat storage and warmth retaining composite fabric.

[0092] Example 4

[0093] This embodiment discloses a method for preparing a heat-storage and heat-retaining composite fabric, comprising the following steps:

[0094] Step (1), heating a 4% sodium hydroxide aqueous solution to 80°C, adding acrylic fiber with a solid-liquid ratio of 20:185, reacting at 80°C for 6 minutes, taking out, washing with deionized water 4 times, and then vacuum drying at 55°C to obtain pretreated acrylic fiber;

[0095] The pretreated acrylic fiber was immersed in a 9% by mass sorbitol aqueous solution for 20 minutes, squeezed and the wet weight was controlled to 190 wt%, first heated at 78°C for 4 minutes, then heated at 180°C for 5 minutes, taken out, washed with distilled water, and dried at 100°C for 60 minutes to obtain functionalized acrylic fiber;

[0096] The functionalized acrylic fiber was immersed in a modified phase change microcapsule / water dispersion at a concentration of 45 g / L for 4 minutes, dried at 58°C for 12 minutes, and then immersed in a 45 g / L aqueous solution of ethylene glycol diglycidyl ether for 8 minutes. The fiber was removed and cured at 105°C for 60 minutes to obtain a modified acrylic fiber.

[0097] Step (2): Cesium carbonate and tungsten oxide were mixed by ball milling at a molar ratio of 1:3, and then heat treated at 600°C for 5 hours 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;

[0098] Cs 0.33WO3 nanoparticles and PA6 / 66 copolymer were mixed in a mass ratio of 0.2:1, extruded at 235°C, and sliced to obtain modified PA6 / 66 slices;

[0099] Modified PA6 / 66 chips and PA6 / 66 copolymer were mixed at a mass ratio of 1:9 and melt-spun at 290°C. The spun fibers were air-cooled, wound, and stretched at a stretch ratio of 1.6 to obtain modified PA6 / 66 hollow fibers.

[0100] Modified acrylic fiber and cotton fiber were blended in a mass ratio of 1:1 to form an outer yarn with a count of 35S (English count), and knitted to obtain a weight of 110g / m 2 Outer fabric;

[0101] The modified PA6 / 66 hollow fiber was spun and knitted to obtain a gram weight of 90g / m 2 The middle layer fabric;

[0102] The inner layer fabric, the middle layer fabric and the outer layer fabric are laminated and cut to obtain a composite fabric; wherein the inner layer fabric is made of pure cotton yarn spun by a knitting process with a gram weight of 110g / m 2 Pure cotton fiber fabric;

[0103] Step (3), adding 0.5 g of nano-carbon black and 0.15 g of dopamine hydrochloride to 110 mL of Tris-HCl buffer solution with a pH of 8.5, stirring at 25° C. for 25 h, centrifuging, washing the resulting precipitate with water and ethanol, and drying at 65° C. for 12 h to obtain modified nano-carbon black;

[0104] In a nitrogen atmosphere, 9 g of polyethylene glycol, 1.9 g of dimethylol propionic acid, and 7.8 g of toluene diisocyanate were mixed and stirred, and then 0.3 g of dibutyltin dilaurate was added. The mixture was heated to 87.5 ° C and stirred for 45 min. Then 0.2 g of modified nano carbon black was added, and the temperature was lowered to 75 ° C. The reaction was continued for 120 min. During the reaction, 12.5 g of acetone was added to reduce the viscosity of the reaction system. The temperature was lowered to 53 ° C, 1.5 g of triethylamine was added and reacted for 45 min, and then 0.07 g of chitosan was added. The chain extension reaction was carried out at 35 ° C for 30 min, and then distilled water was added to obtain a polyurethane finishing liquid with a concentration of 30 g / L;

[0105] The composite fabric was twice dipped and twice rolled in a polyurethane finishing liquid, with the liquid carrying rate of the padding being 75%, and then baked at 150° C. for 3 minutes to obtain a heat storage and warmth retaining composite fabric.

[0106] The modified phase-change microcapsules in the above Examples 2-4 are the modified phase-change microcapsules prepared in Example 1.

[0107] Comparative Example 1

[0108] This comparative example discloses a method for preparing phase-change microcapsules, comprising the following steps:

[0109] Step S1, adding 0.15g of graphene oxide to 90g of ethanol, ultrasonically treating for 1.5h, adjusting the pH of the mixed system to 3 with a 1mol / L hydrochloric acid aqueous solution, then adding 10g of a 3.6% mass fraction of a silane coupling agent KH-570 / ethanol solution under stirring, heating to 60°C and stirring for 24h. After the reaction is completed, filtering, washing the obtained filter residue with deionized water and ethanol, and vacuum drying to obtain a composite modified graphene oxide;

[0110] Step S2, 2.4g of n-butyl stearate and 3.6g of n-octadecane were melted at 42°C, stirred for 15min, and cooled to room temperature to obtain a binary phase change material; 6g of the binary phase change material, 12g of methyl methacrylate, 1.2g of pentaerythritol triacrylate, and 0.004g of composite modified graphene oxide were mixed and ultrasonicated for 50min to obtain an oil phase; 0.7g of alkyl vinyl sulfonate was added to 87.9g of deionized water, stirred for 25min, and then the above oil phase was added and emulsified to obtain an O / W pre-emulsion; 22.5g of a 10% mass fraction of ammonium persulfate aqueous solution was added to the above O / W pre-emulsion within 90min, stirred at 75°C for 5h, filtered, and the obtained filter residue was washed with deionized water and vacuum dried to obtain phase change microcapsules;

[0111] Step S3, adding 1.8 g of nanosilver to 100 g of 80% by volume ethanol aqueous solution, ultrasonicating for 30 min, then adding 0.8 g of silane coupling agent KH-550 in a nitrogen atmosphere, reacting at 42° C. for 9 h, centrifuging, washing, and drying to obtain amino nanosilver;

[0112] 0.6 g of amino-modified nanosilver was ultrasonically dispersed in 70 g of ultrapure water for 30 minutes to obtain a mixed solution A; 12.5 g of phase change microcapsules were ultrasonically dispersed in 135 g of ultrapure water for 1.5 hours to obtain a mixed solution B; the mixed solutions A and B were mixed, and 1.2 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 1.2 g of N-hydroxysuccinimide were added under stirring conditions, and the mixture was reacted at room temperature for 45 hours. After the reaction was completed, the mixture was filtered, and the resulting filter residue was washed with ultrapure water and vacuum dried to obtain modified phase change microcapsules.

[0113] Comparative Example 2

[0114] This comparative example discloses a method for preparing a modified phase-change microcapsule, comprising the following steps:

[0115] Step S1, 2.4g of n-butyl stearate and 3.6g of n-octadecane were melted at 42°C, stirred for 15min, and cooled to room temperature to obtain a binary phase change material; 6g of the binary phase change material, 12g of methyl methacrylate, and 1.2g of pentaerythritol triacrylate were ultrasonically treated for 50min to obtain an oil phase; 0.7g of alkyl vinyl sulfonate was added to 87.9g of deionized water, stirred for 25min, and then the above oil phase was added and emulsified to obtain an O / W pre-emulsion; 22.5g of a 10% by mass ammonium persulfate aqueous solution was added to the above O / W pre-emulsion within 90min, the mixture was stirred at 75°C for 5h, filtered, the obtained filter residue was washed with deionized water, and vacuum dried to obtain phase change microcapsules;

[0116] Step S2, adding 1.8 g of nanosilver to 100 g of 80% by volume ethanol aqueous solution, ultrasonicating for 30 min, then adding 0.8 g of silane coupling agent KH-550 in a nitrogen atmosphere, reacting at 42° C. for 9 h, centrifuging, washing, and drying to obtain amino nanosilver;

[0117] 0.6 g of amino-modified nanosilver was ultrasonically dispersed in 70 g of ultrapure water for 30 minutes to obtain a mixed solution A; 12.5 g of phase change microcapsules were ultrasonically dispersed in 135 g of ultrapure water for 1.5 hours to obtain a mixed solution B; the mixed solutions A and B were mixed, and 1.2 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 1.2 g of N-hydroxysuccinimide were added under stirring conditions, and the mixture was reacted at room temperature for 45 hours. After the reaction was completed, the mixture was filtered, and the resulting filter residue was washed with ultrapure water and vacuum dried to obtain modified phase change microcapsules.

[0118] Comparative Example 3

[0119] This comparative example discloses a method for preparing a modified phase-change microcapsule, comprising the following steps:

[0120] Step S1, graphene oxide, phthalic anhydride, benzene, and p-toluenesulfonic acid are mixed in a mass ratio of 1:2:9.5:0.04, and then glass beads are added. The mixture is refluxed at 100° C. for 3 hours. After the reaction is completed, the mixture is centrifuged, and the centrifuged product is washed with ethanol and dried to obtain modified graphene oxide;

[0121] 3 g of modified graphene oxide was added to 40 g of a 1 mol / L zinc nitrate aqueous solution, and ultrasonicated at 45 kHz for 24 h at room temperature. The mixture was filtered, and the residue was washed with distilled water and then vacuum-dried to obtain zinc ion functionalized graphene oxide.

[0122] 0.15 g of zinc ion functionalized graphene oxide was added to 90 g of ethanol and ultrasonically treated for 1.5 h. The pH of the mixture was adjusted to 3 with a 1 mol / L hydrochloric acid aqueous solution. Then, 10 g of a 3.6% mass fraction silane coupling agent KH-570 / ethanol solution was added under stirring. The mixture was heated to 60° C. and stirred for 24 h. After the reaction was completed, the mixture was filtered, and the resulting residue was washed with deionized water and ethanol and dried in vacuo to obtain a composite modified graphene oxide.

[0123] Step S2, 2.4g of n-butyl stearate and 3.6g of n-octadecane were melted at 42°C, stirred for 15min, and cooled to room temperature to obtain a binary phase change material; 6g of the binary phase change material, 12g of methyl methacrylate, 1.2g of pentaerythritol triacrylate, and 0.004g of composite modified graphene oxide were mixed and ultrasonicated for 50min to obtain an oil phase; 0.7g of alkyl vinyl sulfonate was added to 87.9g of deionized water, stirred for 25min, and then the above oil phase was added and emulsified to obtain an O / W pre-emulsion; 22.5g of a 10% mass fraction of ammonium persulfate aqueous solution was added to the above O / W pre-emulsion within 90min, stirred at 75°C for 5h, filtered, and the resulting filter residue was washed with deionized water and vacuum dried to obtain modified phase change microcapsules;

[0124] Comparative Example 4

[0125] Comparative Example 4 Compared with Example 4, in the process of preparing modified acrylic fiber, Comparative Example 4 adopts the modified phase change microcapsules prepared in Comparative Example 1, and other conditions remain unchanged.

[0126] Comparative Example 5

[0127] Comparative Example 5 Compared with Example 4, in the process of preparing modified acrylic fiber, Comparative Example 5 adopts the modified phase change microcapsules prepared in Comparative Example 2, and other conditions remain unchanged.

[0128] Comparative Example 6

[0129] Comparative Example 6 Compared with Example 4, in the process of preparing modified acrylic fiber, Comparative Example 6 adopts the modified phase change microcapsules prepared in Comparative Example 3, and other conditions remain unchanged.

[0130] Comparative Example 7

[0131] Comparative Example 7 Compared with Example 4, in the process of preparing the polyurethane finishing liquid in Comparative Example 7, no modified nano carbon black was added, and other conditions remained unchanged.

[0132] Comparative Example 8

[0133] Comparative Example 8 Compared with Example 4, in the process of preparing the polyurethane finishing liquid in Comparative Example 8, no chitosan was added, and other conditions remained unchanged.

[0134] In the above embodiments and comparative examples, graphene oxide with a thickness of 0.55-1.2 nm and a diameter of 0.5-3 μm is from Zhongke Leiming (Beijing) Technology Co., Ltd.; nanosilver with a particle size of 20 nm, model ML-Ag-N20, and a spherical micromorphology is from Zhejiang Manli Nanotechnology Co., Ltd.; PA6 / 66 copolymer, brand: BASF, product number: C3309, density: 1.12 g / cm3, melting point: 195-197°C; purchased from Shanghai Juying Plastic Technology Co., Ltd.; nanocarbon black with an average particle size of 30 nm, brand: Cabot, model: BLACKPEARLS2000, product number: 13165, is from Guangzhou Jingyi New Materials Co., Ltd.; polyethylene glycol (PEG, Mn = 600 g / mol) is from Jinan Qihang Chemical Technology Co., Ltd.; chitosan with a viscosity of 200-400 mPas and a deacetylation degree of 95% is from Shanghai Aladdin Biochemical Technology Co., Ltd. (Shanghai, China).

[0135] Experimental example

[0136] Performance tests were performed on the heat storage and warmth retaining composite fabrics of Examples 2-4 and Comparative Examples 4-8.

[0137] 1. Antistatic test: Test in accordance with GB / T12703.2-2009 "Test method for electrostatic properties of textiles - Part 2: Charge surface density".

[0138] 2. Warmth retention test: Tested in accordance with the flat plate method of GB / T35762-2017.

[0139] 3. Anti-pilling performance test: Tested in accordance with the circular locus method of GB / T4802.1-2008 Textile fabric pilling test.

[0140] 4. Hygroscopicity test: The test shall be conducted in accordance with GB / T21655.1-2008 “Evaluation of moisture absorption and quick-drying properties of textiles Part 1: Single combination test method”.

[0141] The test results are shown in Table 1:

[0142] Table 1

[0143] <![CDATA[Surface charge density / μC·m 2 > Insulation rate / % Anti-pilling grade Water absorption / % Example 2 0.61 50.4 Level 5 280 Example 3 0.53 51.6 Level 5 293 Example 4 0.57 50.9 Level 5 286 Comparative Example 4 0.69 49.7 Level 5 279 Comparative Example 5 1.27 45.3 Level 5 266 Comparative Example 6 0.88 48.2 Level 4 258 Comparative Example 7 1.01 46.8 Level 4 233 Comparative Example 8 0.76 50.8 Level 3 212

[0144] The test results in Table 1 show that the heat-storage and thermal insulation composite fabrics prepared in Examples 2-4 of the present invention have excellent antistatic properties, heat-storage and thermal insulation properties, anti-pilling properties, and moisture-absorbing and breathable properties. A comparison of Comparative Example 4 with Example 4 shows that the reaction of phthalic anhydride with graphene oxide introduces more hydrophilic carboxyl groups on the graphene oxide surface, which in turn uniformly fixes zinc ions on the graphene oxide, improving the hydrophilicity and conductivity of the graphene oxide, enhancing the light absorption efficiency of the graphene oxide, and reducing infrared emissivity. Furthermore, the modified phase change microcapsules containing zinc ion-functionalized graphene oxide are attached to the outer fabric layer, improving the antistatic properties, heat-storage and thermal insulation properties, and moisture-absorbing and breathable properties of the fabric. From the comparison of 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 electrical conductivity, thermal conductivity, hydrophilicity, and light-to-heat conversion ability of the phase change microcapsules, thereby improving the antistatic performance, heat storage and warmth retention performance, and moisture absorption and breathability of the composite fabric. The amino-silver on the modified phase change microcapsules, while further improving the above properties, increases the surface roughness of the phase change microcapsules, thereby increasing the surface roughness of the acrylic fiber, thereby increasing the cohesion between the fibers and improving the anti-pilling performance of the fabric. From the comparison of Comparative Example 7 and Example 4, it can be seen that

[0145] The modified nano-carbon black treated with polydopamine in the polyurethane finishing liquid has excellent conductivity, photothermal conversion efficiency, and hydrophilicity, thereby giving the composite fabric better antistatic properties, heat storage and warmth retention properties, and moisture absorption and breathability. In addition, the organic functional groups on the surface of the modified nano-carbon black enhance the bonding strength between the polyurethane finishing liquid and the composite fabric, and also have a positive effect on the anti-pilling properties of the composite fabric. As can be seen from the comparison between Comparative Example 8 and Example 4, the introduction of chitosan into polyurethane improves the hydrophilicity, antistatic properties, and cross-linking density of the polyurethane system, and forms a durable and tough polymer network on the surface of the composite fabric, thereby giving the composite fabric excellent antistatic properties, anti-pilling properties, and moisture absorption and breathability.

[0146] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a heat-storage and heat-retaining composite fabric, characterized in that: The following steps are involved: Step (1), acrylic fiber is pretreated with a sodium hydroxide aqueous solution, then grafted with sorbitol, and finally loaded with modified phase change microcapsules to obtain modified acrylic fiber; The preparation method of the modified phase-change microcapsules comprises the following steps: Step S1, modifying graphene oxide with phthalic anhydride, functionalizing with zinc ions, and treating with a silane coupling agent KH-570 in sequence to obtain a composite modified graphene oxide; Step S2, preparing a phase change microcapsule with n-butyl stearate and n-octadecane as the core material and methyl methacrylate, pentaerythritol triacrylate, and composite modified graphene oxide as the shell; Step S3, nanosilver is surface-treated by amino group and then connected to the phase change microcapsules to obtain modified phase change microcapsules; Step (2): Prepare Cs using cesium carbonate and tungsten oxide as raw materials. 0.33 WO3 nanoparticles; Cs 0.33 WO3 nanoparticles are blended with PA6 / 66 copolymer, extruded, sliced, and then melt-spun with PA6 / 66 copolymer to obtain modified PA6 / 66 hollow fibers; The outer layer fabric is made of modified acrylic fiber and cotton fiber; the middle layer fabric is made of modified PA6 / 66 hollow fiber; the inner layer fabric, the middle layer fabric and the outer layer fabric are laminated to obtain a composite fabric; Step (3), modifying nano carbon black with polydopamine to obtain modified nano carbon black; preparing a polyurethane finishing liquid containing modified nano carbon black and chitosan by reaction; The composite fabric is twice dipped and twice rolled in a polyurethane finishing liquid, and baked to obtain a heat storage and warmth retaining composite fabric.

2. The method for preparing the heat-storage and heat-retaining composite fabric according to claim 1, wherein: In step (1), the method for preparing the modified acrylic fiber specifically comprises the following steps: Heat a 3-5% mass fraction sodium hydroxide aqueous solution to 70-90° C., add acrylic fiber at a solid-liquid ratio of 20:(175-195), react at 70-90° C. for 4-8 minutes, remove, wash, and dry to obtain pretreated acrylic fiber; The pretreated acrylic fiber is immersed in an aqueous solution of sorbitol with a mass fraction of 8-10% for 10-30 minutes, squeezed and the wet weight is controlled to be 180-200wt%, first heated at 75-80°C for 3-5 minutes, then heated at 178-182°C for 4-6 minutes, taken out, washed, and dried to obtain a functionalized acrylic fiber; The functionalized acrylic fiber is immersed in a modified phase change microcapsule / water dispersion with a concentration of 40-50 g / L for 3-5 minutes, dried at 55-60° C. for 10-15 minutes, and then immersed in an aqueous solution of ethylene glycol diglycidyl ether with a concentration of 40-50 g / L for 5-10 minutes. The fiber is taken out and cured at 103-108° C. for 50-70 minutes to obtain the modified acrylic fiber.

3. The method for preparing the heat-storage and heat-retaining composite fabric according to claim 1, wherein: In step (1), the method for preparing the modified phase-change microcapsules specifically comprises the following steps: Step S1, mixing graphene oxide, phthalic anhydride, benzene, and p-toluenesulfonic acid in a mass ratio of 1:(1.5-2.5):(9-10):0.04, reflux reaction at 97-103° C. for 2.5-3.5 hours, and purifying to obtain modified graphene oxide; Modified graphene oxide and a 1 mol / L zinc nitrate aqueous solution were mixed in a mass ratio of (2-4):(30-50), and ultrasonically treated at room temperature under 40-45 kHz for 20-30 h for purification to obtain zinc ion functionalized graphene oxide; The zinc ion functionalized graphene oxide was added to ethanol, ultrasonicated, and the pH of the mixture was adjusted to 2.9-3.1 by aqueous hydrochloric acid solution. Then, a 3.6% by mass fraction of a silane coupling agent KH-570 / ethanol solution was added under stirring, and the mixture was heated to 58-62° C. and stirred for 20-30 hours, and purified to obtain a 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); Step S2, mixing n-butyl stearate and n-octadecane in a mass ratio of (1.6-3.2): (2.4-4.8), melting at 40-44 ° C, stirring for 10-20 minutes, and cooling to room temperature to obtain a binary phase change material; mixing 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), ultrasonicating for 30-60 minutes to obtain an oil phase; and mixing alkyl vinyl sulfonate. and deionized water in a mass ratio of (0.5-0.9):(58.6-117.2), stirred for 20-30 minutes, and then added with the above oil phase, emulsified to obtain an O / W pre-emulsion; adding a 10% by mass fraction of ammonium persulfate aqueous solution to the above O / W pre-emulsion within 60-120 minutes, stirring at 70-80°C for 4.5-5.5 hours, filtering, washing, and drying to obtain phase change microcapsules; wherein the mass ratio of the ammonium persulfate aqueous solution to the O / W pre-emulsion is (15-30):(71.9-143.8); Step S3, adding nanosilver to an 80% by volume ethanol aqueous solution, adding a silane coupling agent KH-550 in a nitrogen atmosphere, reacting at 40-45° C. for 8-10 hours, and purifying to obtain amino nanosilver; wherein the mass ratio of nanosilver, ethanol aqueous solution, and silane coupling agent KH-550 is (0.5-3):(80-120):(0.5-1); Aminated nanosilver is ultrasonically dispersed in ultrapure water for 20-40 minutes to obtain a mixed solution A; phase change microcapsules are ultrasonically dispersed in ultrapure water for 1-2 hours to obtain a mixed solution B; mixed solution A and mixed solution B are mixed, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide are added under stirring conditions, reacted at room temperature for 40-50 hours, and purified to obtain modified phase change microcapsules; wherein the mass ratio of aminated nanosilver, 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 method for preparing the heat-storage and heat-retaining composite fabric according to claim 1, wherein: In step (2), the method for preparing the modified PA6 / 66 hollow fiber specifically comprises the following steps: Cesium carbonate and tungsten oxide were mixed by ball milling at a molar ratio of 1:3, and then heat treated 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; Cs 0.33 WO3 nanoparticles and PA6 / 66 copolymer are mixed in a mass ratio of (0.15-0.25):1, extruded at 230-240°C, and sliced to obtain modified PA6 / 66 slices; Modified PA6 / 66 chips and PA6 / 66 copolymer are mixed in a mass ratio of 1:(8-10), melt-spinned at 280-300°C, and the spun fibers are air-cooled, wound, and stretched with a stretching ratio of 1.5-1.7 to obtain modified PA6 / 66 hollow fibers.

5. The method for preparing the heat-storage and heat-retaining composite fabric according to claim 1, characterized in that: 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 an imperial count of 30-40S, and then knitting; the outer fabric has a gram weight of 100-120g / m 2 .

6. The method for preparing the heat-storage and heat-retaining composite fabric according to claim 1, wherein: In the 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 .

7. The method for preparing the heat-storage and heat-retaining composite fabric according to claim 1, characterized in that: In the step (2), the inner layer fabric is made of pure cotton yarn spun by knitting technology with a gram weight of 100-120g / m 2 Pure cotton fiber fabric.

8. The method for preparing the heat-storage and heat-retaining composite fabric according to claim 1, characterized in that: In step (3), the method for preparing the polyurethane finishing liquid specifically comprises the following steps: Nanocarbon black, dopamine hydrochloride, and a Tris-HCl buffer solution having a pH of 8.5 were mixed in a ratio of (0.4-0.6) g: (0.1-0.2) g: (100-120) mL, stirred at 23-28° C. for 20-30 h, and purified to obtain modified nanocarbon black; In a nitrogen atmosphere, polyethylene glycol, dihydroxymethylpropionic acid, and toluene diisocyanate were mixed and stirred, and then dibutyltin dilaurate was added. The mixture was heated to 85-90°C and stirred for reaction for 40-50 minutes. Then, modified nano carbon black was added, and the temperature was lowered to 70-80°C. The reaction was continued for 100-150 minutes. Acetone was added during the reaction, and the temperature was lowered to 50-55°C. Triethylamine was added and the reaction was continued for 40-50 minutes. Chitosan was added and the reaction was continued at 34-36°C for 20- The mixture was stirred for 40 minutes, and distilled water was added to obtain a polyurethane finishing liquid with a concentration of 20-40 g / L; wherein the mass ratio of polyethylene glycol, dihydroxymethylpropionic acid, toluene diisocyanate, dibutyltin dilaurate, modified nano-carbon black, acetone, triethylamine, and chitosan was (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 method for preparing the heat-storage and heat-retaining composite fabric according to claim 1, wherein: In the step (3), the liquid carrying rate of the composite fabric in the polyurethane finishing liquid is 70-80%; the baking conditions are: baking at 145-155°C for 2-4 minutes.

10. A heat-storage and heat-retaining composite fabric prepared by the method for preparing a heat-storage and heat-retaining composite fabric according to any one of claims 1 to 9.

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