Heat preservation and storage polyester fiber and preparation method thereof

Abstract

The invention relates to the field of chemical fibers, and provides a heat preservation and storage polyester fiber and a preparation method thereof. The heat preservation and storage polyester fiber is prepared from the following raw materials: a hollow nano material A with the porosity of 40-70%, an inorganic powder material B with a photothermal conversion function and moisture absorption modified polyester C with the moisture regain of 0.45-0.83%, the mass of A accounts for 0.1-3.5% of the mass of C, and the mass of B accounts for 0.1-4% of the mass of C. The preparation method of the heat preservation and storage polyester fiber comprises the following steps: uniformly mixing the polyester master batch containing the hollow nano material, the polyester master batch containing the inorganic powder material with the photo-thermal conversion function and the moisture absorption modified polyester chip, and then adding into a spinning machine for fiber forming. The air content in the fiber is increased by using the hollow nano material, and the heat insulation effect is improved; the direct temperature rise of the fiber is realized by using a photothermal conversion functional material; meanwhile, the hygroscopicity of the fiber is improved, certain heat is generated, and the heat preservation performance of the fiber material can be comprehensively improved through cooperation of the multi-stage heat preservation means.

Description

Technical Field

[0001] The invention relates to the field of chemical fibers, and in particular to a heat-insulating and heat-storing polyester fiber and a preparation method thereof. Background Art

[0002] With the convenience of transportation, new entertainment projects such as winter tourism and night play are becoming more and more popular, and people's demand for warm clothing is increasing. In addition, the younger generation is also more pursuing a healthy and comfortable lifestyle, which makes thermal fiber materials have a lot of room for development. The warmth of fiber materials is generally achieved in two ways.

[0003] First, try to keep the original heat from being lost easily, such as increasing the trapped air content in the fiber through special-shaped cross-sections and fluffing processing, thereby reducing the thermal conductivity of the fiber and playing a warming role. Sun et al. (CN205501459U) used a melt direct spinning process to obtain a special-shaped FDY polyester yarn through a special-shaped spinneret. The shape of the new fiber is flat and has a hollow warming effect.

[0004] The second is to obtain new heat from the outside world, such as by introducing some heat-generating materials such as photothermal and electric heating into the fiber to realize the conversion of external energy and achieve heat storage and heat preservation. Zhang et al. (CN103320888A) mixed nano-scale coffee carbon with far-infrared materials containing various metal ions and polyester melt to prepare masterbatch, and then melt-spun the masterbatch with polyester slices to form heat storage and heat preservation health care composite yarn. The composite fiber has good health care functions such as strong heat storage capacity and long heat preservation time. Zhang Baoling (CN1139164A) disclosed a method for preparing far-infrared fabric, which is to add a mixture of aluminum oxide, titanium oxide, magnesium oxide and zirconium oxide (far-infrared ceramic powder) to polypropylene and process it into far-infrared health care clothing. Patent CN1309198A of Zuyang Co., Ltd. discloses a method for manufacturing a fiber with far-infrared radiation, wherein magnesium oxide, calcium oxide, zirconium oxide, silicon oxide, praseodymium and cerium are ground into powder and mixed to make far-infrared ceramic powder, which is used to make far-infrared masterbatch, and finally obtains a fiber with far-infrared radiation that has the functions of heat storage and heat preservation, promoting blood circulation, antibacterial and deodorizing. Ono Hiroshi et al. (CN109642349A) obtains a hygroscopic and heat-generating fiber with a high heating rate and high fluffiness by preparing a parallel composite fiber composed of two acrylonitrile polymers. Patent CN115058792A of Yangzhou Huitong Bio-New Materials Co., Ltd. discloses a polylactic acid-based polyester sheath-core composite long fiber and a preparation method thereof, wherein the low melting point copolyester used in the sheath material is obtained by multi-polymerization of terephthalic acid, ethylene glycol, diethylene glycol, isophthalic acid and polyethylene glycol.

[0005] The preparation of the above-mentioned thermal insulation fiber materials only considers a single thermal insulation principle, and the improvement of the thermal insulation performance of the fiber has certain limitations. Therefore, it is of great significance to propose a new method for preparing a fiber material that integrates multiple thermal insulation principles. Summary of the invention

[0006] In order to overcome the problem of insufficient thermal insulation performance of fibers, the present invention provides a thermal insulation and heat storage polyester fiber and a preparation method thereof. Hollow nanomaterials are used to increase the air content in the fibers to improve the thermal insulation effect. Photothermal conversion functional materials are used to achieve direct heating of the fibers. At the same time, the hygroscopicity of the fibers is improved to generate a certain amount of heat. Such multi-stage thermal insulation means can work together to comprehensively improve the thermal insulation performance of the fiber materials.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions: A heat-insulating and heat-storing polyester fiber, the raw materials of which include a hollow nano material A with a porosity of 40-70%, an inorganic powder material B with a light-heat conversion function and a hygroscopic modified polyester C with a regain of 0.45-0.83%, the mass of A being 0.1-3.5% of the mass of C, and the mass of B being 0.1-4% of the mass of C.

[0008] Preferably, the hollow nanomaterial is selected from one or more of hollow silica, hollow titania, and hollow cerium dioxide, and has a particle size of 300-800 nm.

[0009] Preferably, the inorganic powder material having the photothermal conversion function is selected from one or more of far-infrared ceramics, medical stone, zirconium carbide, and tourmaline, and has a particle size of 200-500 nm.

[0010] The present invention also provides a preparation method of the thermal insulation and heat storage polyester fiber, comprising the following steps: evenly mixing polyester masterbatches containing hollow nanomaterials, polyester masterbatches containing inorganic powder materials with light-to-heat conversion functions, and hygroscopic modified polyester chips, and then adding them into a spinning machine for fiber molding to obtain thermal insulation and heat storage polyester fibers.

[0011] Preferably, the mass ratio of the polyester masterbatch containing hollow nanomaterials, the polyester masterbatch containing inorganic powder material having light-to-heat conversion function, and the hygroscopic modified polyester chips is 10-20:4-7:73-86.

[0012] Preferably, hollow nanomaterials, coupling agents and PET polyester matrix are used as raw materials to prepare polyester masterbatch containing hollow nanomaterials through an extrusion granulation process.

[0013] As further preferred, the mass ratio of the hollow nanomaterial, the coupling agent and the PET polyester matrix is ​​10:0.5-2:88-89.5. The coupling agent is a titanate silane coupling agent, and more preferably a TCA-KTTS coupling agent.

[0014] The present invention prepares polyester masterbatch containing hollow nano materials through an extrusion granulation process. Since the polyhydroxyl groups on the surface of the inorganic nano materials are not compatible with polyester, an amphiphilic titanate silane coupling agent is added as a compatibilizer.

[0015] Preferably, the polyester masterbatch containing the inorganic powder material having the photothermal conversion function is prepared by using the inorganic powder material having the photothermal conversion function, the dispersant and the PET polyester matrix as raw materials through an extrusion granulation process.

[0016] As a further preferred embodiment, the mass ratio of the inorganic powder material with light-to-heat conversion function, the dispersant and the PET polyester matrix is ​​30:0.5-2:68-69.5. The dispersant is selected from polyethylene wax, zinc stearate and calcium stearate.

[0017] The present invention prepares polyester masterbatch with energy storage and heat storage function through an extrusion granulation process, and adds a dispersant to improve the dispersibility.

[0018] Preferably, 95-98 mol% terephthalic acid and 2-5 mol% isophthalic acid, 95-97 mol% ethylene glycol and 3-5 mol% polyethylene glycol are used as polymerization monomers, and the hygroscopic modified copolyester is obtained through esterification and polycondensation reaction, and the molar ratio of alcohol to acid is 1.2-1.5:1.

[0019] Preferably, during the fiber forming process, the spinning temperature is 275-285°C and the winding speed is 2500-3000 m / min.

[0020] Therefore, the beneficial effects of the present invention are: (1) The heat-insulating and heat-storing polyester fiber of the present invention is realized by combining three heat-insulating principles. First, hollow nano-microspheres with a large porosity are introduced into the fiber. The rich cavity structure ensures that a large amount of air with a very low thermal conductivity is retained inside the fiber, which can greatly reduce the conduction and loss of heat, fix the body's heat near the body surface, and thus play a role in keeping warm. Then, inorganic nanomaterials that can directly absorb external light energy and human body heat radiation and convert them into heat are introduced into the fiber to achieve rapid temperature rise. Then, hygroscopic modified polyester is added to improve the fiber's hygroscopic properties, which is conducive to the combination of water molecules with the hydrophilic groups in the fiber material in the form of hydrogen bonds, converting the kinetic energy of water molecules into heat energy; at the same time, the absorbed water molecules are converted from gas to liquid, which also releases latent heat of condensation.

[0021] (2) The infrared radiation speed is the same as that of visible light, and it can travel in a straight line like light; if a reflector is used, its conduction direction can be changed. The present invention adds hollow nano-microspheres with rich pores, and the infrared rays are refracted multiple times in the pores, which can increase the heat energy converted by the inorganic powder material with light-heat conversion function.

[0022] (3) Far infrared rays have strong penetration and radiation power, and have significant temperature control effect and resonance effect. They are easily absorbed by objects and converted into the internal energy of objects. After being absorbed, far infrared rays can cause water molecules to resonate, activate water molecules, and enhance the binding force between molecules. The present invention adds hygroscopic modified polyester to improve the hygroscopicity of the fiber, increase the moisture content of the fiber, and increase the heat energy converted by the inorganic powder material with light-heat conversion function.

[0023] (4) Hollow nanomaterials are introduced to prepare fibers with a cavity structure. The hollow cavities in the obtained fibers are evenly distributed and have strong size adjustability. At the same time, the replacement of spinning components and the purchase of special-shaped spinnerets are avoided. DETAILED DESCRIPTION

[0024] The technical solution of the present invention is further described below through specific embodiments.

[0025] In the present invention, unless otherwise specified, the raw materials and equipment used can be purchased from the market or are commonly used in the art. The methods in the embodiments, unless otherwise specified, are all conventional methods in the art. Unless otherwise specified, parts are all weight parts, temperatures are expressed in ° C or at ambient temperature, and pressures are atmospheric pressure or near atmospheric pressure. There are many variations and combinations of reaction conditions (such as component concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the method, and only reasonable routine experiments will be required to optimize such method conditions.

[0026] Example A method for preparing a multi-stage heat-insulating and heat-storing polyester fiber material comprises the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: hollow nanomaterials (selected from hollow silica, hollow titania, hollow cerium dioxide) with an average particle size of 300-800 nm and a porosity of 40-70%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:0.5-2:88-89.5, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow nanomaterials.

[0027] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: ceramic powder with an average particle size of 200-500nm (selected from tourmaline, medical stone, zirconium carbide), a dispersing aid (selected from polyethylene wax, zinc stearate, calcium stearate) and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:0.5-2:68-69.5, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0028] (3) Preparation of hygroscopic modified polyester chips: using 95-98 mol% terephthalic acid and 2-5 mol% isophthalic acid, 95-97 mol% ethylene glycol and 3-5 mol% polyethylene glycol (preferably PEG2000) as polymerization monomers, and the molar ratio of alcohol to acid is 1.2-1.5:1, and obtaining a hygroscopic modified copolyester through esterification and polycondensation reaction, with a moisture regain of 0.45-0.83%.

[0029] (4) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow nanomaterials, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips are vacuum dried, then evenly mixed in a mass ratio of 10-20:4-7:73-86 and added to a spinning machine for fiber forming. The spinning temperature is 275-285°C and the winding speed is 2500-3000m / min, and finally a polyester fiber with thermal insulation performance is obtained.

[0030] Example 1 A method for preparing a multi-stage thermal insulation and heat storage polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 500 nm and a porosity of 60%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0031] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: Ceramic powder with an average particle size of 400 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0032] (3) Preparation of hygroscopic modified polyester chips: 97 mol% terephthalic acid and 3 mol% isophthalic acid, 97 mol% ethylene glycol and 3 mol% polyethylene glycol (PEG2000) are used as polymerization monomers, and a hygroscopic modified copolyester is obtained by esterification and polycondensation reaction, the molar ratio of alcohol to acid is 1.2:1, and the moisture regain is 0.45-0.83%.

[0033] (4) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 15:5:80 and added to a spinning machine for fiber forming. The spinning temperature was 280°C and the winding speed was 2800 m / min, finally obtaining a polyester fiber with thermal insulation performance.

[0034] Example 2 A method for preparing a multi-stage thermal insulation and heat storage polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 500 nm and a porosity of 60%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:0.5:89.5, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0035] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: Ceramic powder with an average particle size of 400 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0036] (3) Preparation of hygroscopic modified polyester chips: 97 mol% terephthalic acid and 3 mol% isophthalic acid, 97 mol% ethylene glycol and 3 mol% polyethylene glycol (PEG2000) were used as polymerization monomers, and a hygroscopic modified copolyester was obtained by esterification and polycondensation reaction, wherein the molar ratio of alcohol to acid was 1.2:1.

[0037] (4) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 10:4:86 and added to a spinning machine for fiber forming. The spinning temperature was 285°C and the winding speed was 2600 m / min, finally obtaining a polyester fiber with thermal insulation performance.

[0038] Example 3 A method for preparing a multi-stage thermal insulation and heat storage polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow cerium dioxide with an average particle size of 500 nm and a porosity of 60%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow cerium dioxide.

[0039] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: ceramic powder with an average particle size of 400 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:0.5:69.5, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0040] (3) Preparation of hygroscopic modified polyester chips: 97 mol% terephthalic acid and 3 mol% isophthalic acid, 97 mol% ethylene glycol and 3 mol% polyethylene glycol (PEG2000) were used as polymerization monomers, and a hygroscopic modified copolyester was obtained by esterification and polycondensation reaction, and the molar ratio of alcohol to acid was 1.3:1.

[0041] (4) Preparation of multi-stage thermal insulation and heat storage fibers by co-spinning: The polyester masterbatch containing hollow cerium dioxide, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 20:7:73 and added to a spinning machine for fiber forming. The spinning temperature was 275°C and the winding speed was 2900 m / min, finally obtaining polyester fibers with thermal insulation properties.

[0042] Example 4 A method for preparing a multi-stage thermal insulation and heat storage polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow titanium dioxide with an average particle size of 500 nm and a porosity of 60%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:2:88, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow titanium dioxide.

[0043] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: Ceramic powder with an average particle size of 200 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0044] (3) Preparation of hygroscopic modified polyester chips: 95 mol% terephthalic acid and 5 mol% isophthalic acid, 95 mol% ethylene glycol and 5 mol% polyethylene glycol (PEG2000) were used as polymerization monomers, and a hygroscopic modified copolyester was obtained by esterification and polycondensation reaction, and the molar ratio of alcohol to acid was 1.2:1.

[0045] (4) Preparation of multi-stage thermal insulation and heat storage fibers by co-spinning: The polyester masterbatch containing hollow titanium dioxide, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 15:5:80 and added to a spinning machine for fiber forming. The spinning temperature was 280°C and the winding speed was 2800 m / min, finally obtaining polyester fibers with thermal insulation properties.

[0046] Example 5 A method for preparing a multi-stage thermal insulation and heat storage polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow cerium dioxide with an average particle size of 500 nm and a porosity of 40%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow cerium dioxide.

[0047] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: Tourmaline with an average particle size of 400 nm, dispersing aid zinc stearate and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:2:68, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0048] (3) Preparation of hygroscopic modified polyester chips: 98 mol% terephthalic acid and 2 mol% isophthalic acid, 97 mol% ethylene glycol and 3 mol% polyethylene glycol (PEG2000) were used as polymerization monomers, and a hygroscopic modified copolyester was obtained by esterification and polycondensation reaction, and the molar ratio of alcohol to acid was 1.4:1.

[0049] (4) Preparation of multi-stage thermal insulation and heat storage fibers by co-spinning: The polyester masterbatch containing hollow cerium dioxide, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 20:4:76 and added to a spinning machine for fiber forming. The spinning temperature was 282°C and the winding speed was 2700 m / min, finally obtaining polyester fibers with thermal insulation properties.

[0050] Example 6 A method for preparing a multi-stage thermal insulation and heat storage polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 600 nm and a porosity of 70%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0051] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: Medical stone with an average particle size of 300 nm, dispersing aid calcium stearate and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0052] (3) Preparation of hygroscopic modified polyester chips: 97 mol% terephthalic acid and 3 mol% isophthalic acid, 96 mol% ethylene glycol and 4 mol% polyethylene glycol (PEG2000) were used as polymerization monomers, and a hygroscopic modified copolyester was obtained by esterification and polycondensation reaction, and the molar ratio of alcohol to acid was 1.5:1.

[0053] (4) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 10:7:83 and added to a spinning machine for fiber forming. The spinning temperature was 279°C and the winding speed was 2700 m / min, finally obtaining a polyester fiber with thermal insulation performance.

[0054] Example 7 A method for preparing a multi-stage thermal insulation and heat storage polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 600 nm and a porosity of 50%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0055] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: zirconium carbide with an average particle size of 200 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0056] (3) Preparation of hygroscopic modified polyester chips: 98 mol% terephthalic acid and 2 mol% isophthalic acid, 5 mol% ethylene glycol and 5 mol% polyethylene glycol (PEG2000) were used as polymerization monomers, and a hygroscopic modified copolyester was obtained by esterification and polycondensation reaction, and the molar ratio of alcohol to acid was 1.2:1.

[0057] (4) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 10:7:83 and added to a spinning machine for fiber forming. The spinning temperature was 285°C and the winding speed was 2500 m / min, finally obtaining a polyester fiber with thermal insulation performance.

[0058] Example 8 A method for preparing a multi-stage thermal insulation and heat storage polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 600 nm and a porosity of 50%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0059] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: zirconium carbonate with an average particle size of 500 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0060] (3) Preparation of hygroscopic modified polyester chips: 98 mol% terephthalic acid and 2 mol% isophthalic acid, 95 mol% ethylene glycol and 5 mol% polyethylene glycol (PEG2000) were used as polymerization monomers, and a hygroscopic modified copolyester was obtained by esterification and polycondensation reaction, and the molar ratio of alcohol to acid was 1.5:1.

[0061] (4) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 10:7:83 and added to a spinning machine for fiber forming. The spinning temperature was 280°C and the winding speed was 2500 m / min, finally obtaining a polyester fiber with thermal insulation performance.

[0062] Comparative Example Comparative Example 1 The difference from Example 1 is that the raw materials do not contain polyester masterbatch with light-to-heat conversion function and hygroscopic modified polyester chips. A method for preparing a polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 500 nm and a porosity of 60%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0063] (2) Preparation of thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica and conventional PET polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 15:85 and added to a spinning machine for fiber forming. The spinning temperature was 288°C and the winding speed was 2800 m / min to finally obtain polyester fiber.

[0064] Comparative Example 2 The difference from Example 1 is that the raw materials do not contain polyester masterbatch containing hollow nano materials and hygroscopic modified polyester chips. A method for preparing a polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch with photothermal conversion function: Ceramic powder with an average particle size of 400 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0065] (2) Preparation of multi-stage thermal insulation and heat storage fibers by co-spinning: The polyester masterbatch with photothermal conversion function and conventional PET polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 5:95 and added to a spinning machine for fiber forming. The spinning temperature was 285°C and the winding speed was 2700 m / min to finally obtain polyester fibers.

[0066] Comparative Example 3 The difference from Example 1 is that the raw materials do not contain polyester masterbatch containing hollow nano materials and polyester masterbatch with light-heat conversion function. The details are as follows: A method for preparing a polyester fiber material, comprising the following steps: (1) Preparation of hygroscopic modified polyester chips: 97 mol% terephthalic acid and 3 mol% isophthalic acid, 97 mol% ethylene glycol and 3 mol% polyethylene glycol (PEG2000) were used as polymerization monomers, and a hygroscopic modified copolyester was obtained by esterification and polycondensation reaction, with the alcohol-acid molar ratio being 1.2:1.

[0067] (2) Preparation of multi-stage thermal insulation and heat storage fibers by co-spinning: The hygroscopic modified polyester chips and conventional PET polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 80:20 and added to a spinning machine for fiber forming. The spinning temperature was 275°C and the winding speed was 2700 m / min to finally obtain polyester fibers.

[0068] Comparative Example 4 The difference from Example 1 is that the raw materials do not contain polyester masterbatch containing hollow nano materials, polyester masterbatch with light-heat conversion function and hygroscopic modified polyester chips. A method for preparing a polyester fiber material comprises the following steps: vacuum drying conventional PET polyester chips at 120° C. for 24 hours, then adding the chips to a spinning machine for fiber forming, with a spinning temperature of 290° C. and a winding speed of 2800 m / min, to finally obtain polyester fibers.

[0069] Comparative Example 5 The difference from Example 1 is that there is no hygroscopic modified polyester chips in the raw materials. A method for preparing a polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 500 nm and a porosity of 60%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0070] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: Ceramic powder with an average particle size of 400 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0071] (3) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica, the polyester masterbatch with photothermal conversion function and the conventional PET polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 15:5:80 and added to a spinning machine for fiber forming. The spinning temperature was 280°C and the winding speed was 2800 m / min to finally obtain polyester fiber.

[0072] Comparative Example 6 The difference from Example 1 is that the raw materials do not contain polyester masterbatch with light-to-heat conversion function. A method for preparing a polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 500 nm and a porosity of 60%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0073] (2) Preparation of hygroscopic modified polyester chips: 97 mol% terephthalic acid and 3 mol% isophthalic acid, 97 mol% ethylene glycol and 3 mol% polyethylene glycol (PEG2000) are used as polymerization monomers, and a hygroscopic modified copolyester is obtained by esterification and polycondensation reaction, the molar ratio of alcohol to acid is 1.2:1, and the moisture regain is 0.45-0.83%.

[0074] (3) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 15:85 and added to a spinning machine for fiber forming. The spinning temperature was 280°C and the winding speed was 2800 m / min to finally obtain polyester fiber.

[0075] Comparative Example 7 The difference from Example 1 is that the raw material does not contain polyester masterbatch containing hollow nano materials. The details are as follows: A method for preparing a polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: ceramic powder with an average particle size of 400 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0076] (2) Preparation of hygroscopic modified polyester chips: 97 mol% terephthalic acid and 3 mol% isophthalic acid, 97 mol% ethylene glycol and 3 mol% polyethylene glycol (PEG2000) are used as polymerization monomers, and a hygroscopic modified copolyester is obtained by esterification and polycondensation reaction, the molar ratio of alcohol to acid is 1.2:1, and the moisture regain is 0.45-0.83%.

[0077] (3) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 5:95 and added to a spinning machine for fiber forming. The spinning temperature was 284°C and the winding speed was 2500 m / min to finally obtain polyester fiber.

[0078] Comparative Example 8 The difference from Example 1 is that the porosity of the hollow silica is 75%, which is beyond the preferred range.

[0079] Comparative Example 9 The difference from Example 1 is that the porosity of the hollow silica is 30%, which is lower than the preferred range.

[0080] Comparative Example 10 The difference from Example 1 is that the moisture regain of the hygroscopic modified polyester chips is too high. Specifically as follows: A method for preparing a polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 500 nm and a porosity of 60%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0081] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: Ceramic powder with an average particle size of 400 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0082] (3) Preparation of hygroscopic modified polyester chips: 90 mol% terephthalic acid and 10 mol% isophthalic acid, 92 mol% ethylene glycol and 8 mol% polyethylene glycol (PEG2000) were used as polymerization monomers, and a hygroscopic modified copolyester was obtained by esterification and polycondensation reaction, the molar ratio of alcohol to acid was 1.2:1, and the moisture regain was greater than 0.85%.

[0083] (4) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 15:5:80 and added to a spinning machine for fiber forming. The spinning temperature was 280°C and the winding speed was 2800 m / min to finally obtain polyester fiber.

[0084] Comparative Example 11 The difference from Example 1 is that the raw material contains excessive nano-silicon dioxide. The details are as follows: A method for preparing a polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 500 nm and a porosity of 60%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0085] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: Ceramic powder with an average particle size of 400 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0086] (3) Preparation of hygroscopic modified polyester chips: 97 mol% terephthalic acid and 3 mol% isophthalic acid, 97 mol% ethylene glycol and 3 mol% polyethylene glycol (PEG2000) are used as polymerization monomers, and a hygroscopic modified copolyester is obtained by esterification and polycondensation reaction, the molar ratio of alcohol to acid is 1.2:1, and the moisture regain is 0.45-0.83%.

[0087] (4) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 25:5:70 and added to a spinning machine for fiber forming. The spinning temperature was 280°C and the winding speed was 2800 m / min to finally obtain polyester fiber.

[0088] Comparative Example 12 The difference from Example 1 is that the raw material contains excessive ceramic powder. A method for preparing a polyester fiber material, comprising the following steps: (1) Preparation of polyester masterbatch containing hollow nanomaterials: Hollow silica with an average particle size of 500 nm and a porosity of 60%, coupling agent TCA-KTTS and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 10:1:89, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain polyester masterbatch containing hollow silica.

[0089] (2) Preparation of polyester masterbatch containing inorganic powder material with photothermal conversion function: Ceramic powder with an average particle size of 400 nm, dispersing aid polyethylene wax and PET polyester matrix powder are pre-blended in a high-speed mixer at a mass ratio of 30:1:69, and then melted, blended, extruded and granulated by a twin-screw extruder to obtain a polyester masterbatch with photothermal conversion function.

[0090] (3) Preparation of hygroscopic modified polyester chips: 97 mol% terephthalic acid and 3 mol% isophthalic acid, 97 mol% ethylene glycol and 3 mol% polyethylene glycol (PEG2000) are used as polymerization monomers, and a hygroscopic modified copolyester is obtained by esterification and polycondensation reaction, the molar ratio of alcohol to acid is 1.2:1, and the moisture regain is 0.45-0.83%.

[0091] (4) Preparation of multi-stage thermal insulation and heat storage fiber by co-spinning: The polyester masterbatch containing hollow silica, the polyester masterbatch with photothermal conversion function and the hygroscopic modified polyester chips were vacuum dried at 120°C for 24 h, then mixed evenly in a mass ratio of 15:10:70 and added to a spinning machine for fiber forming. The spinning temperature was 280°C and the winding speed was 2800 m / min to finally obtain polyester fiber.

[0092] Performance Testing The polyester fibers of the embodiments and comparative examples were tested for performance, and the results are shown in Table 1. The test method is: (1) After the polyester fiber is stretched and deformed, the tensile strength and elongation at break are evaluated according to the standard "GB / T 14344-2022 Test method for tensile properties of chemical fiber filaments"; the moisture regain is evaluated with reference to "GB / T 6503-2017 Test method for moisture regain of chemical fibers"; (2) After knitting, the thermal insulation and heat storage performance of polyester fiber was evaluated. The warmth retention rate was assessed with reference to "FZ / T 73022-2019 Knitted Thermal Underwear"; the far-infrared radiation temperature rise was assessed with reference to "GB / T 30127-2013 Testing and Evaluation of Far-Infrared Performance of Textiles".

[0093] Table 1. In Table 1, the four indicators related to the prepared thermal insulation and heat storage polyester fiber materials and their applications are mainly focused on. The mechanical properties mainly examine the application of the fiber materials in subsequent weaving processing, the moisture regain mainly examines the improvement of the hydrophilic properties of the hygroscopic modified polyester matrix, the Cros value mainly examines the thermal insulation performance of the fabric, and the far-infrared radiation temperature rise value examines the light-heat conversion ability of the fabric.

[0094] As can be seen from the above table, the present invention reduces its own heat conduction while increasing additional heat sources by introducing hollow nano-microspheres with larger porosity, inorganic nano-materials with photothermal conversion function and hygroscopic modified polyester matrix, thereby achieving the synergistic effect of the three thermal insulation and heat storage means and greatly improving the thermal insulation performance of polyester fiber materials and fabrics.

[0095] First, through the performance test of comparative example 4, that is, conventional polyester materials, it can be found that its mechanical properties are excellent, but its hygroscopicity, thermal insulation and heat storage capacity are poor. Then, through the test results of comparative examples 1-3, it is found that the introduction of different modification methods has different focuses on improving the thermal insulation performance of the material. Comparative example 1 only introduces hollow silica masterbatch, which increases the air content of the material, so its thermal insulation performance (Crow value) is significantly improved. Comparative example 2 only introduces photothermal conversion functional masterbatch, so its light absorption and heating performance (far-infrared radiation temperature rise) is significantly improved. Comparative example 3 only introduces hygroscopic modified polyester, so its moisture regain is significantly improved. When all three modification methods are introduced, the corresponding three indicators related to thermal insulation performance are improved. As shown in the test results of Examples 1-7, the material not only reduces its own heat loss, but also converts external energy into additional heat, thereby improving the thermal insulation performance in all aspects. It is not difficult to find that by changing the preparation process and mixing ratio before spinning of hollow silica masterbatch, photothermal conversion functional masterbatch and hygroscopic modified polyester, different indicators of the thermal insulation performance of the material can be adjusted.

[0096] Compared with Example 1: (1) Comparative Example 5 only has hollow nanomaterials and photothermal conversion materials, and lacks a hygroscopic modified polyester matrix. Because hygroscopic modified polyester increases the moisture content of the fiber, after the far infrared rays are absorbed, the water molecules can be resonantly activated to increase thermal energy. Therefore, without the cooperation of the hygroscopic modified polyester matrix, the warming effect will also decrease. (2) Comparative Example 6 only has hollow nanomaterials and hygroscopic modified polyester, and lacks photothermal conversion materials. The warming effect is significantly reduced. (3) Comparative Example 7 only has photothermal conversion materials and hygroscopic modified polyester, and lacks hollow nanomaterials. The infrared rays are not refracted multiple times in the pores of the hollow nanomaterials to increase the conversion of thermal energy, and the warming effect is also reduced. It proves that the hollow nanomaterial has a gain on the warming effect. The porosity of Comparative Example 8 is low, so the gain effect is reduced. The porosity of silica in Comparative Example 9 is high, which is not good for mechanical properties.

[0097] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent embodiments of equivalent changes using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A heat-insulating and heat-storing polyester fiber, characterized in that: The raw materials include hollow nanomaterial A with a porosity of 40-70%, inorganic powder material B with light-heat conversion function and hygroscopic modified polyester C with a regain of 0.45-0.83%, the mass of A is 0.1-3.5% of the mass of C, and the mass of B is 0.1-4% of the mass of C.

2. The heat-insulating and heat-storing polyester fiber according to claim 1, characterized in that: The hollow nanomaterial is selected from one or more of hollow silica, hollow titania, and hollow cerium dioxide, and has a particle size of 300-800 nm.

3. The heat-insulating and heat-storing polyester fiber according to claim 1 or 2, characterized in that: The inorganic powder material with light-heat conversion function is selected from one or more of far-infrared ceramics, medical stone, zirconium carbide, and tourmaline, and has a particle size of 200-500nm.

4. The method for preparing a heat-insulating and heat-storing polyester fiber according to any one of claims 1 to 3, characterized in that: The following steps are involved: The polyester masterbatch containing hollow nano materials, the polyester masterbatch containing inorganic powder materials with light-heat conversion function and the hygroscopic modified polyester chips are mixed evenly and added into a spinning machine for fiber forming to obtain heat-insulating heat-storing polyester fibers.

5. The method for preparing a heat-insulating and heat-storing polyester fiber according to claim 4, characterized in that: With hollow nanomaterials, coupling agent and PET polyester matrix as raw materials, polyester masterbatch containing hollow nanomaterials is prepared through extrusion granulation process.

6. The method for preparing a heat-insulating and heat-storing polyester fiber according to claim 5, characterized in that: The mass ratio of the hollow nano material, the coupling agent and the PET polyester matrix is ​​10:0.5-2:88-89.

5.

7. The method for preparing a heat-insulating and heat-storing polyester fiber according to claim 4, characterized in that: With inorganic powder material with photothermal conversion function, dispersant and PET polyester matrix as raw materials, polyester masterbatch containing inorganic powder material with photothermal conversion function is prepared through extrusion granulation process.

8. The method for preparing a heat-insulating and heat-storing polyester fiber according to claim 7, characterized in that: The mass ratio of the inorganic powder material with light-to-heat conversion function, the dispersant and the PET polyester matrix is ​​30:0.5-2:68-69.

5.

9. The method for preparing a heat-insulating and heat-storing polyester fiber according to claim 4, characterized in that: The hygroscopic modified copolyester is obtained by taking 95-98 mol% of terephthalic acid and 2-5 mol% of isophthalic acid, 95-97 mol% of ethylene glycol and 3-5 mol% of polyethylene glycol as polymerization monomers through esterification and polycondensation reaction, and the molar ratio of alcohol to acid is 1.2-1.5:

1.

10. The method for preparing a heat-insulating and heat-storing polyester fiber according to claim 4 or 9, characterized in that: During the fiber forming process, the spinning temperature is 275-285 ºC and the winding speed is 2500-3000 m / min.

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