WO2022148401A1 - 一种湿法纺丝辐射制冷纤维、制备方法及其应用 - Google Patents

一种湿法纺丝辐射制冷纤维、制备方法及其应用 Download PDF

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WO2022148401A1
WO2022148401A1 PCT/CN2022/070532 CN2022070532W WO2022148401A1 WO 2022148401 A1 WO2022148401 A1 WO 2022148401A1 CN 2022070532 W CN2022070532 W CN 2022070532W WO 2022148401 A1 WO2022148401 A1 WO 2022148401A1
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nano particles
base material
spinning
micro
preparation
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French (fr)
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陶光明
曾少宁
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华中科技大学
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments

Definitions

  • the invention relates to the technical field of radiation refrigeration, in particular to a radiation refrigeration fiber, a preparation method and an application thereof.
  • the traditional space thermal control system achieves the purpose of temperature control by heating and cooling the entire space. This process is often accompanied by a large amount of energy consumption. The resulting energy waste and environmental pollution problems have extremely adverse effects on human production and life. . Refrigeration occupies a major part of the global power consumption, and such a large cooling energy consumption will pose a serious threat to the human production economy. Therefore, by reducing the space cooling demand, not only can efficient and economical personal comfort be achieved, but also has positive significance for the sustainable development of human beings.
  • Radiation cooling technology can achieve high emissivity at 8-13 ⁇ m and high reflectivity in the solar radiation band of 0.3-2.5 ⁇ m through material selection and structural control. This method of spectral selective control can effectively radiate heat. And block the energy input, thereby achieving the purpose of refrigeration. Unlike most current cooling methods that require energy to take away heat, radiant cooling does not require any power input, which has a positive effect on reducing global energy consumption and environmental protection.
  • the Stanford University team theoretically designed a metal-dielectric photonic structure that can achieve radiation cooling.
  • the micro-nano structure of this periodic hole can theoretically achieve passive cooling at a temperature of 40-60 °C lower than the ambient temperature. Over 100W/ m2 net cooling power.
  • the team fabricated a photon radiation cooler integrating a solar reflector and a thermal emitter by means of micro-nano fabrication, realizing daytime radiation cooling for the first time.
  • the photon radiation cooler is a multi-layer film structure with a silver film as a substrate, which realizes strong selective emission of the atmospheric transparent window while reflecting 97% of the solar radiation.
  • Chinese patent application CN110042564A proposes a radiation refrigeration fiber membrane and its preparation method and application.
  • the radiation particles with good monodispersity are randomly dispersed among the polymer fibers by electrospinning to prepare a fiber membrane with a simple structure that can be used for heat dissipation and cooling of the human body.
  • the fiber film can make the surface temperature of the object lower than the ambient temperature by 1.6°C-2.7°C, but this method has low production efficiency, complicated process, high equipment cost, and no weaving, and the application scene is limited. Textiles for radiative cooling of the human body cannot be prepared.
  • Chinese patent application CN202010261971.7 proposes a design method of radiative cooling fiber and the radiative cooling fiber, using FDTD Soultions based on finite difference time domain method to build a simulation model of doped medium micro-nano particles in the base material, by accurately controlling the scattering
  • the concentration and size of the medium achieve the highest solar spectral reflection efficiency under the same volume percentage, which provides a complete design method for radiative cooling fibers and achieves good compatibility with existing industrial technologies.
  • Chinese patent application CN202010261972.1 proposes a preparation method of a highly doped radiation refrigeration composite fiber and its fabric.
  • the thermal drawing method is used to introduce micro-nano particles into the fiber to prepare the fiber, and woven into a fabric suitable for cooling the human body, so as to realize solar High reflectivity of radiation and high emissivity of the atmospheric window, with excellent radiative cooling effect.
  • Chinese patent application CN202010261960.9 proposes a preparation method of radiation refrigeration fiber and its fabric.
  • Inorganic micro-nano particles are introduced into polymer fibers by melt-composite spinning method.
  • the fibers thus prepared have excellent radiation refrigeration performance.
  • With good mechanical properties, elastic stability and high comfort, a radiation cooling fabric suitable for cooling the surface of human skin is obtained.
  • Chinese patent application CN202010261965.1 proposes a composite yarn with radiation cooling function and a preparation method for its fabric.
  • the padding method and the wrapping method are used to introduce high-concentration inorganic micro-nano particles into the outside and inside of the yarn, and the preparation is suitable for human skin cooling.
  • the composite yarn of radiation refrigeration is obtained, and textiles with excellent radiation refrigeration performance and high comfort are obtained by weaving technology, which provides an effective method for preparing clothing fabrics with excellent radiation refrigeration performance. Therefore, based on the selection of substrate materials and the control of particle size concentration of micro-nano particles, it can effectively block solar radiation energy input and maximize infrared radiation heat output, with excellent radiative cooling performance and good compatibility with existing industrial technologies. .
  • dry and wet spinning prepares fibers by dissolving the polymer in a solvent to prepare a spinning solution with a suitable concentration.
  • Post-processing processes such as stretching, shaping, washing, and drying.
  • the advantage of this process is that high-viscosity spinning dope can be spun, thereby reducing solvent recovery and consumption, high forming speed, uniform fiber structure, approximately circular cross-section, and improved strength and elasticity. Dyeability and color are good.
  • the physical changes that occur through the air layer are beneficial to the formation of fine-specified, densified and homogenized strands, and can effectively adjust the structure-forming process of the fibers.
  • the spun fibers have high density, smooth surface without grooves, and can achieve high-speed spinning. They can be used to produce high-performance, high-quality fiber precursors.
  • the prepared fibers have high flexibility and greatly enhance human comfort. Ideal fiber for thermal management of the human body.
  • the Chinese patent of CN101805934B discloses an ice-cool viscose fiber, which is prepared by adding 3-20wt% mica powder based on the dry weight of the fiber to the viscose fiber using bamboo pulp as a raw material, and using dry and wet spinning as a process.
  • the fiber has anti-ultraviolet, moisture-wicking, far-infrared health care effects, especially suitable for the production of summer clothing and apparel products.
  • the functions of fibers prepared by dry and wet spinning in this method are limited to anti-ultraviolet, and cannot control solar radiation and human thermal radiation, and cannot be used for personal thermal management.
  • the Chinese patent application of CN107955984A discloses a graphene-grafted polysaccharide Lyocell fiber and a preparation method thereof.
  • the cellulose, the graphene of the grafted polysaccharide and the N-methylmorpholine-N-oxide (NMMO) aqueous solution are mixed A spinning dope containing graphene is obtained, and the Lyocell fiber prepared by dry and wet spinning has the advantages of excellent electrical and thermal conductivity, far-infrared and ultraviolet protection functions, and good mechanical properties.
  • the grafting steps involved in this method are relatively complicated, and human radiation cannot be controlled.
  • the Chinese patent of CN106498538B discloses a method for preparing high thermal conductivity aromatic polyamide fiber and its application.
  • Graphene oxide is dispersed in an organic solvent to prepare a dispersion; under the protection of inert gas, m-phenylenediamine
  • the body is added into the aforementioned dispersion liquid for dissolution to obtain a meta-aromatic polyamide resin solution; the dry and wet spinning process is used for spinning, and finally the high thermal conductivity aromatic polyamide fiber is obtained.
  • this method has low production efficiency, complicated process, high equipment cost, and cannot control human radiation.
  • the present invention provides a batch preparation method of dry-wet spinning radiation refrigeration fibers and fabrics thereof, which can introduce inorganic micro-nano particles by dry-wet spinning process, and can precisely control the size of the micro-nano particles and fiber structure.
  • the invention utilizes dry and wet spinning, and uses common polymer materials such as cellulose as a base to prepare radiation refrigeration fibers doped with inorganic micro-nano particles, and achieves excellent mechanical properties by regulating the size, concentration and fiber structure of the micro-nano particles. And radiation cooling effect, and woven into a flexible fabric suitable for cooling the surface of human skin.
  • a preparation method of radiation refrigeration fiber it comprises the steps:
  • Dry-wet spinning is performed on the micro-nano particles and the base material spinning dope to obtain radiation refrigeration fibers.
  • the base material is 1-999 parts by weight, preferably 1.5-4 parts by weight, more preferably 2.33-4 parts by weight 3 parts by weight.
  • the inorganic micro-nano particles are selected from titanium dioxide, silicon dioxide, zinc oxide, silicon carbide, silicon nitride, zinc sulfide, aluminum oxide, iron oxide, nitride
  • the inorganic micro-nano particles are selected from titanium dioxide, silicon dioxide, zinc oxide, silicon carbide, silicon nitride, zinc sulfide, aluminum oxide, iron oxide, nitride
  • boron, magnesium oxide, barium sulfate, barium carbonate and aluminum silicate preferably titanium dioxide, zinc oxide or silicon nitride.
  • the base material is selected from cellulose, polylactic acid, polyethylene, polypropylene, polyamide, polyvinyl chloride, polystyrene, polyacetic acid Vinyl ester, polyvinyl alcohol, polyacrylonitrile, polyparabenzamide, polyethylene terephthalate, chitosan, polyparaphenylene terephthalamide, meta-aromatic polyamide, poly One or more of vinylidene fluoride, chitin dibutyryl, polybenzimidazole and polybenzobisbisoxazole, preferably cellulose, polyacrylonitrile, polyvinyl alcohol or chitosan.
  • mixing the inorganic micro-nano particles and the base material to obtain the micro-nano particles and the base material spinning stock solution comprises adding the inorganic micro-nano particles and the base material to a solvent.
  • the micro-nano particles and the base material spinning dope are obtained.
  • the inorganic micro-nano particles comprise first inorganic micro-nano particles and second inorganic micro-nano particles; preferably, the first inorganic micro-nano particles
  • the particles and the second inorganic micro-nano particles are the same inorganic micro-nano particles or different inorganic micro-nano particles.
  • the base material comprises a base material 1 and a base material 2, preferably, the base material 1 and the base material 2 are the same base material or different base materials .
  • the second inorganic micro-nano particles and the base material 2 are mixed to form a spinning dope of the second micro-nano particles and the base material.
  • the second inorganic micro-nano particles is 0 or the second
  • the amount of the inorganic micro-nano particles is 1 part by weight, and the amount of the base material 2 is 4-49 parts by weight, preferably 9-19 parts by weight, more preferably 10-12.5 parts by weight.
  • the second inorganic micro-nano particles and the base material 2 are 1-70%, preferably 20-40%.
  • micro-nano particles and the base material spinning dope are sent to the spinning device, and then ejected from the spinneret holes of the spinneret in the spinning device to obtain the ejected liquid;
  • the ejected liquid enters the coagulation bath through the air layer to form primary fibers
  • the nascent fibers are washed and stretched to form radiation refrigeration fibers.
  • a radiation refrigeration fiber prepared by the preparation method of any one of items 1-14.
  • the structure of the radiation refrigeration fiber is a circular structure, a skin-core structure, a hollow structure, a herringbone structure, a cross-shaped structure, a side-by-side structure, a radial structure, and an island-in-the-sea structure. at least one of the structures.
  • a radiation refrigeration fabric obtained by weaving the radiation refrigeration fiber prepared by the preparation method of any one of items 1-14 or the radiation refrigeration fiber of any one of items 15-16.
  • the invention can use the dry and wet spinning process to prepare the radiation refrigeration fiber doped with inorganic micro-nano particles, achieve excellent radiation refrigeration effect by regulating the size and concentration of the micro-nano particles, and weave into a flexible fabric suitable for cooling the surface of human skin .
  • the radiation refrigeration fabric prepared by the invention has an average emissivity of ⁇ 0.9 in the 8-13 ⁇ m waveband, and an average reflectance of ⁇ 0.9 in the solar light waveband.
  • the preparation method of the invention can design the internal composite structure of the fiber, so that the fiber has both good mechanical properties and high comfort while having excellent radiation cooling performance.
  • the invention adopts dry and wet spinning as the spinning process, which can effectively reduce the degradation amount of the polymer in the spinning process and improve the comprehensive performance of the fiber.
  • the prepared radiation refrigeration fibers and fabrics have high flexibility and greatly enhance human comfort.
  • the dry and wet spinning process can utilize natural materials such as cellulose and chitosan as fiber base materials, so that the prepared cellulose fibers and fabrics have good degradability, recyclability and green regeneration.
  • Fig. 1 is the model schematic diagram of the present invention based on Monte Carlo multilayer medium simulation model statistics
  • Fig. 2 is the basic flow chart of the present invention based on Monte Carlo multilayer medium simulation
  • Fig. 3 is the simulation schematic diagram that the solar spectrum weighted reflectance obtained by the present invention changes with particle size and thickness;
  • FIG. 4 is a schematic cross-sectional view of the radiation refrigeration fibers prepared in Examples 1, 2, 3, and 4 of the present invention.
  • Example 5 is a schematic cross-sectional view of the radiation refrigeration fiber prepared in Example 5 of the present invention.
  • Example 6 is a schematic cross-sectional view of the radiation refrigeration fiber prepared in Example 6 of the present invention.
  • Example 7 is a schematic cross-sectional view of the radiation refrigeration fiber prepared in Example 7 of the present invention.
  • FIG. 8 is a schematic diagram of a device used for dry and wet spinning according to an embodiment of the present invention.
  • FIG. 9 is a schematic diagram of the prepared radiant refrigeration fiber according to the embodiment of the present invention after being woven into a fabric.
  • 1- spinning medicine tank 2- air layer; 3- coagulation bath; 4- heating roller; 5- spinning roller.
  • the invention provides a preparation method of radiation refrigeration fiber, which comprises the following steps:
  • Dry-wet spinning is performed on the micro-nano particles and the base material spinning dope to obtain radiation refrigeration fibers.
  • the radiation cooling fiber refers to the fiber with radiation cooling function, which can discharge its own heat in the form of 8-13 ⁇ m electromagnetic waves through the "atmospheric window" to the outer space where the temperature is close to absolute zero, so as to achieve the purpose of self-cooling.
  • the inorganic micro-nano particles have the characteristics of high refractive index, can produce high scattering efficiency in the base material, and can make the radiation refrigeration fiber have high solar radiation reflectivity, which is selected from titanium dioxide, silicon dioxide, zinc oxide, carbonized One or more of silicon, silicon nitride, zinc sulfide, aluminum oxide, iron oxide, boron nitride, magnesium oxide, barium sulfate, barium carbonate and aluminum silicate, preferably titanium dioxide, silicon dioxide, aluminum oxide ,Barium sulfate.
  • the base material has the characteristics of high infrared emissivity, and the base material is selected from the group consisting of cellulose, polylactic acid, polyethylene, polypropylene, polyamide, polyvinyl chloride, polystyrene, polyvinyl acetate, polyvinyl Vinyl alcohol, polyacrylonitrile, polyparabenzamide, polyethylene terephthalate, chitosan, polyparaphenylene terephthalamide, meta-aramid, polyvinylidene fluoride, di- One or more of butyryl chitin, polybenzimidazole and polybenzobisbisoxazole, preferably cellulose, polyacrylonitrile or chitosan.
  • the base material is 1-49 parts by weight, preferably 1.5-4 parts by weight, more preferably 2.33 parts by weight -3 parts by weight.
  • the base material may be 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.33 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight parts by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 49 parts by weight, etc.
  • the inorganic micro-nano particles are selected from titanium dioxide (TiO 2 ), silicon dioxide (SiO 2 ), zinc oxide (ZnO), silicon carbide (SiC), nitride Silicon (Si 3 N 4 ), Zinc Sulfide (ZnS), Aluminum Oxide (Al 2 O 3 ), Iron Oxide (Fe 2 O 3 ), Boron Nitride (BN), Magnesium Oxide (MgO), Barium Sulfate (BaSO 4 ) ), barium carbonate (BaCO 3 ) and aluminum silicate (Al 2 SiO 5 ), one or a mixture of two or more, preferably titanium dioxide, zinc oxide or silicon nitride.
  • the particle size of the inorganic micro-nano particles is 0.03-25 ⁇ m, preferably 0.1-10 ⁇ m, more preferably 0.4 ⁇ m, for example, the particle size of the inorganic micro-nano particles is 0.03 ⁇ m, 0.05 ⁇ m, 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1 ⁇ m, 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, or any range in between.
  • the base material is selected from cellulose, polylactic acid, polyethylene, polyimide, polypropylene, polyamide, polyvinyl chloride, polystyrene, polyacetic acid Vinyl ester, polyvinyl alcohol, polyacrylonitrile, polyparabenzamide, polyethylene terephthalate, chitosan, polyparaphenylene terephthalamide, meta-aromatic polyamide, poly One or more mixtures of vinylidene fluoride, chitin dibutyryl, polybenzimidazole and polybenzobisbisoxazole, preferably cellulose, polyacrylonitrile, polyvinyl alcohol or chitosan.
  • Polylactic acid is a polymer obtained by polymerizing lactic acid as the main raw material. It is a new type of biodegradable material with good mechanical and physical properties, as well as good tensile strength and ductility.
  • PE Polyethylene
  • PE is a thermoplastic resin obtained by polymerization of ethylene. It has excellent low temperature resistance, good chemical stability, and is resistant to the erosion of most acids and alkalis (not resistant to acids with oxidative properties).
  • Polypropylene is a polymer obtained by addition polymerization of propylene. It is resistant to corrosion by acid, alkali, salt solution and various organic solvents below 80 °C, and can be decomposed under high temperature and oxidation. Polypropylene is widely used in clothing. , blankets and other fiber products, medical equipment, automobiles, bicycles, parts, transportation pipelines, chemical containers, etc., and also used for food and drug packaging.
  • Polyamide commonly known as nylon (Nylon)
  • nylon is a general term for thermoplastic resins containing repeating amide groups - [NHCO] - on the main chain of the molecule. It has good comprehensive properties, including mechanical properties, heat resistance, wear resistance, Chemical resistance and self-lubrication, low friction coefficient, certain flame retardancy, easy to process, suitable for filling with glass fiber and other fillers for reinforcement and modification, to improve performance and expand the scope of application.
  • Polyvinyl chloride is vinyl chloride monomer (vinyl chloride monomer, referred to as VCM) in peroxides, azo compounds and other initiators; or under the action of light and heat according to the free radical polymerization mechanism. , used to be the world's largest general-purpose plastic, with a wide range of applications. It is widely used in building materials, industrial products, daily necessities, floor leather, floor tiles, artificial leather, pipes, wires and cables, packaging films, bottles, foam materials, sealing materials, fibers, etc.
  • Polystyrene refers to a polymer synthesized by free radical addition polymerization of styrene monomer. It has good heat insulation and excellent optical properties. It is an excellent electrical insulating material and has good corrosion resistance.
  • Polyvinyl acetate also known as polyvinyl acetate, is a polymer of vinyl acetate (vinyl acetate).
  • Polyvinyl alcohol is an important chemical raw material used in the manufacture of polyvinyl acetal, gasoline-resistant pipes and vinylon synthetic fibers, fabric treatments, emulsifiers, paper coatings, adhesives, glues, etc.
  • Polyacrylonitrile is obtained by radical polymerization of monomer acrylonitrile.
  • the advantages of polyacrylonitrile fiber are good weather resistance and sunlight resistance, and it can maintain 77% of its original strength after being placed outdoors for 18 months. %, it is also resistant to chemical reagents, especially inorganic acids, bleaching powder, hydrogen peroxide and general organic reagents.
  • the polyparabenzamide (PBA) takes p-aminobenzoic acid as a unit, N-methylpyrrolidone as a solvent, and reacts for 3 hours in the presence of a catalyst and a co-catalyst at 80-90°C. Then, the material is precipitated into alcohol, the resin is washed with water, and dried to obtain a resin for spinning.
  • Polyparabenzamide fiber is an aramid fiber with high strength, high modulus and low density.
  • PET Polyethylene terephthalate
  • Chitosan is the product of natural polysaccharide chitin removing part of the acetyl group. It has various physiological functions such as biodegradability, biocompatibility, non-toxicity, antibacterial, anti-cancer, lipid-lowering, and immunity enhancement. It is widely used in food. Additives, textiles, agriculture, environmental protection, beauty care, cosmetics, antibacterial agents, medical fibers, medical dressings, artificial tissue materials, drug sustained-release materials, gene transduction carriers, biomedical fields, medical absorbable materials, tissue engineering carrier materials, Medical and pharmaceutical development and many other fields and other daily chemical industries.
  • Poly(p-phenylene terephthalamide) is an all-para polyaramide obtained by the condensation polymerization of p-phenylenediamine and terephthaloyl chloride. It has high heat resistance, high tensile strength and initial elasticity. Modulus, thermal shrinkage and creep properties are stable, in addition to high insulation and chemical resistance.
  • Polymetaphenylene isophthalamide also known as meta-aramid fiber, is a linear macromolecular structure composed of amide groups interconnected with meta-phenyl groups.
  • PMIA has a high content of benzene ring groups. It is easy to form a trapezoidal structure, so the obtained fibers not only have excellent mechanical properties, but also have good high temperature resistance, so they have been widely used in many fields such as thermal protective clothing, filter materials, and flame retardant decorative cloth.
  • PVDF Polyvinylidene fluoride
  • Polyvinylidene fluoride mainly refers to vinylidene fluoride homopolymer or copolymer of vinylidene fluoride and other small amount of fluorine-containing vinyl monomers.
  • high temperature resistance, oxidation resistance, weather resistance, and radiation resistance it also has special properties such as piezoelectricity, dielectricity, and pyroelectricity.
  • Polyimide polymers refer to a class of polymers containing an imide ring (-CO-NH-CO-) on the main chain, among which polymers containing a phthalimide structure are the most important.
  • polyimide has been widely used in aviation, aerospace, microelectronics, nano, liquid crystal, separation membrane, laser and other fields.
  • the modulus of elasticity is second only to carbon fiber, which is used as a filter material for high temperature media and radioactive substances, as well as bulletproof and fireproof fabrics.
  • Dibutyryl chitin is a butyrylated chitin product obtained by reacting under heterogeneous conditions with perchloric acid as a catalyst. It is easily soluble in common solvents such as acetone, DMF and ethanol.
  • Polybenzimidazole is a benzofive-membered heterocyclic rigid chain polymer containing two nitrogen atoms, which is generally formed by polycondensation and cyclization of aromatic tetraamine and diphenyl phthalate. Excellent solvent and chemical resistance. It can be used as a high temperature resistant adhesive and to make high-performance composite materials. It is widely used in aerospace, chemical machinery, oil exploration, automobiles and other fields. Fiber fabrics are used as protective clothing against fire and atomic radiation.
  • Polybenzobisbisoxazole is a lyotropic liquid crystal heterocyclic polymer.
  • the macromolecular chain has a high degree of aromaticity, which makes it have excellent characteristics such as high strength, high modulus, high temperature resistance and corrosion resistance.
  • mixing the inorganic micro-nano particles and the base material to obtain the micro-nano particles and the base material spinning dope comprises adding the inorganic micro-nano particles and the base material into a solvent to obtain the micro-nano particles and base material spinning dope.
  • the solvent described in the present invention is not limited, such as water, DMF, DMAc, nitric acid, acetic acid, toluene, cyclohexane, tetrahydrofuran-dioxane blend solution, benzene, carbon tetrachloride, amyl acetate, Acetone, 4-Methylmorpholine-N-oxide, N-ethylpyridine chloride, 1-butyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 1- Allyl 3-methylimidazole fluoride, 1-butyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole phosphoric acid Diethyl ester, NaOH/urea/water, NaOH/thiourea/water, NaOH/thiourea/urea/water, NaOH/polyethylene glycol/water
  • the solvent of NaOH/urea/water is a solvent formed by NaOH, urea and water, and the three can be in any mass ratio. is 8%, urea is 10%, and the balance is water;
  • NaOH/thiourea/water it is a solvent formed by NaOH, thiourea and water, and the three can be in any mass ratio, for example, in the mass percentage of NaOH/thiourea/water solvent , NaOH can be 8%, thiourea can be 6.5%, and the balance is water;
  • NaOH/thiourea/urea/water it is a solvent formed by NaOH, thiourea, urea and water, and the four can be in any mass ratio, for example, NaOH/thiourea/urea/water solvent accounts for In terms of mass percentage, NaOH can be 8%, thiourea can be 6.5%, urea can be 8%, and the balance can be water;
  • urea/caprolactam/sodium hydroxide/water it is a solvent formed by urea, caprolactam, sodium hydroxide and water, and the four can be in any mass ratio, such as in urea/caprolactam/sodium hydroxide/ In terms of the mass percentage of the water solvent, urea can be 10%, caprolactam can be 4%, sodium hydroxide can be 8%, and the balance can be water;
  • the solvent of NaOH/ZnO/water is a solvent formed by NaOH, ZnO and water, and the three can be in any mass ratio. 8%, ZnO can be 10%, and the balance is water;
  • the solvent of NaOH/ethanol/water is a solvent formed by NaOH, ethanol and water, and the three can be in any mass ratio.
  • NaOH can be 8%
  • ethanol can be 10%
  • the balance is water.
  • the present invention does not limit the volume ratio of tetrahydrofuran and dioxane, for example, the volume ratio can be 1:1.
  • the particle size of the inorganic micro-nano particles is 0.03-25 ⁇ m, preferably 0.1-10 ⁇ m, and more preferably 0.4 ⁇ m.
  • the particle size of the inorganic micro-nano particles may be 0.03 ⁇ m, 0.05 ⁇ m, 0.1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m , 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25 ⁇ m, etc.
  • the particle size refers to the average diameter of the inorganic micro-nano particles.
  • the particle size is determined by the rice scattering theory combined with the Monte Carlo multilayer medium simulation model, and the specific operation method is as follows.
  • the inorganic micro-nano particles and the base material are 1-70%, preferably 20% -40%.
  • the inorganic micro-nano particles and the base material can be 1%, 5%, 10%, 15%, 20%, 25% in terms of the weight percentage of the micro-nano particles and the base material spinning dope. , 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or any range in between.
  • the inorganic micro-nano particles include first inorganic micro-nano particles and second inorganic micro-nano particles; preferably, the first inorganic micro-nano particles and the second inorganic micro-nano particles
  • the two inorganic micro-nano particles are the same inorganic micro-nano particles or different inorganic micro-nano particles;
  • the base material includes a base material 1 and a base material 2.
  • the base material 1 and the base material 2 may be the same base material or different base materials.
  • the different base materials require the use of the same coagulation bath, that is, a coagulation bath capable of coagulating both the cladding layer described below and the core layer described below.
  • the first inorganic micro-nano particles and the base material 1 are mixed to form the first micro-nano particles and the base material spinning dope, and the first micro-nano particles and the base material spinning dope finally form the core layer of the radiation refrigeration fiber.
  • the base material 1 is 1-49 parts by weight, preferably 1.5-4 parts by weight, more preferably 2.33-3 parts by weight;
  • the second inorganic micro-nano particles and the base material 2 are mixed to form the second micro-nano particles and the base material spinning dope, and the second micro-nano particles and the base material spinning dope finally form the radiation cooling fiber wrapping.
  • the second inorganic micro-nano particle is 0 or based on the second inorganic micro-nano particle being 1 weight part, the base material 2 is 4-49 weight parts, preferably 9-19 weight parts, more preferably 10 weight parts -12.5 parts by weight.
  • the base material 1 may be 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.33 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight parts, 4 parts by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 49 parts by weight, etc.
  • the base material 2 can be 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight parts, 49 parts by weight, etc.
  • the mass percentage of the second inorganic micro-nano particles in the cladding layer in the cladding layer is less than or equal to the mass percentage of the first inorganic micro-nano particles in the core layer in the core layer.
  • the first inorganic micro-nano particles and the base material 1 are 1-70 %, preferably 20-40%;
  • the second inorganic micro-nano particles and the base material 2 are 1-70%, preferably 20-40%, in terms of the mass percentage of the second micro-nano particles and the base material spinning dope.
  • the first inorganic micro-nano particles and the base material 1 can be 1%, 5%, 10%, 15%, 20% in terms of the mass percentage of the first micro-nano particles and the base material spinning solution. , 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, or any range therebetween;
  • the second inorganic micro-nano particles and the base material 2 may be 1%, 2%, 3%, 4%, 5%, 6 %, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or any range in between;
  • the dry and wet spinning comprises the following steps:
  • micro-nano particles and the base material spinning dope are sent to the spinning device, and then ejected from the spinneret holes of the spinneret in the spinning device to obtain the ejected liquid;
  • the ejected liquid enters the coagulation bath through the air layer to form primary fibers
  • the nascent fibers are washed and stretched to form radiation refrigeration fibers.
  • the diameter of the spinneret hole is 0.01-0.8 mm, and the diameter of the fiber is 0.005-0.5 mm.
  • the diameter of the spinneret holes is 0.01mm, 0.02mm, 0.03mm, 0.04mm, 0.05mm, 0.06mm, 0.07mm, 0.08mm, 0.09mm, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, etc.
  • the present invention does not limit the spinning device as long as it can perform spinning.
  • the spinning device can be a spinning pot or a spinning box.
  • the spinning temperature is not limited in the present invention, for example, the spinning temperature can be 10-150°C, such as 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C , 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, etc.
  • the spinning speed is not limited in the present invention, for example, the spinning speed can be 0.6-3000m/min, such as 0.6m/min, 1m/min, 10m/min, 50m/min, 100m/min, 500m/min , 1000m/min, 1500m/min, 2000m/min, 2500m/min, 3000m/min, etc.
  • the viscosity of the spinning dope of the micro-nano particles and the base material is 50-400 Pa s, preferably 300 Pa s, for example, the viscosity of the spinning dope of the micro-nano particles and the base material may be 50 Pa s, 100Pa ⁇ s, 150Pa ⁇ s, 200Pa ⁇ s, 250Pa ⁇ s, 300Pa ⁇ s, 350Pa ⁇ s, 400Pa ⁇ s, etc.
  • the viscosity is measured by a viscometer known in the art, such as NDJ-5S viscometer, NDJ-8S viscometer or NDJ-9S viscometer from Shanghai Lichen Technology.
  • the length of the air layer is 2-500mm, for example, the length of the air layer is 2mm, 5mm, 10mm, 50mm, 100mm, 150mm, 200mm, 250mm, 300mm, 350mm, 400mm, 450mm, 500mm, etc.
  • the length refers to the distance from the spinneret hole to the coagulation bath.
  • the temperature of the coagulation bath is 0-100°C, such as 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C , 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, etc.
  • the number of coagulation baths is not limited in the present invention. Those skilled in the art can set the number of coagulation baths as required.
  • the coagulation bath includes 2 coagulation baths.
  • the temperature of coagulation bath I ⁇ coagulation bath II
  • the temperature of the coagulation bath I refers to that the coagulation bath that the spray liquid enters for the first time after passing through the air layer is the coagulation bath I, and the coagulation bath that enters the second time is the coagulation bath II.
  • the solute of the coagulation bath can be water, dimethyl sulfoxide (DMSO), sulfuric acid (H 2 SO 4 ), sodium sulfate (Na 2 SO 4 ), amine sulfate ( (NH 4 ) 2 SO 4 );
  • DMSO dimethyl sulfoxide
  • H 2 SO 4 sulfuric acid
  • Na 2 SO 4 sodium sulfate
  • NH 4 ) 2 SO 4 amine sulfate
  • the mass percentage of the solute in the coagulation bath may be 0-80%, for example, 0, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% , 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.
  • the present invention provides a radiation refrigeration fiber, which is prepared by the above-mentioned preparation method.
  • the structure of the radiation refrigeration fiber is a circular structure, a skin-core structure, a hollow structure, a herringbone structure, a cross-shaped structure, a side-by-side structure, a radial structure, At least one of the sea-island structures.
  • the present invention provides a radiation refrigeration fabric, which is obtained by knitting the radiation refrigeration fiber prepared by the above-mentioned preparation method or the above-mentioned radiation refrigeration fiber.
  • the weaving may be knitting or weaving.
  • the average reflectance of the radiation cooling fabric in the solar wavelength band is greater than or equal to 0.9, preferably 0.9-0.95.
  • the average reflectivity of the radiation cooling fabric in the solar wavelength band may be 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, etc.
  • the average emissivity of the radiation cooling fabric in the 8-13 ⁇ m waveband is greater than or equal to 0.9, preferably 0.90-0.95.
  • the average emissivity of the radiative cooling fabric in the 8-13 ⁇ m band may be 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, etc.
  • the invention provides a preparation method of radiation refrigeration fabric, which comprises the following steps:
  • the radiant refrigeration fibers prepared by the above-mentioned preparation method or the above-mentioned radiant refrigeration fibers are woven as warp yarns and weft yarns.
  • the further preferred particle size of the inorganic micro-nano particles is 0.4 ⁇ m, which is determined by the rice scattering theory combined with the Monte Carlo multilayer medium simulation model.
  • the specific operations are:
  • the core idea of determining the optimal particle size is that the reflectivity to the solar radiation band (0.3-2.5 ⁇ m) reaches the maximum value under the condition of keeping the particle volume concentration constant.
  • the fabric woven from radiation cooling fibers is equivalent to a parallel flat film, and the reflectivity of the cellulose film to the sunlight band is given according to the Monte Carlo multilayer medium simulation and the Mie scattering theory.
  • the Monte Carlo multilayer dielectric simulation model is a statistical model.
  • the model to be simulated is shown in Figure 1.
  • the flat film model has three characteristic parameters: equivalent scattering coefficient ⁇ s ⁇ , equivalent absorption coefficient ⁇ ⁇ , and asymmetric parameters g, the simulation requires a large number of iterations (usually more than 1000 times), each iteration injects a photon beam with a unit energy (the arrow in Figure 1, the thickness represents the energy, the length represents the propagation distance without scattering, and the direction represents the propagation direction),
  • the photon beam enters the composite material after a specular reflection on the surface, and starts to circulate, absorb and scatter. In the nth cycle, the photon beam travels for a distance of sn.
  • the beam is attenuated due to absorption.
  • the photon beam changes its propagation direction due to scattering and enters the next cycle until the photon beam energy is completely absorbed or escapes from the thin film structure.
  • ⁇ 1 is a random number in the interval of 0-1.
  • E is the initial energy of the photon beam in the nth cycle.
  • the deflection angle ⁇ of the photon beam propagation direction in the n+1th cycle is determined by the following equation
  • ⁇ 2 is a random number in the interval of 0-1.
  • azimuth angle ⁇ of the n+1th propagation direction is determined by the following formula
  • ⁇ 3 is a random number in the interval of 0-1.
  • k is the imaginary part of the refractive index of cellulose
  • d is the diameter of titanium oxide particles
  • ⁇ is the wavelength in vacuum
  • m 0 is the refractive index of cellulose
  • m 1 is the refractive index of titanium oxide
  • ⁇ n is Riccati–Bessel functions.
  • the weighted reflectivity is:
  • I sun ( ⁇ ) is the predetermined solar spectrum
  • ⁇ 1 and ⁇ 2 are the lower and upper limits of the weighted wavelength range, respectively
  • h is the thickness of the equivalent structure.
  • the predetermined range of the solar spectrum is 0.3-2.5 ⁇ m.
  • the scanning thickness range of the equivalent structure is 100-500 ⁇ m
  • the scanning diameter of the particles is in the range of 100-1000 m
  • the obtained solar spectrum weighted reflectance varies with particle size and thickness as shown in Figure 3.
  • the black curve in the figure is the reflectance contour line. It can be seen that for different thicknesses, the weighted reflectance is always obtained at the particle size of 0.4 ⁇ m. Therefore, the optimum particle size of titanium oxide is determined to be 0.4 ⁇ m.
  • the invention prepares the radiation refrigeration fiber doped with inorganic micro-nano particles through a dry and wet spinning process, achieves excellent radiation refrigeration effect by regulating the size and concentration of the micro-nano particles, and is woven into a flexible fabric suitable for cooling the surface of human skin.
  • the preparation method can design the internal composite structure of the fiber, so that the fiber has good mechanical properties and high comfort while having excellent radiation cooling performance; using the dry and wet spinning process can effectively reduce the polymer
  • the amount of degradation in the spinning process improves the comprehensive performance of the fiber, and the prepared radiant refrigeration fiber and fabric have high flexibility, which greatly enhances the comfort of the human body.
  • the radiation refrigeration fabric prepared by the invention has an average emissivity of ⁇ 0.9 in the 8-13 ⁇ m waveband, and an average reflectance of ⁇ 0.9 in the solar light waveband.
  • the present invention generally and/or specifically describes the materials and test methods used in the test.
  • % represents wt.%, that is, weight percentage.
  • the reagents or instruments used without the manufacturer's indication are all conventional reagent products that can be obtained from the market.
  • Preparation of cellulose and TiO2 spinning stock solution configure 18000g of 7wt.%NaOH/12wt.%urea aqueous solution, add 1600g of cellulose pulp and 400g of TiO2 particles (diameter) dried in a 100°C vacuum oven for 24h 400 nm), stirred at 1500 rpm for 30 minutes, centrifuged at 8000 rpm and 10 °C for 10 minutes to deaerate and remove insolubles to obtain a spinning dope with cellulose and TiO 2 in the spinning dope with a weight ratio of 10 wt.%.
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 80 ° C, the spinning speed is 500 m/min, and the It was sprayed out through a spinneret hole with a diameter of 0.21mm and passed through an air layer of 50mm into a coagulation bath composed of 15wt.%H 2 SO 4 /10wt.% Na 2 SO 4 /water.
  • the temperature of the coagulation bath was 25°C. As-spun fibers are obtained after coagulation bath drawing.
  • the nascent fibers were bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water at 60°C, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiation refrigeration fibers.
  • the screenshot is shown in Figure 4. shown, and then collected on a winding roll without drafting.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound, thereby obtaining a radiative refrigeration fabric uniformly doped with 20 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • Preparation of PAN and TiO 2 spinning stock solution 1500 g of PAN polymer was prepared with 19305 g of DMF as solvent to prepare a spinning solution with a concentration of 7.2 wt. Dry 24h TiO2 particles (400 nm in diameter) were mixed with the spinning solution, stirred at 90 °C for 7h, and left to stand for deaeration for 9h to obtain a spinning solution with PAN and TiO2 in the spinning dope with a weight ratio of 10 wt.%. Silk stock solution.
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 90 °C, the spinning speed is 1000 m/min, and then the The first coagulation bath with DMSO as the solute at 25°C (the concentration of DMSO is (70wt.%)) and the second coagulation bath at 20°C with the solute as DMSO (The concentration of DMSO is (70 wt.%)), the spun fibers are obtained after stretching in a coagulation bath, and the spun fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water at 50°C, oiled, and dried. Densification, dry-heat drawing, crimping, and heat-setting are performed to obtain radiation refrigeration fibers. The cross-section of the radiation refrigeration fibers is shown in Fig. 4, and the obtained radiation refrigeration fibers are collected on a winding roller.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound, thereby obtaining a radiative refrigeration fabric uniformly doped with 30 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • chitosan and Si 4 N 3 spinning stock solution 1200g of chitosan was prepared with 18000g of 4wt.% acetic acid aqueous solution as solvent to prepare 6.25wt.% spinning solution, vigorously stirred until completely dissolved, 800g was mixed with 100 The Si 4 N 3 particles (400 nm in diameter) dried in a vacuum oven for 24 hours were mixed with the spinning solution, and after fully stirring for 7 hours, the solution was placed at 20 ° C for static defoaming, and finally chitosan and Si 4 were obtained.
  • the weight ratio of N 3 in the spinning dope is 10 wt.% of the spinning dope.
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 80 °C, and the spinning speed is 1500 m/min. It is then sprayed through a pinhole with a diameter of 0.21mm, and then passed through an air layer of 40mm to a coagulation bath of 15% NaOH/30% absolute ethanol at 25 ° C. After the coagulation bath is stretched, primary fibers are obtained, and the primary fibers are bundled. , preheating bath stretching, boiling water or steam bath stretching, hot water washing, oiling, drying and densification, dry heat stretching, crimping, and heat setting to obtain radiation refrigeration fibers. The cross-section of the radiation refrigeration fibers is shown in Figure 4. The resulting radiant refrigeration fibers are collected on winding rolls.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound, thereby obtaining a radiative refrigeration fabric uniformly doped with 40 wt. % silicon nitride particles, as shown in FIG. 9 .
  • PVA and TiO2 spinning stock solution 1000g of PVA polymer was prepared with 18000g of DMF as solvent to prepare a spinning solution with a concentration of 5.3 wt.%, and 1000g of TiO2 particles were dried in a vacuum oven at 100 °C for 24h (400 nm in diameter), stir evenly at 80 °C, and place the solution at 20 °C to stand for defoaming, and finally obtain a spinning dope with PVA and TiO 2 in the spinning dope with a weight ratio of 10 wt.%.
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 80 °C, and the spinning speed is 2000 m/min. It is sprayed out from a spinneret with a diameter of 0.25 mm, passed through an air layer of about 10 mm into an absolute ethanol coagulation bath, and coagulated at room temperature to form primary fibers.
  • the primary fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiation cooling fibers.
  • the cross-section of the radiation cooling fibers is shown in Figure 4. shown, the resulting radiant refrigeration fibers were then collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound to obtain a radiative refrigeration fabric uniformly doped with 50 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • cellulose and TiO2 spinning dope 18000 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 1200 g of cellulose pulp and 800g of TiO 2 particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was left to stand at 20 °C for defoaming. Finally, the weight ratio of cellulose and TiO 2 in the spinning dope was 10wt. .% spinning dope, that is, the first spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • Dry and wet spinning to prepare radiant refrigeration fiber transfer the first spinning stock solution and the second spinning stock solution to the first spinning medicine tank and the second spinning medicine tank through a metering pump and a candle filter respectively, and then spin the fiber.
  • the silk temperature is 110°C
  • the spinning speed is 500m/min
  • it is sprayed through the skin-core double jet pinholes through a 50mm air layer to a water coagulation bath of 80°C, and the primary fibers are obtained after stretching in the coagulation bath.
  • the spun fibers are bundled, stretched in a preheating bath, stretched in a boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain a skin with a core layer uniformly doped with 40 wt.% titanium dioxide particles
  • the core structure of the radiative cooling fiber, the cross section of the radiative cooling fiber is shown in Fig. 5, and then the obtained radiative cooling fiber is collected to the winding roller.
  • the obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the fabric is wound and pulled away to obtain a fabric woven by skin-core structure radiation refrigeration fibers whose core layer is uniformly doped with 40 wt.% titanium dioxide particles.
  • the fabric is shown in FIG. 9 .
  • cellulose and TiO spinning dope 18000 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 1600 g of cellulose pulp and 1600 g of cellulose pulp were added under vigorous stirring. 400 g of TiO 2 particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was placed at 20 °C for static defoaming to obtain cellulose and TiO 2 in the spinning dope with a weight ratio of 10 wt. % of spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 110 °C, and the spinning speed is 500 m/min. And at room temperature, through a herringbone spinneret with a diameter of 0.2mm, it was sprayed through an air layer of 50mm into a water coagulation bath, and the temperature of the coagulation bath was 80°C.
  • the nascent fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiant cooling fibers.
  • the cross-section of the radiative cooling fibers is shown in Figure 6. shown, the resulting radiant refrigeration fibers were then collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound, thereby obtaining a radiative refrigeration fabric uniformly doped with 20 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • cellulose and TiO spinning dope 18000 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 1600 g of cellulose pulp and 1600 g of cellulose pulp were added under vigorous stirring. 400 g of TiO 2 particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was placed at 20 °C for static defoaming to obtain cellulose and TiO 2 in the spinning dope with a weight ratio of 10 wt. % of spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 110 °C, and the spinning speed is 500 m/min. And at room temperature, it was sprayed through a cross-shaped spinneret with a diameter of 0.2 mm, passed through an air layer of 50 mm, and was placed in a water coagulation bath at 80 °C, and the primary fibers were obtained after stretching in the coagulation bath.
  • the nascent fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiation cooling fibers.
  • the cross-section of the radiation cooling fibers is shown in Figure 7. As shown, the resulting radiant refrigeration fibers were collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound, thereby obtaining a radiative refrigeration fabric uniformly doped with 20 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • cellulose and TiO spinning dope 8000 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 1500 g of cellulose pulp and 1500 g of cellulose pulp were added under vigorous stirring. 500 g of TiO particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was left to stand at 20 °C for defoaming to obtain a weight ratio of 20 wt cellulose and TiO in the spinning dope. % of spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 110 °C, and the spinning speed is 500 m/min. And at room temperature, it was sprayed through a spinneret hole with a diameter of 0.2 mm and passed through an air layer of 50 mm into a water coagulation bath.
  • the primary fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiation cooling fibers.
  • the cross-section of the radiation cooling fibers is shown in Figure 4. shown, the resulting radiant refrigeration fibers were then collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound to obtain a radiative refrigeration fabric uniformly doped with 25 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • cellulose and TiO spinning dope 2250 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 1000 g of cellulose pulp and 1000 g of cellulose pulp were added under vigorous stirring. 500 g of TiO 2 particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was placed at 20 °C for static defoaming to obtain cellulose and TiO 2 in the spinning dope with a weight ratio of 40 wt. % of spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 110 °C, and the spinning speed is 500 m/min. And at room temperature, through a spinneret with a diameter of 0.2mm, it was sprayed through a 50mm air layer into a water coagulation bath. The temperature of the coagulation bath was 80°C, and the primary fiber was obtained after stretching in the coagulation bath.
  • the primary fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiation cooling fibers.
  • the cross-section of the radiation cooling fibers is shown in Figure 4. shown, the resulting radiant refrigeration fibers were then collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound, thereby obtaining a radiative refrigeration fabric uniformly doped with 30 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • cellulose and TiO spinning dope 3267 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 1000 g of cellulose pulp and 1000 g of cellulose pulp were added under vigorous stirring. 400 g of TiO particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was left to stand at 20 °C for defoaming to obtain a weight ratio of 20 wt cellulose and TiO in the spinning dope. % of spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 110 °C, and the spinning speed is 500 m/min. And at room temperature, through a spinneret with a diameter of 0.2mm, it was sprayed through a 50mm air layer into a water coagulation bath. The temperature of the coagulation bath was 80°C, and the primary fiber was obtained after stretching in the coagulation bath.
  • the primary fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiation cooling fibers.
  • the cross-section of the radiation cooling fibers is shown in Figure 4. shown, the resulting radiant refrigeration fibers were then collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound, thereby obtaining a radiative refrigeration fabric uniformly doped with 28.6 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • cellulose and Si 4 N 3 spinning dope 5000 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, and 750 g of cellulose pulp was added with vigorous stirring The meal and 500 g of Si 4 N 3 particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was placed at 20 ° C for static defoaming to obtain cellulose and Si 4 N 3 in the spinning dope. 20 wt.% spinning dope by weight.
  • NMMO 4-methylmorpholine-N-oxide
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 110 °C, and the spinning speed is 500 m/min. And at room temperature, through a spinneret with a diameter of 0.2mm, it was sprayed through a 50mm air layer into a water coagulation bath. The temperature of the coagulation bath was 80°C, and the primary fiber was obtained after stretching in the coagulation bath.
  • the primary fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiation cooling fibers.
  • the cross-section of the radiation cooling fibers is shown in Figure 4. shown, the resulting radiant refrigeration fibers were then collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound to obtain a radiative refrigeration fabric uniformly doped with 40 wt. % silicon nitride particles, as shown in FIG. 9 .
  • cellulose and TiO spinning dope 3500 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 1200 g of cellulose pulp and 1200 g of cellulose pulp were added under vigorous stirring. 300 g of TiO 2 particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was placed at 20 °C for static defoaming to obtain a weight ratio of 30 wt cellulose and TiO 2 in the spinning dope. % of spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 110 °C, and the spinning speed is 500 m/min. And at room temperature, through a spinneret with a diameter of 0.2mm, it was sprayed through a 50mm air layer into a water coagulation bath. The temperature of the coagulation bath was 80°C, and the primary fiber was obtained after stretching in the coagulation bath.
  • the primary fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiation cooling fibers.
  • the cross-section of the radiation cooling fibers is shown in Figure 4. shown, the resulting radiant refrigeration fibers were then collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound, thereby obtaining a radiative refrigeration fabric uniformly doped with 20 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • cellulose and ZnO spinning dope 4500 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110°C until completely melted, 1000 g of cellulose pulp and 500 g of cellulose pulp were added under vigorous stirring The ZnO particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was left to stand at 20 °C for defoaming to obtain a spinning solution with cellulose and ZnO in the spinning dope with a weight ratio of 25 wt.%. Silk stock solution.
  • NMMO 4-methylmorpholine-N-oxide
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 110 °C, and the spinning speed is 500 m/min. And at room temperature, through a spinneret with a diameter of 0.2mm, it was sprayed through a 50mm air layer into a water coagulation bath. The temperature of the coagulation bath was 80°C, and the primary fiber was obtained after stretching in the coagulation bath.
  • the primary fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiation cooling fibers.
  • the cross-section of the radiation cooling fibers is shown in Figure 4. shown, the resulting radiant refrigeration fibers were then collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound, thereby obtaining a radiative refrigeration fabric uniformly doped with 33.3 wt. % zinc oxide particles, as shown in FIG. 9 .
  • cellulose and TiO spinning dope 4950 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 49 g of cellulose pulp and 49 g of cellulose pulp were added under vigorous stirring. 1 g of TiO 2 particles with a particle size of 10 ⁇ m dried in a vacuum oven at 100 °C for 24 h, and the solution was placed at 20 °C for static defoaming to obtain cellulose and TiO 2 in the spinning dope with a weight ratio of 1wt .% spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 110 °C, and the spinning speed is 0.6 m/min. And at room temperature, through a spinneret with a diameter of 0.8mm, it was sprayed through a 50mm air layer into a water coagulation bath, and the temperature of the coagulation bath was 80°C.
  • the primary fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiation cooling fibers.
  • the cross-section of the radiation cooling fibers is shown in Figure 4. shown, the resulting radiant refrigeration fibers were then collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound, thereby obtaining a radiative refrigeration fabric uniformly doped with 2 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • cellulose and TiO spinning dope 3000 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, and 3500 g of cellulose pulp and cellulose pulp were added under vigorous stirring. 3500 g of TiO 2 particles with a particle size of 0.1 ⁇ m were dried in a vacuum oven at 100 °C for 24 h, and the solution was placed at 20 °C for static defoaming to obtain the weight ratio of cellulose and TiO 2 in the spinning dope: 70 wt.% spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • the spinning dope is transferred to a spinning medicine tank through a metering pump and a candle filter, the spinning temperature is 110 °C, and the spinning speed is 3000 m/min. And at room temperature, through a spinneret with a diameter of 0.01mm, it was sprayed through a 50mm air layer into a water coagulation bath, and the temperature of the coagulation bath was 80°C.
  • the nascent fibers are bundled, stretched in a preheating bath, stretched in a boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain radiant refrigeration fibers.
  • the cross-section of the radiant refrigeration fibers is shown in Figure 4. shown, the resulting radiant refrigeration fibers were then collected on a winding roll.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the pull-off fabric was wound to obtain a radiative refrigeration fabric uniformly doped with 50 wt. % titanium dioxide particles, as shown in FIG. 9 .
  • cellulose and TiO spinning dope 2800 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C to complete melting, 900 g of cellulose pulp and cellulose pulp were added under vigorous stirring. 300 g of TiO 2 particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was left to stand at 20 °C for defoaming, and finally the weight ratio of cellulose and TiO 2 in the spinning dope was 30wt. .% spinning dope, that is, the first spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • Dry and wet spinning to prepare radiant refrigeration fiber transfer the first spinning stock solution and the second spinning stock solution to the first spinning medicine tank and the second spinning medicine tank through a metering pump and a candle filter respectively, and then spin the fiber.
  • the silk temperature is 110°C
  • the spinning speed is 500m/min
  • it is sprayed through the skin-core double jet pinholes through a 50mm air layer to a water coagulation bath of 80°C, and the primary fibers are obtained after stretching in the coagulation bath.
  • the spun fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain a core layer uniformly doped with 25wt.% titanium dioxide particles, a skin layer
  • the skin-core structure radiation cooling fiber uniformly doped with 9 wt.% titanium dioxide particles, the cross section of the radiation cooling fiber is shown in Figure 5, and then the obtained radiation cooling fiber is collected into a winding roller.
  • the obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the fabric is wound and pulled away to obtain a fabric woven by skin-core structure radiation refrigeration fibers whose core layer is uniformly doped with 25 wt.% titanium dioxide particles.
  • the fabric is shown in FIG. 9 .
  • cellulose and TiO spinning dope 2250 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 1000 g of cellulose pulp and 1000 g of cellulose pulp were added under vigorous stirring. 500 g of TiO particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was left to stand at 20 °C for defoaming to obtain cellulose and TiO in the spinning dope with a weight ratio of 30 wt. % of the spinning dope, that is, the first spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • Dry and wet spinning to prepare radiant refrigeration fiber transfer the first spinning stock solution and the second spinning stock solution to the first spinning medicine tank and the second spinning medicine tank through a metering pump and a candle filter respectively, and then spin the fiber.
  • the silk temperature is 110°C
  • the spinning speed is 500m/min
  • it is sprayed through the skin-core double jet pinholes through a 50mm air layer to a water coagulation bath of 80°C, and the primary fibers are obtained after stretching in the coagulation bath.
  • the spun fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain a core layer uniformly doped with 30wt.% titanium dioxide particles, a skin layer
  • the skin-core structure radiation cooling fiber uniformly doped with 7 wt.% titanium dioxide particles, the cross section of the radiation cooling fiber is shown in Figure 5, and then the obtained radiation cooling fiber is collected into a winding roller.
  • the obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the fabric was wound and pulled away to obtain a fabric woven by skin-core structure radiation refrigeration fibers with the core layer uniformly doped with 30wt.% titanium dioxide particles and the skin layer uniformly doped with 7wt.% titanium dioxide particles.
  • cellulose and TiO spinning dope 8500 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 1200 g of cellulose pulp and 1200 g of cellulose pulp were added under vigorous stirring. 300 g of TiO particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was left to stand at 20 °C for defoaming to obtain a weight ratio of 15 wt of cellulose and TiO in the spinning dope. % of the spinning dope, that is, the first spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • Dry and wet spinning to prepare radiant refrigeration fiber transfer the first spinning stock solution and the second spinning stock solution to the first spinning medicine tank and the second spinning medicine tank through a metering pump and a candle filter respectively, and then spin the fiber.
  • the silk temperature is 110°C
  • the spinning speed is 500m/min
  • it is sprayed through the skin-core double jet pinholes through a 50mm air layer to a water coagulation bath of 80°C, and the primary fibers are obtained after stretching in the coagulation bath.
  • the spun fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain a core layer uniformly doped with 20wt.% titanium dioxide particles, a skin layer
  • the skin-core structure radiation cooling fiber uniformly doped with 10 wt.% titanium dioxide particles, the cross section of the radiation cooling fiber is shown in Fig. 5, and then the obtained radiation cooling fiber is collected into a winding roller.
  • the obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the fabric is wound and pulled out to obtain a fabric woven by skin-core structure radiation refrigeration fibers with the core layer uniformly doped with 20wt.% titanium dioxide particles and the skin layer uniformly doped with 10wt.% titanium dioxide particles.
  • cellulose and Si 4 N 3 spinning dope 2550 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, and 450 g of cellulose pulp was added under vigorous stirring The meal and 300 g of Si 4 N 3 particles (400 nm in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was placed at 20 ° C for static defoaming to obtain cellulose and Si 4 N 3 in the spinning dope. 15 wt.% spinning dope by weight. , namely the first spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • NMMO solvent 3400 g was heated at 110 °C until completely melted, 570 g of cellulose pulp and 30 g of TiO 2 particles (400 nm in diameter) were added under vigorous stirring and dried in a vacuum oven at 100 °C for 24 h. The solution was left to stand at 20°C for defoaming, and finally a spinning dope in which cellulose and TiO 2 accounted for 15 wt.% by weight in the spinning dope was obtained, that is, the second spinning dope.
  • Dry and wet spinning to prepare radiant refrigeration fiber transfer the first spinning stock solution and the second spinning stock solution to the first spinning medicine tank and the second spinning medicine tank through a metering pump and a candle filter respectively, and then spin the fiber.
  • the silk temperature is 110°C
  • the spinning speed is 500m/min
  • it is sprayed through the skin-core double jet pinholes through a 50mm air layer to a water coagulation bath of 80°C, and the primary fibers are obtained after stretching in the coagulation bath.
  • the spun fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain a core layer uniformly doped with 40 wt.% silicon nitride particles ,
  • the skin layer is uniformly doped with 5 wt.% titanium dioxide particles of the skin-core structure radiation refrigeration fiber, the cross section of the radiation refrigeration fiber is shown in Figure 5, and then the obtained radiation refrigeration fiber is collected on the winding roller.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the fabric is wound and pulled out to obtain a fabric woven by skin-core structure radiation refrigeration fibers with the core layer uniformly doped with 40 wt.% silicon nitride particles and the skin layer uniformly doped with 5 wt.% titanium dioxide particles.
  • cellulose and TiO spinning dope 9900 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 50 g of cellulose pulp and 50 g of cellulose pulp were added under vigorous stirring. 50 g of TiO 2 particles (5 ⁇ m in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was placed at 20 °C to stand for defoaming to obtain cellulose and TiO 2 in the spinning dope with a weight ratio of 1 wt. % of the spinning dope, that is, the first spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • Dry and wet spinning to prepare radiant refrigeration fiber transfer the first spinning stock solution and the second spinning stock solution to the first spinning medicine tank and the second spinning medicine tank through a metering pump and a candle filter respectively, and then spin the fiber.
  • the silk temperature is 110°C
  • the spinning speed is 500m/min
  • it is sprayed through the skin-core double jet pinholes through a 50mm air layer to a water coagulation bath of 80°C, and the primary fibers are obtained after stretching in the coagulation bath.
  • the spun fibers are bundled, stretched in a preheating bath, stretched in boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain a core layer uniformly doped with 50wt.% titanium dioxide particles, a skin layer
  • the skin-core structure radiation cooling fiber uniformly doped with 20 wt.% titanium dioxide particles, the cross section of the radiation cooling fiber is shown in Fig. 5, and then the obtained radiation cooling fiber is collected into a winding roller.
  • Preparation of radiant refrigeration fabric The obtained radiant refrigeration fibers were used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller were adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarns, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarns is adjusted in coordination with other mechanisms on the loom.
  • the fabric is wound and pulled out to obtain a fabric woven by skin-core structure radiation refrigeration fibers with the core layer uniformly doped with 50 wt.% titanium dioxide particles and the skin layer uniformly doped with 20 wt.% titanium dioxide particles.
  • cellulose and TiO spinning dope 2143 g of 4-methylmorpholine-N-oxide (NMMO) solvent was heated at 110 °C until completely melted, 4900 g of cellulose pulp and 100 g of TiO 2 particles (10 ⁇ m in diameter) were dried in a vacuum oven at 100 °C for 24 h, and the solution was placed at 20 °C for static defoaming, and the weight ratio of cellulose and TiO 2 in the spinning dope was 70 wt. % of the spinning dope, that is, the first spinning dope.
  • NMMO 4-methylmorpholine-N-oxide
  • NMMO solvent 2143g was heated at 110°C until completely melted, 4900g of cellulose pulp and 100g of ZnO particles (10 ⁇ m in diameter) were added under vigorous stirring and dried in a vacuum oven at 100°C for 24 hours. It was placed at 20° C. for static deaeration, and finally a spinning dope in which the weight ratio of cellulose and ZnO in the spinning dope was 70 wt.% was obtained, that is, the second spinning dope.
  • Dry and wet spinning to prepare radiant refrigeration fiber transfer the first spinning stock solution and the second spinning stock solution to the first spinning medicine tank and the second spinning medicine tank through a metering pump and a candle filter respectively, and then spin the fiber.
  • the silk temperature is 110°C
  • the spinning speed is 500m/min
  • it is sprayed through the skin-core double jet pinholes through a 50mm air layer to a water coagulation bath of 80°C, and the primary fibers are obtained after stretching in the coagulation bath.
  • the spun fibers are bundled, stretched in a preheating bath, stretched in a boiling water or steam bath, washed with hot water, oiled, dried and densified, stretched by dry heat, crimped, and heat-set to obtain a skin-core layer uniformly doped with 2wt.% titanium dioxide particles,
  • the skin-core structure radiation cooling fiber with the skin layer uniformly doped with 2 wt.% zinc oxide particles, the cross section of the radiation cooling fiber is shown in Figure 5, and then the obtained radiation cooling fiber is collected on the winding roller.
  • the obtained radiant refrigeration fibers are used as weft yarns and warp yarns respectively.
  • the warp yarns of the cloth winding roller are adjusted to make the tension uniform and the tightness moderate;
  • the upper and lower layers of warp yarns are driven in sequence to form a shed channel; fibers are wound on the shuttle as weft yarn, the shuttle is alternately woven through the shed channel, and the arrangement density of the weft yarn is adjusted in coordination with other mechanisms on the loom.
  • the fabric is wound and pulled out to obtain a fabric woven by skin-core structure radiation refrigeration fibers with the core layer uniformly doped with 2 wt.% titanium dioxide particles and the skin layer uniformly doped with 2 wt.% zinc oxide particles.
  • Comparative Example 1 is prepared by electrospinning, and the specific operation steps are carried out by the method described in Example 1 in Chinese Patent Application CN110042564A to obtain radiation refrigeration fibers.
  • Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that the radiation refrigeration fiber obtained in Comparative Example 2 does not contain inorganic micro-nano particles.
  • Example 1-14 The radiation refrigeration fabric obtained in Example 1-14 and the radiation refrigeration fabric obtained in Comparative Example 1-2 were tested, and the specific operation method was: use UV-VIS-NIR spectrophotometer in conjunction with integrating sphere to test the fabric in solar radiation ( 0.3-2.5 ⁇ m) band reflectance, using Fourier transform infrared spectrometer combined with integrating sphere to test the fabric emissivity in the mid-infrared (8-13 ⁇ m) band. The obtained results are shown in Table 2.
  • Table 2 The reflectance results of radiative cooling fabrics in the solar band and the average emissivity results in the mid-infrared band
  • Example 1 0.92 0.92
  • Example 2 0.93 0.91
  • Example 3 0.92 0.90
  • Example 4 0.91 0.93
  • Example 5 0.92 0.91
  • Example 6 0.92 0.92
  • Example 7 0.92 0.92
  • Example 8 0.95 0.95
  • Example 9 0.95 0.95
  • Example 10 0.95 0.95
  • Example 11 0.92 0.94
  • Example 12 0.93 0.93
  • Example 13 0.94 0.94
  • Example 14 0.90 0.90
  • Example 15 0.91 0.90
  • Example 16 0.95 0.94
  • Example 17 0.95 0.94
  • Example 18 0.93 0.92
  • Example 19 0.93 0.92
  • Example 20 0.90 0.90
  • Example 21 0.90 0.90 Comparative Example 1 0.90 0.85 Comparative Example 2 0.90 0.60
  • Comparing Example 1 and Example 1 the difference is only in the method used. Comparative Example 1 uses the electrospinning method to prepare radiation cooling fibers, and its average emissivity in the 8-13 ⁇ m band and in the sunlight band The results of the average reflectance are shown in Table 2. It can be seen from Table 2 that the average emissivity of the fabric described in Example 1 in the 8-13 ⁇ m band is 0.92, and the average reflectance in the sunlight band is not 0.92. The ratios 1 are 0.90 and 0.85 respectively, indicating that the fabric woven by the radiation refrigeration fibers prepared by the method of the present invention has a good effect.
  • Example 2 Comparing Example 2 and Example 1, the difference is that the radiation cooling fiber prepared without inorganic micro-nano particles in Comparative Example 2, the average emissivity of the woven fabric in the 8-13 ⁇ m band and the average emissivity in the sunlight band
  • Table 2 The results of reflectance are shown in Table 2. It can be seen from Table 2 that the average emissivity of the fabric described in Example 1 in the 8-13 ⁇ m band is 0.92, and the average reflectance in the sunlight band is less than 0.92, while Comparative Example 2 are 0.90 and 0.60, respectively, indicating that the fabric containing inorganic micro-nano particles has better effect.
  • the present invention uses the dry and wet spinning process to prepare the radiation refrigeration fiber doped with inorganic micro-nano particles, which has excellent radiation refrigeration effect, and is woven into a flexible fabric suitable for cooling the surface of human skin.
  • the average emissivity of the cooling fabric in the 8-13 ⁇ m band is ⁇ 0.9
  • the average reflectivity in the sunlight band is ⁇ 0.9.

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Abstract

一种辐射制冷纤维、制备方法及其应用。一种辐射制冷纤维的制备方法，其包括下述步骤：将无机微纳颗粒和基底材料混合得到微纳颗粒和基底材料纺丝原液；将所述微纳颗粒和基底材料纺丝原液进行干湿法纺丝，得到辐射制冷纤维。使用上述方法制备，能够使纤维在具有优异辐射制冷性能的同时兼具良好的力学性能以及高舒适性，并且有效减少聚合物在纺丝过程中的降解量，提升纤维的综合性能。制备的辐射制冷纤维与织物具有高柔性，极大增强人体舒适感，且通过调控微纳颗粒的尺寸和浓度达到优异的辐射制冷效果，能编织成适用于人体皮肤表面降温的柔性织物，并且柔性织物8-13μm波段的平均发射率≥0.9，在太阳光波段的平均反射率≥0.9。

Description

一种湿法纺丝辐射制冷纤维、制备方法及其应用 技术领域
本发明涉及辐射制冷技术领域，尤其涉及一种辐射制冷纤维、制备方法及其应用。
背景技术
传统空间热调控系统是通过对整个空间加热和制冷的方式达到温度调控目的，此过程往往伴随着大量的能源消耗，由此产生的能源浪费和环境污染问题给人类生产生活带来极为不利的影响。在全球电力能耗中，制冷占据主要部分，如此大的制冷耗能将对人类生产经济造成严重威胁。因此通过降低空间冷量需求，不仅能够实现有效经济的个人舒适，更对人类可持续发展具有积极意义。
辐射制冷技术通过材料选择和结构调控，可使物体在8-13μm获得高发射率，而在0.3-2.5μm的太阳辐射波段实现高反射率，利用这种光谱选择性调控的方式有效地辐射热量并阻挡能量输入，由此达到制冷的目的。与目前大多数需要能源将热量带走的制冷方式不同，辐射制冷无需任何电力输入，对降低全球能耗和环境保护具有积极的推动作用。
2013年斯坦福大学团队通过理论设计出能实现辐射制冷的金属电介质光子结构，通过纳米光学材料设计，该周期孔洞的微纳结构理论上可实现低于环境温度40-60℃的被动制冷，实现了超过100W/m 2净冷却功率。随后该团队通过微纳加工手段制备了集成了太阳反射器和热发射器的光子辐射制冷器，首次实现了日间辐射制冷。该光子辐射制冷器是以银膜作为衬底的多层膜结构，在反射97％的太阳辐射的同时，实现了大气透明窗口强烈的选择性发射。
自此，通过材料选择和结构设计的日间辐射制冷系统逐渐引起越来越多人的关注。在2017年，美国科罗拉多大学有团队制备了一种随机玻璃-聚合物混合超材料，在透明聚合物甲基戊烯中嵌入随机分布的共振电介质SiO 2微球，并用银薄膜作为背衬，其制备的200nm银涂层背衬的50μm厚的超材 料能够反射约96％的太阳辐射，在8-13μm之间具有大于93％的高发射率，直射阳光下能够产生大于100W﹒m -2的辐射冷却功率。美国哥伦比亚大学Yang和Yu教授团队基于相分离法制备了P(VdF-HFP)分级多孔涂层，通过涂层内的微纳孔隙实现了0.96的高太阳辐射反射率和0.97的高红外发射率，在阳光下可实现低于环境温度～6℃的被动制冷效果。
尽管日间被动辐射制冷已经实现并取得了优异的降温效果，但现有的涂层态、薄膜态辐射制冷材料由于缺乏必要的透气透湿性、柔软性和舒适性而无法适用于人体皮肤降温。因此，需要开发柔软舒适的纤维织物态辐射制冷材料，从而满足个人热舒适需求。
中国专利申请CN110042564A提出了一种辐射制冷纤维膜及其制备方法和应用。通过静电纺丝将单分散性好的辐射粒子随机分散在聚合物纤维之间，制备得到结构简单的、可用于人体散热降温的纤维膜。在阳光下进行测试，该纤维膜可使物体表面温度低于环境温度1.6℃-2.7℃，但此方法生产效率低，工艺复杂，设备成本高，且不具备可编织性，应用场景受到限制，无法制备用于人体辐射制冷的纺织品。
中国专利申请CN202010261971.7提出了一种辐射制冷纤维的设计方法以及该辐射制冷纤维，利用基于时域有限差分法的FDTD Soultions构建基底材料中掺杂介质微纳颗粒的仿真模型，通过精确控制散射介质的浓度和尺寸实现了在相同体积百分数下最高的太阳光谱反射效率，为辐射制冷纤维提供了完备的设计方法，实现与现有的工业技术良好兼容。
中国专利申请CN202010261972.1提出一种高掺杂辐射制冷复合纤维及其织物的制备方法，利用热拉制法在纤维内部引入微纳颗粒制备纤维，并编织成适用于人体降温的织物，实现太阳辐射的高反射率和大气窗口的高发射率，具有优异的辐射制冷效果。
中国专利申请CN202010261960.9提出了一种辐射制冷纤维及其织物的制备方法，利用熔融复合纺丝法在聚合物纤维内引入无机微纳颗粒，由此制备的纤维具有优异辐射制冷性能，同时兼具良好的力学性能、弹性稳定性以及高舒适性，得到适用于人体皮肤表面降温的辐射制冷织物。
中国专利申请CN202010261965.1提出了一种辐射制冷功能复合纱及其面料的制备方法，利用浸轧法和包覆法在纱线外部和内部引入高浓度无机微纳颗粒，制备适用于人体皮肤降温的辐射制冷复合纱，并通过编织技术得到 兼具优异辐射制冷性能和高舒适性的纺织品，为制备具有优异辐射制冷性能的服装面料提供有效的方法。因此，基于基底材料的选择和微纳颗粒的粒径浓度控制，可以有效阻挡太阳辐射能量输入，并最大化红外辐射热量输出，具有优异的辐射制冷性能，并能与现有的工业技术良好兼容。
众多纤维制备工艺中，干湿法纺丝制备纤维是将聚合物溶解于溶剂中制备得到合适浓度的纺丝液，经过一段空气层后再通过凝固浴将聚合物析出成固体丝条，经拉伸、定型、洗涤、干燥等后处理过程。该工艺的优势在于可以纺高粘度的纺丝原液，从而减小溶剂的回收及消耗，其成形速度较高，所得到的纤维结构均匀，横截面近似圆形，强度和弹性均有所提高，染色性和色泽较好。经过空气层发生的物理变化有利于形成细特化、致密化和均质化的丝条，且能比较有效的调节纤维的结构形成过程。纺出的纤维体密度较高,表面平滑无沟槽,且可实现速纺,可用于生产高性能、高质量的纤维原丝，制备的纤维具有高柔性，极大增强人体舒适感，是用于实现人体热管理的理想纤维。
CN101805934B的中国专利公开了一种冰凉粘胶纤维，以竹浆粕为原料的粘胶纤维中添加纤维干基重量的3～20wt％的云母粉体，以干湿法纺丝为工艺，所制备的纤维具有抗紫外线、吸湿排汗、远红外的保健作用，特别适用于生产夏季服装服饰制品。但此方法利用干湿法纺丝制备的纤维功能仅限于抗紫外，无法调控太阳辐射和人体热辐射，无法用于个人热管理。
CN107955984A的中国专利申请公开了一种石墨烯接枝多糖Lyocell纤维及其制备方法，将纤维素、接枝有多糖的石墨烯与N-甲基吗啉-N-氧化物(NMMO)水溶液进行混合得到含有石墨烯的纺丝原液，通过干湿法纺丝制备的Lyocell纤维具有优良导电导热性能、远红外和防紫外功能、力学性能好等优势。但此方法所涉及接枝步骤较为复杂，且无法调控人体辐射。
CN106498538B的中国专利公开了一种高导热性芳香族聚酰胺纤维的制备方法及其应用，将氧化石墨烯分散于有机溶剂中，制备得到分散液；在惰性气体保护下，将间苯二胺单体加入到前述分散液中溶解，得到间位芳香族聚酰胺树脂溶液；采用干湿法纺丝工艺进行纺丝，最终制得高导热性芳香族聚酰胺纤维。但此方法生产效率低，工艺复杂，设备成本高，且无法调控人体辐射。
综上所述，现缺乏基于干湿法纺丝工艺批量制备得到高柔性辐射制冷纤 维的方法。
发明内容
为了解决上述问题，本发明提供了一种干湿法纺丝辐射制冷纤维及其织物的批量制备方法，能够利用干湿法纺丝工艺引入无机微纳颗粒，并且能够精准调控微纳颗粒的尺寸以及纤维的结构。
本发明利用干湿法纺丝，以纤维素等常用聚合物材料为基底，制备掺杂无机微纳颗粒的辐射制冷纤维，通过调控微纳颗粒的尺寸、浓度以及纤维的结构达到优异的力学性能和辐射制冷效果，并编织成适用于人体皮肤表面降温的柔性织物。
本发明具体技术方案如下：
1.一种辐射制冷纤维的制备方法，其包括下述步骤：
将无机微纳颗粒和基底材料混合得到微纳颗粒和基底材料纺丝原液；
将所述微纳颗粒和基底材料纺丝原液进行干湿法纺丝，得到辐射制冷纤维。
2.根据项1所述的制备方法，其中，以所述无机微纳颗粒为1重量份计，所述基底材料为1-999重量份，优选为1.5-4重量份，进一步优选为2.33-3重量份。
3.根据项1或2所述的制备方法，其中，所述无机微纳颗粒选自二氧化钛、二氧化硅、氧化锌、碳化硅、氮化硅、硫化锌、氧化铝、氧化铁、氮化硼、氧化镁、硫酸钡、碳酸钡和硅酸铝中的一种或两种以上，优选为二氧化钛、氧化锌或氮化硅。
4.根据项1-3中任一项所述的制备方法，其中，所述基底材料选自纤维素、聚乳酸、聚乙烯、聚丙烯、聚酰胺、聚氯乙烯、聚苯乙烯、聚醋酸乙烯酯、聚乙烯醇、聚丙烯腈、聚对苯甲酰胺、聚对苯二甲酸乙二醇酯、壳聚糖、聚对苯二甲酰对苯二胺、间位芳香族聚酰胺、聚偏氟乙烯、二丁酰甲壳质、聚苯并咪唑和聚苯并双二噁唑中的一种或两种以上，优选为纤维素、聚丙烯腈、聚乙烯醇或壳聚糖。
5.根据项1-4中任一项所述的制备方法，其中，将无机微纳颗粒和基底材料混合得到微纳颗粒和基底材料纺丝原液包括将无机微纳颗粒和基底材料加入到溶剂中得到微纳颗粒和基底材料纺丝原液。
6.根据项5所述的制备方法，其中，所述溶剂选自水、DMF、DMAc、硝酸、醋酸、甲苯、环己烷、四氢呋喃-二氧六环共混溶液、苯、四氯化碳、醋酸戊酯、丙酮、4-甲基吗啉-N-氧化物、N-乙基吡啶氯化物、1-丁基-3-甲基咪唑氯化物、1-乙基-3-甲基咪唑氯化物、1-烯丙基3-甲基咪唑氣盐、1-丁基-3-甲基咪唑醋酸盐、1-乙基-3-甲基咪唑醋酸盐、1-乙基-3-甲基咪唑磷酸二乙酯盐、NaOH/尿素/水、NaOH/硫脲/水、NaOH/硫脲/尿素/水、尿素/已内酰胺/NaOH/水、NaOH/ZnO/水、NaOH/乙醇/水、四氢化萘、萘、矿物油、石蜡油、十氢萘和石蜡中的一种或两种以上，优选为NaOH/尿素/水、DMF、醋酸或4-甲基吗啉-N-氧化物。
7.根据项1-6中任一项所述的制备方法，其中，所述无机微纳颗粒的粒径为0.03-25μm，优选为0.1-10μm，进一步优选为0.4μm。
8.根据项1-7中任一项所述的制备方法，其中，以在纺丝原液所占的重量百分比计，所述无机微纳颗粒和基底材料为1-70％，优选为20-40％。
9.根据项1-8中任一项所述的制备方法，其中，所述无机微纳颗粒包括第一无机微纳颗粒和第二无机微纳颗粒；优选的，所述第一无机微纳颗粒和所述第二无机微纳颗粒是相同的无机微纳颗粒或者是不同的无机微纳颗粒。
10.根据项9所述的制备方法，其中，所述基底材料包括基底材料1和基底材料2，优选的，所述基底材料1和所述基底材料2是相同的基底材料或者不同的基底材料。
11.根据项10所述的制备方法，其中，所述第一无机微纳颗粒和所述基底材料1混合形成第一微纳颗粒和基底材料纺丝原液；优选的，以所述第一无机微纳颗粒为1重量份计，所述基底材料1为1-49重量份，优选为1.5-4重量份，进一步优选为2.33-3重量份；
优选的，所述第二无机微纳颗粒和所述基底材料2混合形成第二微纳颗粒和基底材料纺丝原液，优选的，所述第二无机微纳颗粒为0或者以所述第二无机微纳颗粒为1重量份计，所述基底材料2为4-49重量份，优选为9-19重量份，进一步优选为10-12.5重量份。
12.根据项11所述的制备方法，其中，以在第一微纳颗粒和基底材料在纺丝原液所占的质量百分比计，所述第一无机微纳颗粒和基底材料1为1-70％，优选为20-40％；
优选的，以在第二微纳颗粒和基底材料在纺丝原液所占的质量百分比计，所述第二无机微纳颗粒和基材材料2为1-70％，优选为20-40％。
13.根据项1-12中任一项所述的制备方法，其中，所述干湿法纺丝包括下述步骤：
将所述微纳颗粒和基底材料纺丝原液送至纺丝装置中，然后从纺丝装置中喷丝头的喷丝孔中喷出得到喷出液；
喷出液经过空气层进入到凝固浴中形成初生纤维；
将初生纤维进行水洗、拉伸形成辐射制冷纤维。
14.根据项1-13中任一项所述的制备方法，其中，所述微纳颗粒和基底材料纺丝原液的粘度为50-400Pa·s，优选为300Pa·s。
15.一种辐射制冷纤维，其通过项1-14中任一项所述的制备方法制备得到。
16.根据项15所述的辐射制冷纤维，所述辐射制冷纤维的结构为圆形结构、皮芯结构、中空结构、人字型结构、十字型结构、并列型结构、放射型结构、海岛型结构中的至少一种。
17.一种辐射制冷织物，其是将项1-14中任一项所述的制备方法制备得到的辐射制冷纤维或者项15-16中任一项所述的辐射制冷纤维进行编织得到。
18.根据项17所述的辐射制冷织物，其中，所述辐射制冷织物在太阳光波段的平均反射率大于等于0.9，优选为0.9-0.95。
19.根据项17所述的辐射制冷织物，其中，所述辐射制冷织物在8-13μm波段的平均发射率大于等于0.9，优选为0.90-0.95。
发明的效果
本发明能够利用干湿法纺丝工艺制备掺杂无机微纳颗粒的辐射制冷纤维，通过调控微纳颗粒的尺寸和浓度达到优异的辐射制冷效果，并编织成适用于人体皮肤表面降温的柔性织物。
本发明所制备的辐射制冷织物在8-13μm波段的平均发射率≥0.9，在太阳光波段的平均反射率≥0.9。
本发明的制备方法可对纤维内部复合结构进行设计，从而使纤维在具有优异辐射制冷性能的同时兼具良好的力学性能以及高舒适性。
本发明采用干湿法纺丝作为纺丝工艺，能够有效减少聚合物在纺丝过程中的降解量，提升纤维的综合性能。制备的辐射制冷纤维与织物具有高柔性，极大增强人体舒适感。
本发明采用干湿法纺丝工艺可利用纤维素、壳聚糖等天然材料作为纤维基底材料，从而使制备的纤维素纤维和织物具有良好的可降解性、可回收性、绿色再生性。
附图说明
图1为本发明基于蒙特卡洛多层介质仿真模型统计的模型示意图；
图2为本发明基于蒙特卡洛多层介质仿真的基本流程图；
图3为本发明得到的太阳光谱加权反射率随粒径和厚度变化仿真示意图；
图4为本发明实施例1、2、3、4所制备的辐射制冷纤维的截面示意图；
图5为本发明实施例5所制备的辐射制冷纤维的截面示意图；
图6为本发明实施例6所制备的辐射制冷纤维的截面示意图；
图7为本发明实施例7所制备的辐射制冷纤维的截面示意图；
图8为本发明实施例的干湿法纺丝所用的装置的示意图；
图9为本发明实施例的制备的辐射制冷纤维编织成织物后的示意图。
其中，1-纺丝药罐；2-空气层；3-凝固浴；4-加热辊；5-收丝辊。
具体实施方式
下面对本发明做以详细说明。虽然显示了本发明的具体实施例，然而应当理解，可以以各种形式实现本发明而不应被这里阐述的实施例所限制。相反，提供这些实施例是为了能够更透彻地理解本发明，并且能够将本发明的范围完整的传达给本领域的技术人员。
需要说明的是，在说明书及权利要求当中使用了某些词汇来指称特定组件。本领域技术人员应可以理解，技术人员可能会用不同名词来称呼同一个组件。本说明书及权利要求并不以名词的差异作为区分组件的方式，而是以组件在功能上的差异作为区分的准则。如在通篇说明书及权利要求当中所提及的“包含”或“包括”为开放式用语，故应解释成“包含但不限定于”。说明书后续描述为实施本发明的较佳实施方式，然而所述描述乃以说明书的一般原则为目的，并非用以限定本发明的范围。本发明的保护范围当视所附权利要 求所界定者为准。
本发明提供了一种辐射制冷纤维的制备方法，其包括下述步骤：
将无机微纳颗粒和基底材料混合得到微纳颗粒和基底材料纺丝原液；
将所述微纳颗粒和基底材料纺丝原液进行干湿法纺丝，得到辐射制冷纤维。
所述辐射制冷纤维指的是纤维具有辐射制冷功能，能够将自身热量以8-13μm电磁波的形式通过“大气窗口”排放到温度接近绝对零度的外部太空，以达到自身冷却的目的。
所述无机微纳颗粒为具有高折射率的特性，在基底材料中可产生高的散射效率，可使辐射制冷纤维具有高太阳辐射反射率，其选自二氧化钛、二氧化硅、氧化锌、碳化硅、氮化硅、硫化锌、氧化铝、氧化铁、氮化硼、氧化镁、硫酸钡、碳酸钡和硅酸铝中的一种或两种以上，优选为二氧化钛、二氧化硅、氧化铝、硫酸钡。
所述基底材料为具有高红外发射率的特性，选自所述基底材料选自纤维素、聚乳酸、聚乙烯、聚丙烯、聚酰胺、聚氯乙烯、聚苯乙烯、聚醋酸乙烯酯、聚乙烯醇、聚丙烯腈、聚对苯甲酰胺、聚对苯二甲酸乙二酯、壳聚糖、聚对苯二甲酰对苯二胺、间位芳香族聚酰胺、聚偏氟乙烯、二丁酰甲壳素、聚苯并咪唑和聚苯并双二噁唑中的一种或两种以上，优选为纤维素、聚丙烯腈或壳聚糖。
在本发明优选的一种具体实施方式中，其中，以所述无机微纳颗粒为1重量份计，所述基底材料为1-49重量份，优选为1.5-4重量份，进一步优选为2.33-3重量份。
例如，以所述无机微纳颗粒为1重量份计，所述基底材料可以为1重量份、1.5重量份、2重量份、2.33重量份、2.5重量份、3重量份、3.5重量份、4重量份、5重量份、10重量份、20重量份、49重量份等。
在本发明优选的一种具体实施方式中，其中，所述无机微纳颗粒选自二氧化钛(TiO 2)、二氧化硅(SiO 2)、氧化锌(ZnO)、碳化硅(SiC)、氮化硅(Si 3N 4)、硫化锌(ZnS)、氧化铝(Al 2O 3)、氧化铁(Fe 2O 3)、氮化硼(BN)、氧化镁(MgO)、硫酸钡(BaSO 4)、碳酸钡(BaCO 3)和硅酸铝(Al 2SiO 5)中的一种或两种以上的混合物，优选为二氧化钛、氧化锌或氮化硅。
优选的，所述无机微纳颗粒的粒径为0.03-25μm，优选为0.1-10μm，进 一步优选为0.4μm，例如，所述无机微纳颗粒的粒径为0.03μm、0.05μm、0.1μm、0.2μm、0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm、1μm、5μm、10μm、15μm、20μm、25μm或其之间的任意范围。
在本发明优选的一种具体实施方式中，其中，所述基底材料选自纤维素、聚乳酸、聚乙烯、聚酰亚胺、聚丙烯、聚酰胺、聚氯乙烯、聚苯乙烯、聚醋酸乙烯酯、聚乙烯醇、聚丙烯腈、聚对苯甲酰胺、聚对苯二甲酸乙二醇酯、壳聚糖、聚对苯二甲酰对苯二胺、间位芳香族聚酰胺、聚偏氟乙烯、二丁酰甲壳质、聚苯并咪唑和聚苯并双二噁唑中的一种或两种以上的混合物，优选为纤维素、聚丙烯腈、聚乙烯醇或壳聚糖。
聚乳酸(PLA)是以乳酸为主要原料聚合得到的聚合物，是一种新型的生物降解材料，机械性能及物理性能良好，具有良好的抗拉强度及延展度。
聚乙烯(PE)是乙烯经聚合制得的一种热塑性树脂，具有优良的耐低温性能，化学稳定性好，能耐大多数酸碱的侵蚀(不耐具有氧化性质的酸)。
聚丙烯(PP)是丙烯加聚反应而成的聚合物，在80℃以下能耐酸、碱、盐液及多种有机溶剂的腐蚀，能在高温和氧化作用下分解，聚丙烯广泛应用于服装、毛毯等纤维制品、医疗器械、汽车、自行车、零件、输送管道、化工容器等生产，也用于食品、药品包装。
聚酰胺(PA)俗称尼龙(Nylon)，是分子主链上含有重复酰胺基团—[NHCO]—的热塑性树脂总称，具有良好的综合性能，包括力学性能、耐热性、耐磨损性、耐化学药品性和自润滑性，且摩擦系数低，有一定的阻燃性，易于加工，适于用玻璃纤维和其它填料填充增强改性，提高性能和扩大应用范围。
聚氯乙烯(PVC)是氯乙烯单体(vinyl chloride monomer，简称VCM)在过氧化物、偶氮化合物等引发剂；或在光、热作用下按自由基聚合反应机理聚合而成的聚合物，曾是世界上产量最大的通用塑料，应用非常广泛。在建筑材料、工业制品、日用品、地板革、地板砖、人造革、管材、电线电缆、包装膜、瓶、发泡材料、密封材料、纤维等方面均有广泛应用。
聚苯乙烯(PS)是指由苯乙烯单体经自由基加聚反应合成的聚合物，具有良好的隔热性和优良的光学性能，是优异电绝缘材料，耐腐蚀较好。
聚醋酸乙烯酯(PVAC)又称为聚乙酸乙烯酯，是乙酸乙烯酯(醋酸乙烯酯)的聚合物。
聚乙烯醇(PVA)是重要的化工原料，用于制造聚乙烯醇缩醛、耐汽油管道和维尼纶合成纤维、织物处理剂、乳化剂、纸张涂层、粘合剂、胶水等。
聚丙烯腈(PAN)由单体丙烯腈经自由基聚合反应而得到，聚丙烯腈纤维的优点是耐候性和耐日晒性好，在室外放置18个月后还能保持原有强度的77％，它还耐化学试剂，特别是无机酸、漂白粉、过氧化氢及一般有机试剂。
聚对苯甲酰胺(PBA)以对氨基苯甲酸为单位、N-甲基吡咯烷酮为溶剂，在催化剂、助催化剂存在和80～90℃的条件下，反应3小时。然后，将物料沉析到酒精中，用水洗涤树脂，干燥，即可得到纺丝用树脂聚对苯甲酰胺纤维是一种高强度、高模量、低密度的芳核酰胺纤维。
聚对苯二甲酸乙二醇酯(PET)由对苯二甲酸二甲酯与乙二醇酯交换或以对苯二甲酸与乙二醇酯化先合成对苯二甲酸双羟乙酯，然后再进行缩聚反应制得，属结晶型饱和聚酯，在较宽的温度范围内具有优良的物理机械性能，长期使用温度可达120℃，电绝缘性优良，甚至在高温高频下，其电性能仍较好，但耐电晕性较差，抗蠕变性，耐疲劳性，耐摩擦性、尺寸稳定性都很好。
壳聚糖为天然多糖甲壳素脱除部分乙酰基的产物，具有生物降解性、生物相容性、无毒性、抑菌、抗癌、降脂、增强免疫等多种生理功能，广泛应用于食品添加剂、纺织、农业、环保、美容保健、化妆品、抗菌剂、医用纤维、医用敷料、人造组织材料、药物缓释材料、基因转导载体、生物医用领域、医用可吸收材料、组织工程载体材料、医疗以及药物开发等众多领域和其他日用化学工业。
聚对苯二甲酰对苯二胺(PPTA)是对苯二胺与对苯二甲酰氯缩合聚合而成的全对位聚芳酰胺，具有高耐热性和高抗拉强度和起始弹性模量，热收缩和蠕变性能稳定，此外还有高绝缘性和耐化学腐蚀性。
聚间苯二甲酰间苯二胺(PMIA)又称间位芳纶，是一种由酰胺基团相互连接间位苯基所构成的线性大分子结构，PMIA因为苯环基团含量高,易形成梯形结构,因此制得的纤维不仅具备优良的力学性能,同时具有良好的耐高温性能,因此在热防护服、滤材、阻燃装饰布等很多领域都得到了广泛的应用。
聚偏氟乙烯(PVDF)主要指偏氟乙烯均聚物或者偏氟乙烯与其他少量含氟乙烯基单体的共聚物，兼具有氟树脂和通用树脂的特性，除具有良好的耐 化学腐蚀性、耐高温性、耐氧化性、耐候性、耐射线辐射性能外，还具有压电性、介电性、热电性等特殊性能。
聚酰亚胺类聚合物指主链上含有酰亚胺环(-CO-NH-CO-)的一类聚合物，其中以含有酞酰亚胺结构的聚合物最为重要。聚酰亚胺作为一种特种工程材料，已广泛应用在航空、航天、微电子、纳米、液晶、分离膜、激光等领域。弹性模量仅次于碳纤维，作为高温介质及放射性物质的过滤材料和防弹、防火织物。
二丁酰甲壳质(DBCH)是在以过氯酸为催化剂的多相条件下进行反应得到的一种丁酰化甲壳质产品，易溶于丙酮、DMF、乙醇等常用溶剂中。
聚苯并咪唑是含两个氮原子的苯并五元杂环刚性链聚合物，一般由芳族四胺与苯二甲酸二苯酯经缩聚和环化而成，耐辐射、耐沸水、耐溶剂、耐化学药品性能优良。可用作耐高温黏合剂和制作高性能复合材料，广泛应用于宇航、化工机械、石油开采、汽车等领域，纤维织物则用作防火、防原子辐射的防护服。
聚苯并双二噁唑(PBO)是一种溶致性液晶杂环聚合物，大分子链具有高度的芳香性，使它具有高强、高模、耐高温、耐腐蚀等优良特性。
在本发明优选的一种具体实施方式中，其中，将无机微纳颗粒和基底材料混合得到微纳颗粒和基底材料纺丝原液包括将无机微纳颗粒和基底材料加入到溶剂中得到微纳颗粒和基底材料纺丝原液。
本发明所述的溶剂不受限制，例如可以为水、DMF、DMAc、硝酸、醋酸、甲苯、环己烷、四氢呋喃-二氧六环共混溶液、苯、四氯化碳、醋酸戊酯、丙酮、4-甲基吗啉-N-氧化物、N-乙基吡啶氯化物、1-丁基-3-甲基咪唑氯化物、1-乙基-3-甲基咪唑氯化物、1-烯丙基3-甲基咪唑氣盐、1-丁基-3-甲基咪唑醋酸盐、1-乙基-3-甲基咪唑醋酸盐、1-乙基-3-甲基咪唑磷酸二乙酯、NaOH/尿素/水、NaOH/硫脲/水、NaOH/硫脲/尿素/水、NaOH/聚乙二醇/水、NaOH/ZnO/水、NaOH/乙醇/水、四氢化萘、萘、矿物油、石蜡油、十氢萘和石蜡中的一种或两种以上的混合物，优选为NaOH/尿素/水、DMF、醋酸或4-甲基吗啉-N-氧化物。
对于NaOH/尿素/水的溶剂，其是NaOH、尿素和水所形成的溶剂，三者之间可以是任意质量比例，例如以在NaOH/尿素/水溶剂中所占的质量百分比计，NaOH可以为8％，尿素为10％，余量为水；
对于NaOH/硫脲/水的溶剂，其是NaOH、硫脲和水所形成的溶剂，三者之间可以是任意质量比例，例如以在NaOH/硫脲/水溶剂中所占的质量百分比计，NaOH可以为8％，硫脲可以为6.5％，余量为水；
对于NaOH/硫脲/尿素/水的溶剂，其是NaOH、硫脲、尿素和水所形成的溶剂，四者之间可以是任意质量比例，例如以NaOH/硫脲/尿素/水溶剂所占的质量百分比计，NaOH可以为8％，硫脲可以为6.5％，尿素可以为8％，余量为水；
对于尿素/己内酰胺/氢氧化钠/水的溶剂，其是尿素、己内酰胺、氢氧化钠和水所形成的溶剂，四者之间可以是任意质量比例，例如以在尿素/己内酰胺/氢氧化钠/水溶剂中所占的质量百分比计，尿素可以为10％，己内酰胺可以为4％，氢氧化钠可以为8％，余量为水；
对于NaOH/ZnO/水的溶剂，其是NaOH、ZnO和水所形成的溶剂，三者之间可以是任意质量比例，例如以在NaOH/ZnO/水溶剂中所占的质量百分比计，NaOH可以为8％，ZnO可以为10％，余量为水；
对于NaOH/乙醇/水的溶剂，其是NaOH、乙醇和水所形成的溶剂，三者之间可以是任意质量比例，例如以NaOH/乙醇/水溶剂中所占的质量百分比计，NaOH可以为8％，乙醇可以为10％，余量为水。
对于四氢呋喃-二氧六环共混溶液，其是由四氢呋喃和二氧六环所形成的溶液，本发明对四氢呋喃和二氧六环的体积比例不作限制，例如体积比例可以为1:1。
在本发明优选的一种具体实施方式中，其中，所述无机微纳颗粒的粒径为0.03-25μm，优选为0.1-10μm，进一步优选为0.4μm。
例如，所述无机微纳颗粒的粒径可以为0.03μm、0.05μm、0.1μm、0.5μm、1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm、25μm等。
所述粒径指的是：无机微纳颗粒的平均直径。
所述粒径由米散射理论结合蒙特卡洛多层介质仿真模型确定，其具体操作方法如下文所示。
在本发明优选的一种具体实施方式中，以在所述微纳颗粒和基底材料纺丝原液所占的重量百分比计，所述无机微纳颗粒和基底材料为1-70％，优选 为20-40％。
例如，以在所述微纳颗粒和基底材料纺丝原液所占的重量百分比计，所述无机微纳颗粒和基底材料可以为1％、5％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％或其之间的任意范围。
在本发明优选的一种具体实施方式中，其中，所述无机微纳颗粒包括第一无机微纳颗粒和第二无机微纳颗粒；优选的，所述第一无机微纳颗粒和所述第二无机微纳颗粒是相同的无机微纳颗粒或者是不同的无机微纳颗粒；
优选的，所述基底材料包括基底材料1和基底材料2，优选的，所述基底材料1和所述基底材料2可以是相同的基底材料或者是不同的基底材料。
所述不同的基底材料需要使用同一种凝固浴，即既能凝固下述所述的包层也能凝固下述所述芯层的凝固浴。
在本发明优选的一种具体实施方式中，其中，
所述第一无机微纳颗粒和所述基底材料1混合形成第一微纳颗粒和基底材料纺丝原液，所述第一微纳颗粒和基底材料纺丝原液最终形成辐射制冷纤维的芯层。
优选的，以所述第一无机微纳颗粒为1重量份计，所述基底材料1为1-49重量份，优选为1.5-4重量份，进一步优选为2.33-3重量份；
优选的，所述第二无机微纳颗粒和所述基底材料2混合形成第二微纳颗粒和基底材料纺丝原液，所述第二微纳颗粒和基底材料纺丝原液最终形成辐射制冷纤维的包层。
所述第二无机微纳颗粒为0或者以所述第二无机微纳颗粒为1重量份计，所述基底材料2为4-49重量份，优选为9-19重量份，进一步优选为10-12.5重量份。
例如，以所述第一无机微纳颗粒为1重量份计，所述基底材料1可以为1重量份、1.5重量份、2重量份、2.33重量份、2.5重量份、3重量份、3.5重量份、4重量份、5重量份、10重量份、20重量份、30重量份、40重量份、49重量份等。
以所述第二无机微纳颗粒为1重量份计，所述基底材料2可以为4重量份、5重量份、6重量份、7重量份、8重量份、9重量份、10重量份、11重量份、12重量份、12.5重量份、13重量份、14重量份、15重量份、16重量份、17重量份、18重量份、19重量份、20重量份、30重量份、40重 量份、49重量份等。
所述包层中的第二无机微纳颗粒在包层中所占的质量百分比小于等于芯层中的第一无机微纳颗粒在芯层中所占的质量百分比。
在本发明优选的一种具体实施方式中，其中，以在第一微纳颗粒和基底材料纺丝原液所占的质量百分比计，所述第一无机微纳颗粒和基底材料1为1-70％，优选为20-40％；
优选的，以在第二微纳颗粒和基底材料纺丝原液所占的质量百分比计，所述第二无机微纳颗粒和基底材料2为1-70％，优选为20-40％。
例如，以在第一微纳颗粒和基底材料纺丝原液所占的质量百分比计，所述第一无机微纳颗粒和基底材料1可以为1％、5％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％或其之间的任意范围；
以在第二微纳颗粒和基底材料纺丝原液所占的质量百分比计，所述第二无机微纳颗粒和基底材料2可以为1％、2％、3％、4％、5％、6％、7％、8％、9％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％或其之间的任意范围；
在本发明优选的一种具体实施方式中，其中，所述干湿法纺丝包括下述步骤：
将所述微纳颗粒和基底材料纺丝原液送至纺丝装置中，然后从纺丝装置中喷丝头的喷丝孔中喷出得到喷出液；
喷出液经过空气层进入到凝固浴中形成初生纤维；
将初生纤维进行水洗、拉伸形成辐射制冷纤维。
优选的，所述喷丝孔的直径为0.01-0.8mm，纤维直径为0.005-0.5mm。
例如，喷丝孔的直径为0.01mm、0.02mm、0.03mm、0.04mm、0.05mm、0.06mm、0.07mm、0.08mm、0.09mm、0.1mm、0.2mm、0.3mm、0.4mm、0.5mm、0.6mm、0.7mm、0.8mm等。
本发明对于纺丝装置不作限制，只要能进行纺丝即可，例如纺丝装置可以为纺丝罐或者纺丝箱。
对于纺丝温度，本发明不作限制，例如纺丝温度可以为10-150℃，例如可以为10℃、20℃、30℃、40℃、50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃等。
对于纺丝速度，本发明不作限制，例如，纺丝速度可以为0.6-3000m/min，例如可以为0.6m/min、1m/min、10m/min、50m/min、100m/min、500m/min、1000m/min、1500m/min、2000m/min、2500m/min、3000m/min等。
优选的，所述微纳颗粒和基底材料纺丝原液的粘度为50-400Pa·s，优选为300Pa·s，例如，所述微纳颗粒和基底材料纺丝原液的粘度可以为50Pa·s、100Pa·s、150Pa·s、200Pa·s、250Pa·s、300Pa·s、350Pa·s、400Pa·s等。
所述的粘度通过本领域公知的粘度测定仪进行测定，例如可以为上海力辰科技的NDJ-5S粘度测定仪、NDJ-8S粘度测定仪或者NDJ-9S粘度测定仪。
优选的，所述空气层的长度为2-500mm，例如，所述空气层的长度为2mm、5mm、10mm、50mm、100mm、150mm、200mm、250mm、300mm、350mm、400mm、450mm、500mm等
所述长度指的从喷丝孔到凝固浴之间的距离。
优选的，所述凝固浴的温度为0-100℃，例如可以为0℃、5℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃等。
对于凝固浴的个数，本发明不作限制，本领域技术人员根据需要设定凝固浴的个数，例如，所述凝固浴包括2个凝固浴，优选的，凝固浴Ⅰ的温度≥凝固浴Ⅱ的温度，所述凝固浴Ⅰ指的是喷出液经过空气层后首次进入的凝固浴为凝固浴Ⅰ，其次再进入的凝固浴为凝固浴Ⅱ。
对于凝固浴，本发明不作限制，例如，所述凝固浴的溶质可以为水、二甲基亚砜(DMSO)、硫酸(H 2SO 4)、硫酸钠(Na 2SO 4)、硫酸胺((NH 4) 2SO 4)；
所述凝固浴中的溶质的质量百分比可以为0-80％，例如，0、1％、5％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％等。
本发明提供了一种辐射制冷纤维，其是通过上述所述的制备方法制备得到。
在本发明优选的一种具体实施方式中，其中，所述辐射制冷纤维的结构为圆形结构、皮芯结构、中空结构、人字型结构、十字型结构、并列型结构、放射型结构、海岛型结构中的至少一种。
本发明提供了一种辐射制冷织物，其是通过上述所述的制备方法制备得到的辐射制冷纤维或者上述所述的辐射制冷纤维进行编织得到。
所述编织可以为针织，也可以为机织。
在本发明优选的一种具体实施方式中，其中，所述辐射制冷织物在太阳光波段的平均反射率大于等于0.9，优选为0.9-0.95。
例如，所述辐射制冷织物在太阳光波段的平均反射率可以为0.90、0.91、0.92、0.93、0.94、0.95等。
在本发明优选的一种具体实施方式中，其中，所述辐射制冷织物在8-13μm波段的平均发射率大于等于0.9，优选为0.90-0.95。
例如，所述辐射制冷织物在8-13μm波段的平均发射率可以为0.90、0.91、0.92、0.93、0.94、0.95等
本发明提供了一种辐射制冷织物的制备方法，其包括下述步骤：
将上述所述的制备方法制备得到的辐射制冷纤维或者上述所述的辐射制冷纤维作为经纱和纬纱进行编织。
所述无机微纳颗粒的进一步优选的粒径为0.4μm，其是由米散射理论结合蒙特卡洛多层介质仿真模型确定，具体操作为：
确定最佳粒径的核心思想是，在保持颗粒体积浓度不变的情况下，对太阳辐射波段(0.3-2.5μm)的反射率达到最大值。
为了简化优化过程，将辐射制冷纤维织成的织物等效为一个平行平板薄膜，该纤维素薄膜对太阳光波段的反射率根据蒙特卡洛多层介质仿真和Mie散射理论给出。
蒙特卡洛多层介质仿真模型是一种统计模型，待仿真模型如图1所示，该平板薄膜模型具有三个特征参数：等效散射系数σ sλ、等效吸收系数κ λ、非对称参数g，仿真需要进行大量迭代(通常大于1000次)，每次迭代打入一个单位能量的光子束(图1中箭头，粗细表示能量，长度代表未经历散射的传播距离，方向代表传播方向)，光子束在表面经历一次镜面反射后进入复合材料，并开始循环进行传播、吸收和散射过程，第n次循环中光子束传播距离为sn，在传播过程中光束由于吸收发生衰减，一次传播结束后，光子束由于散射改变传播方向，进入下一次循环，直至光子束能量被完全吸收或者逃逸出薄膜结构。最终，通过记录并统计每次迭代过程中光子束被反射、透射、吸收的能量，并求算术平均，可以求得薄膜介质的反射率、透射率以及吸收率。
进一步，仿真中第n次循环的传播距离
sn＝-ln(ξ 1)/σ sλ
ξ 1为0-1区间内的随机数。
进一步，每次循环，传播过程中吸收掉的光子能量为
Figure PCTCN2022070532-appb-000001
E为第n次循环中光子束初始能量。
进一步，第n+1次循环中光子束传播方向的偏转角θ由下式决定
Figure PCTCN2022070532-appb-000002
ξ 2为0-1区间内的随机数。
进一步，第n+1次传播方向的方位角φ由下式决定
φ＝2πξ 3
ξ 3为0-1区间内的随机数。
其中
Figure PCTCN2022070532-appb-000003
Figure PCTCN2022070532-appb-000004
Figure PCTCN2022070532-appb-000005
式中
Figure PCTCN2022070532-appb-000006
Figure PCTCN2022070532-appb-000007
Figure PCTCN2022070532-appb-000008
其中k为纤维素折射率虚部，
Figure PCTCN2022070532-appb-000009
d为氧化钛颗粒直径，λ为真空中波长。
Figure PCTCN2022070532-appb-000010
Figure PCTCN2022070532-appb-000011
其中m 0为纤维素折射率，m 1为氧化钛折射率，
Figure PCTCN2022070532-appb-000012
为真空波数，
Figure PCTCN2022070532-appb-000013
ψ n、ξ n为Riccati–Bessel函数。
蒙特卡洛多层介质仿真基本流程图如图2所示。
利用上述模型，计算不同相同体积浓度、不同厚度、不同粒径下等效平板薄膜结构的的反射率数据，计算在预定太阳光谱下、各个等效结构对太阳辐射的加权反射率，根据所述加权反射率，得出不同厚度下微纳颗粒的最佳粒径。
上述步骤中，所述加权反射率为：
Figure PCTCN2022070532-appb-000014
其中I sun(λ)为预定太阳光谱，λ1和λ2分别为加权的波长范围的下限和上限，h为等效结构的厚度。
所述太阳光谱预定范围为0.3-2.5μm。
所述等效结构的扫描厚度范围为100-500μm
所述颗粒的扫描直径范围为100-1000m
得到的太阳光谱加权反射率随粒径和厚度变化如图3所示，图中黑色曲线为反射率等高线，可以看到，对于不同厚度，加权反射率始终在粒径为0.4μm处得到最大值，故氧化钛最佳粒径确定为0.4μm。
本发明通过干湿法纺丝工艺制备掺杂无机微纳颗粒的辐射制冷纤维，通过调控微纳颗粒的尺寸和浓度达到优异的辐射制冷效果，并编织成适用于人体皮肤表面降温的柔性织物，并且所述的制备方法可对纤维内部复合结构进行设计，从而使纤维在具有优异辐射制冷性能的同时兼具良好的力学性能以及高舒适性；使用干湿法纺丝工艺，能够有效减少聚合物在纺丝过程中的降解量，提升纤维的综合性能，制备的辐射制冷纤维与织物具有高柔性，极大增强人体舒适感。
本发明所制备的辐射制冷织物在8-13μm波段的平均发射率≥0.9，在太阳光波段的平均反射率≥0.9。
实施例
本发明对试验中所用到的材料以及试验方法进行一般性和/或具体的描述，在下面的实施例中，如果无其他特别的说明，％表示wt.％，即重量百分数。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试 剂产品。
实施例1
纤维素和TiO 2纺丝原液的制备：配置18000g的7wt.％NaOH/12wt.％尿素的水溶液，加入1600g的纤维素浆粕和400g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，在1500rpm下搅拌30分钟，在8000rpm、10℃下离心10min进行脱泡和除去不溶物得到纤维素和TiO 2在纺丝原液中重量占比为10wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为80℃，纺丝速度为500m/min，并在室温下经直径为0.21mm的喷丝孔喷出经50mm的空气层后至15wt.％H 2SO 4/10wt.％Na 2SO 4/水组成的凝固浴中，凝固浴温度为25℃，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、60℃热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型制得辐射制冷纤维，其截图如图4所示，然后在无牵伸的情况下收集到缠绕辊上。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂20wt.％二氧化钛颗粒的辐射制冷织物，如图9所示。
实施例2
PAN和TiO 2纺丝原液的制备：1500g的PAN聚合物用19305g的DMF为溶剂，配成浓度为7.2wt.％的纺丝溶液，强力搅拌至完全溶解，将645g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)与纺丝溶液混合，并在90℃下搅拌7h，静置脱泡9h后得到PAN和TiO 2在纺丝原液中重量占比为10wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为90℃，纺丝速度为1000m/min，再经直径为0.2mm的喷丝孔喷出经50mm的空气层后至25℃的溶质为DMSO的第一凝固浴(DMSO的浓度为(70wt.％))和20℃的溶质为DMSO的第二凝固浴 (DMSO的浓度为(70wt.％))中，经凝固浴拉伸后获得初生纤维，初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、50℃热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂30wt.％二氧化钛颗粒的辐射制冷织物，如图9所示。
实施例3
壳聚糖和Si 4N 3纺丝原液的制备：1200g的壳聚糖用18000g的4wt.％醋酸水溶液为溶剂，配制6.25wt.％的纺丝溶液，强力搅拌至完全溶解，将800g于100℃真空烘箱中烘干24h的Si 4N 3颗粒(直径为400nm)与纺丝溶液混合经充分搅拌7h后，将溶液置于20℃条件下静置脱泡，最终得到壳聚糖和Si 4N 3在纺丝原液中重量占比为10wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为80℃，纺丝速度为1500m/min。再经直径为0.21mm的针孔喷出，经40mm的空气层后至25℃的15％NaOH/30％无水乙醇的凝固浴中，经凝固浴拉伸后获得初生纤维，初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂40wt.％氮化硅颗粒的辐射制冷织物，如图9所示。
实施例4
PVA和TiO 2纺丝原液的制备：1000g的PVA聚合物用18000g的DMF为溶剂，配成浓度为5.3wt.％的纺丝溶液，将1000g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)在80℃下搅拌均匀，将溶液置于20℃条件下静置脱泡，最终得到PVA和TiO 2在纺丝原液中重量占比为10wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为80℃，纺丝速度为2000m/min。由直径为0.25mm的喷丝板喷出，经过约10mm的空气层进人无水乙醇凝固浴中，在室温下凝固成形，得到初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂50wt.％二氧化钛颗粒的辐射制冷织物，织物如图9所示。
实施例5
纤维素和TiO 2纺丝原液的制备：18000g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入的1200g的纤维素浆粕和800g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，最终得到纤维素和TiO 2在纺丝原液中重量占比为10wt.％的纺丝原液，即第一纺丝原液。
同理，10800g的NMMO溶剂在110℃下加热至完全融化，在剧烈搅拌下加入1200g的纤维素浆粕，得到纤维素在纺丝原液中重量占比为10wt.％的纺丝原液，即第二纺丝原液。
干湿法纺丝制备辐射制冷纤维：将第一纺丝原液和第二纺丝原液分别经计量泵，烛形过滤器后转移至第一纺丝药罐与第二纺丝药罐中，纺丝温度为 110℃，纺丝速度为500m/min，再经皮芯双喷针孔喷出经50mm的空气层后至80℃的水凝固浴中，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到芯层均匀掺杂40wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维，，辐射制冷纤维的截面如图5所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到芯层均匀掺杂40wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维所编织的织物，织物如图9所示。
实施例6
纤维素和TiO 2纺丝原液的制备：将18000g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入1600g的纤维素浆粕和400g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为10wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min。并在室温下经直径为0.2mm的人字型喷丝孔喷出经50mm的空气层后至水凝固浴中，凝固浴温度为80℃，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图6所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织 机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂20wt.％二氧化钛颗粒的辐射制冷织物，织物如图9所示。
实施例7
纤维素和TiO 2纺丝原液的制备：将18000g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入1600g的纤维素浆粕和400g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为10wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min。并在室温下经直径为0.2mm的十字型喷丝孔喷出经50mm的空气层后至80℃的水凝固浴中，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图7所示，将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂20wt.％二氧化钛颗粒的辐射制冷织物，织物如图9所示。
实施例8
纤维素和TiO 2纺丝原液的制备：将8000g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入1500g的纤维素浆粕和500g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为20wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min。并在室温下 经直径为0.2mm的喷丝孔喷出经50mm的空气层后至水凝固浴中，凝固浴温度为80℃，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂25wt.％二氧化钛颗粒的辐射制冷织物，织物如图9所示。
实施例9
纤维素和TiO 2纺丝原液的制备：将2250g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入1000g的纤维素浆粕和500g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为40wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min。并在室温下经直径为0.2mm的喷丝孔喷出经50mm的空气层后至水凝固浴中，凝固浴温度为80℃，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂30wt.％二氧化钛颗粒的辐射制冷织物，织物如图9所示。
实施例10
纤维素和TiO 2纺丝原液的制备：将3267g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入1000g的纤维素浆粕和400g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为20wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min。并在室温下经直径为0.2mm的喷丝孔喷出经50mm的空气层后至水凝固浴中，凝固浴温度为80℃，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂28.6wt.％二氧化钛颗粒的辐射制冷织物，织物如图9所示。
实施例11
纤维素和Si 4N 3纺丝原液的制备：将5000g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入750g的纤维素浆粕和500g于100℃真空烘箱中烘干24h的Si 4N 3颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和Si 4N 3在纺丝原液中重量占比为20wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min。并在室温下经直径为0.2mm的喷丝孔喷出经50mm的空气层后至水凝固浴中，凝固浴温度为80℃，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉 伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂40wt.％氮化硅颗粒的辐射制冷织物，织物如图9所示。
实施例12
纤维素和TiO 2纺丝原液的制备：将3500g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入1200g的纤维素浆粕和300g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为30wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min。并在室温下经直径为0.2mm的喷丝孔喷出经50mm的空气层后至水凝固浴中，凝固浴温度为80℃，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂20wt.％二氧化钛颗粒的辐射制冷织物，织物如图9所示。
实施例13
纤维素和ZnO纺丝原液的制备：将4500g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入1000g的纤维素浆粕和500g于100℃真空烘箱中烘干24h的ZnO颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和ZnO在纺丝原液中重量占比为25wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min。并在室温下经直径为0.2mm的喷丝孔喷出经50mm的空气层后至水凝固浴中，凝固浴温度为80℃，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂33.3wt.％氧化锌颗粒的辐射制冷织物，织物如图9所示。
实施例14
纤维素和TiO 2纺丝原液的制备：将4950g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入49g的纤维素浆粕和1g于100℃真空烘箱中烘干24h的、粒径为10μm的TiO 2颗粒，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为1wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为110℃，纺丝速度为0.6m/min。并在室温下经直径为0.8mm的喷丝孔喷出经50mm的空气层后至水凝固浴中，凝固浴温度为80℃，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，然后将得到的辐 射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂2wt.％二氧化钛颗粒的辐射制冷织物，织物如图9所示。
实施例15
纤维素和TiO 2纺丝原液的制备：将3000g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入3500g的纤维素浆粕和3500g于100℃真空烘箱中烘干24h的、粒径为0.1μm的TiO 2颗粒，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为70wt.％的纺丝原液。
干湿法纺丝制备辐射制冷纤维：将该纺丝原液经计量泵，烛形过滤器后转移至纺丝药罐中，纺丝温度为110℃，纺丝速度为3000m/min。并在室温下经直径为0.01mm的喷丝孔喷出经50mm的空气层后至水凝固浴中，凝固浴温度为80℃，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到辐射制冷纤维，辐射制冷纤维的截面如图4所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到均匀掺杂50wt.％二氧化钛颗粒的辐射制冷织物，织物如图9所示。
实施例16
纤维素和TiO 2纺丝原液的制备：2800g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入的900g的纤维素浆粕和 300g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，最终得到纤维素和TiO 2在纺丝原液中重量占比为30wt.％的纺丝原液，即第一纺丝原液。
同理，7700g的NMMO溶剂在110℃下加热至完全融化，在剧烈搅拌下加入的3000g的纤维素浆粕和300g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，最终得到纤维素和TiO 2在纺丝原液中重量占比为30wt.％的纺丝原液，即第二纺丝原液。
干湿法纺丝制备辐射制冷纤维：将第一纺丝原液和第二纺丝原液分别经计量泵，烛形过滤器后转移至第一纺丝药罐与第二纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min，再经皮芯双喷针孔喷出经50mm的空气层后至80℃的水凝固浴中，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到芯层均匀掺杂25wt.％二氧化钛颗粒、皮层均匀掺杂9wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维，，辐射制冷纤维的截面如图5所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到芯层均匀掺杂25wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维所编织的织物，织物如图9所示。
实施例17
纤维素和TiO 2纺丝原液的制备：将2250g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入1000g的纤维素浆粕和500g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为30wt.％的纺丝原液，即第一纺丝原液。
同理，9450g的NMMO溶剂在110℃下加热至完全融化，在剧烈搅拌下加入的3750g的纤维素浆粕和300g于100℃真空烘箱中烘干24h的TiO 2颗 粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，最终得到纤维素和TiO 2在纺丝原液中重量占比为30wt.％的纺丝原液，即第二纺丝原液。
干湿法纺丝制备辐射制冷纤维：将第一纺丝原液和第二纺丝原液分别经计量泵，烛形过滤器后转移至第一纺丝药罐与第二纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min，再经皮芯双喷针孔喷出经50mm的空气层后至80℃的水凝固浴中，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到芯层均匀掺杂30wt.％二氧化钛颗粒、皮层均匀掺杂7wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维，辐射制冷纤维的截面如图5所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到芯层均匀掺杂30wt.％二氧化钛颗粒、皮层均匀掺杂7wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维所编织的织物，织物如图9所示。
实施例18
纤维素和TiO 2纺丝原液的制备：将8500g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入1200g的纤维素浆粕和300g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为15wt.％的纺丝原液，即第一纺丝原液。
同理，5667g的NMMO溶剂在110℃下加热至完全融化，在剧烈搅拌下加入的900g的纤维素浆粕和100g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，最终得到纤维素和TiO 2在纺丝原液中重量占比为15wt.％的纺丝原液，即第二纺丝原液。
干湿法纺丝制备辐射制冷纤维：将第一纺丝原液和第二纺丝原液分别经计量泵，烛形过滤器后转移至第一纺丝药罐与第二纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min，再经皮芯双喷针孔喷出经50mm的空气层后 至80℃的水凝固浴中，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到芯层均匀掺杂20wt.％二氧化钛颗粒、皮层均匀掺杂10wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维，辐射制冷纤维的截面如图5所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到芯层均匀掺杂20wt.％二氧化钛颗粒、皮层均匀掺杂10wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维所编织的织物，织物如图9所示。
实施例19
纤维素和Si 4N 3纺丝原液的制备：将2550g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入450g的纤维素浆粕和300g于100℃真空烘箱中烘干24h的Si 4N 3颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，得到纤维素和Si 4N 3在纺丝原液中重量占比为15wt.％的纺丝原液。，即第一纺丝原液。
同理，3400g的NMMO溶剂在110℃下加热至完全融化，在剧烈搅拌下加入的570g的纤维素浆粕和30g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为400nm)，将溶液置于20℃条件下静置脱泡，最终得到纤维素和TiO 2在纺丝原液中重量占比为15wt.％的纺丝原液，即第二纺丝原液。
干湿法纺丝制备辐射制冷纤维：将第一纺丝原液和第二纺丝原液分别经计量泵，烛形过滤器后转移至第一纺丝药罐与第二纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min，再经皮芯双喷针孔喷出经50mm的空气层后至80℃的水凝固浴中，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到芯层均匀掺杂40wt.％氮化硅颗粒、皮层均匀掺杂5wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维，辐射制冷纤维的截面如图5所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到芯层均匀掺杂40wt.％氮化硅颗粒、皮层均匀掺杂5wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维所编织的织物，织物如图9所示。
实施例20
纤维素和TiO 2纺丝原液的制备：将9900g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入50g的纤维素浆粕和50g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为5μm)，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为1wt.％的纺丝原液，即第一纺丝原液。
同理，2475g的NMMO溶剂在110℃下加热至完全融化，在剧烈搅拌下加入的200g的纤维素浆粕和50g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为5μm)，将溶液置于20℃条件下静置脱泡，最终得到纤维素和TiO 2在纺丝原液中重量占比为1wt.％的纺丝原液，即第二纺丝原液。
干湿法纺丝制备辐射制冷纤维：将第一纺丝原液和第二纺丝原液分别经计量泵，烛形过滤器后转移至第一纺丝药罐与第二纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min，再经皮芯双喷针孔喷出经50mm的空气层后至80℃的水凝固浴中，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到芯层均匀掺杂50wt.％二氧化钛颗粒、皮层均匀掺杂20wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维，辐射制冷纤维的截面如图5所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由 此得到芯层均匀掺杂50wt.％二氧化钛颗粒、皮层均匀掺杂20wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维所编织的织物，织物如图9所示。
实施例21
纤维素和TiO 2纺丝原液的制备：将2143g的4-甲基吗啉-N-氧化物(NMMO)溶剂在110℃下加热至完全融化，在剧烈搅拌下加入4900g的纤维素浆粕和100g于100℃真空烘箱中烘干24h的TiO 2颗粒(直径为10μm)，将溶液置于20℃条件下静置脱泡，得到纤维素和TiO 2在纺丝原液中重量占比为70wt.％的纺丝原液，即第一纺丝原液。
同理，2143g的NMMO溶剂在110℃下加热至完全融化，在剧烈搅拌下加入的4900g的纤维素浆粕和100g于100℃真空烘箱中烘干24h的ZnO颗粒(直径为10μm)，将溶液置于20℃条件下静置脱泡，最终得到纤维素和ZnO在纺丝原液中重量占比为70wt.％的纺丝原液，即第二纺丝原液。
干湿法纺丝制备辐射制冷纤维：将第一纺丝原液和第二纺丝原液分别经计量泵，烛形过滤器后转移至第一纺丝药罐与第二纺丝药罐中，纺丝温度为110℃，纺丝速度为500m/min，再经皮芯双喷针孔喷出经50mm的空气层后至80℃的水凝固浴中，经凝固浴拉伸后获得初生纤维。初生纤维进行集束、预热浴拉伸、沸水或蒸汽浴拉伸、热水洗、上油、干燥致密化、干热拉伸、卷曲、热定型得到皮芯层均匀掺杂2wt.％二氧化钛颗粒、皮层均匀掺杂2wt.％氧化锌颗粒的皮芯结构辐射制冷纤维，辐射制冷纤维的截面如图5所示，然后将得到的辐射制冷纤维收集到缠绕辊。
辐射制冷织物的制备：将得到的辐射制冷纤维分别作为纬纱和经纱，为避免过强的摩擦作用磨损纤维，调整卷布辊经纱使张力均匀且松紧适度；根据经纬交织的变化规律，利用开口机构按序带动上下两层经纱形成梭口通道；在梭子上缠绕纤维作为纬纱，将梭子往复交替通过梭口通道进行编织，与织机上的其他机构相配合调整纬纱的排列密度，在卷布辊上卷绕引离织物，由此得到芯层均匀掺杂2wt.％二氧化钛颗粒、皮层均匀掺杂2wt.％氧化锌颗粒的皮芯结构辐射制冷纤维所编织的织物，织物如图9所示。
对比例1
对比例1和实施例1的区别仅在于，对比例1是采用静电纺丝法制备， 其具体操作步骤参见中国专利申请CN110042564A中实施例1所述的方法进行，得到辐射制冷纤维。
对比例2
对比例2和实施例1的区别仅在于，对比例2中不含有无机微纳颗粒所得到的辐射制冷纤维。
表1实施例和对比例中各种组分的用量表
Figure PCTCN2022070532-appb-000015
Figure PCTCN2022070532-appb-000016
实验例
将实施例1-14所得到的辐射制冷织物以及对比例1-2所得到的辐射制冷织物进行实验，具体操作方法为：利用UV-VIS-NIR分光光度计结合积分球测试织物在太阳辐射(0.3-2.5μm)波段的反射率，利用傅里叶变换红外光谱仪结合积分球测试织物在中红外(8-13μm)波段的发射率。得到的结果如表2所示。
表2辐射制冷织物在太阳波段的反射率结果以及在中红外波段的平均发射率结果
  在8-13μm波段的平均发射率 在太阳光波段的平均反射率
实施例1 0.92 0.92
实施例2 0.93 0.91
实施例3 0.92 0.90
实施例4 0.91 0.93
实施例5 0.92 0.91
实施例6 0.92 0.92
实施例7 0.92 0.92
实施例8 0.95 0.95
实施例9 0.95 0.95
实施例10 0.95 0.95
实施例11 0.92 0.94
实施例12 0.93 0.93
实施例13 0.94 0.94
实施例14 0.90 0.90
实施例15 0.91 0.90
实施例16 0.95 0.94
实施例17 0.95 0.94
实施例18 0.93 0.92
实施例19 0.93 0.92
实施例20 0.90 0.90
实施例21 0.90 0.90
对比例1 0.90 0.85
对比例2 0.90 0.60
从表2可以看出，实施例所述的辐射制冷织物在8-13μm波段的平均发射率在0.90以上，在太阳光波段的平均反射率也在0.90以上，说明使用本发明所述的辐射制冷纤维所制得的织物具有较好的性能。
将对比例1和实施例1进行对比，其区别仅在于使用的方法不同，对比例1使用的是静电纺丝法制备辐射制冷纤维，其在8-13μm波段的平均发射率以及在太阳光波段的平均反射率的结果如表2所示，从表2可以看出，实施例1所述织物在8-13μm波段的平均发射率为0.92，在太阳光波段的平均反射率未0.92，而对比例1分别为0.90和0.85，说明采用本发明所述的方法制备得到的辐射制冷纤维所编织的织物具有较好的效果。
将对比例2和实施例1进行对比，其区别在于，对比例2中不含有无机微纳颗粒制备辐射制冷纤维，所编织的织物在8-13μm波段的平均发射率以及在太阳光波段的平均反射率的结果如表2所示，从表2可以看出，实施例1所述织物在8-13μm波段的平均发射率为0.92，在太阳光波段的平均反射率未0.92，而对比例2分别为0.90和0.60，说明含有无机微纳颗粒的织物具有较好的效果。
综上所述，本发明使用干湿法纺丝工艺制备掺杂无机微纳颗粒的辐射制冷纤维，具有优异的辐射制冷效果，并编织成适用于人体皮肤表面降温的柔性织物，所制备的辐射制冷织物在8-13μm波段的平均发射率≥0.9，在太阳光波段的平均反射率≥0.9。
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。

Claims (19)

  1. 一种辐射制冷纤维的制备方法，其包括下述步骤：
    将无机微纳颗粒和基底材料混合得到微纳颗粒和基底材料纺丝原液；
    将所述微纳颗粒和基底材料纺丝原液进行干湿法纺丝，得到辐射制冷纤维。
  2. 根据权利要求1所述的制备方法，其中，以所述无机微纳颗粒为1重量份计，所述基底材料为1-999重量份，优选为1.5-4重量份，进一步优选为2.33-3重量份。
  3. 根据权利要求1或2所述的制备方法，其中，所述无机微纳颗粒选自二氧化钛、二氧化硅、氧化锌、碳化硅、氮化硅、硫化锌、氧化铝、氧化铁、氮化硼、氧化镁、硫酸钡、碳酸钡和硅酸铝中的一种或两种以上，优选为二氧化钛、氧化锌或氮化硅。
  4. 根据权利要求1-3中任一项所述的制备方法，其中，所述基底材料选自纤维素、聚乳酸、聚乙烯、聚丙烯、聚酰胺、聚氯乙烯、聚苯乙烯、聚醋酸乙烯酯、聚乙烯醇、聚丙烯腈、聚对苯甲酰胺、聚对苯二甲酸乙二醇酯、壳聚糖、聚对苯二甲酰对苯二胺、间位芳香族聚酰胺、聚偏氟乙烯、二丁酰甲壳质、聚苯并咪唑和聚苯并双二噁唑中的一种或两种以上，优选为纤维素、聚丙烯腈、聚乙烯醇或壳聚糖。
  5. 根据权利要求1-4中任一项所述的制备方法，其中，将无机微纳颗粒和基底材料混合得到微纳颗粒和基底材料纺丝原液包括将无机微纳颗粒和基底材料加入到溶剂中得到微纳颗粒和基底材料纺丝原液。
  6. 根据权利要求5所述的制备方法，其中，所述溶剂选自水、DMF、DMAc、硝酸、醋酸、甲苯、环己烷、四氢呋喃-二氧六环共混溶液、苯、四氯化碳、醋酸戊酯、丙酮、4-甲基吗啉-N-氧化物、N-乙基吡啶氯化物、1-丁基-3-甲基咪唑氯化物、1-乙基-3-甲基咪唑氯化物、1-烯丙基3-甲基咪唑氣盐、1-丁基-3-甲基咪唑醋酸盐、1-乙基-3-甲基咪唑醋酸盐、1-乙基-3-甲基咪唑磷酸二乙酯盐、NaOH/尿素/水、NaOH/硫脲/水、NaOH/硫脲/尿素/水、尿素/已内酰胺/NaOH/水、NaOH/ZnO/水、NaOH/乙醇/水、四氢化萘、萘、矿物油、石蜡油、十氢萘和石蜡中的一种或两种以上，优选为NaOH/尿素/水、DMF、 醋酸或4-甲基吗啉-N-氧化物。
  7. 根据权利要求1-6中任一项所述的制备方法，其中，所述无机微纳颗粒的粒径为0.03-25μm，优选为0.1-10μm，进一步优选为0.4μm。
  8. 根据权利要求1-7中任一项所述的制备方法，其中，以在纺丝原液所占的重量百分比计，所述无机微纳颗粒和基底材料为1-70％，优选为20-40％。
  9. 根据权利要求1-8中任一项所述的制备方法，其中，所述无机微纳颗粒包括第一无机微纳颗粒和第二无机微纳颗粒；优选的，所述第一无机微纳颗粒和所述第二无机微纳颗粒是相同的无机微纳颗粒或者是不同的无机微纳颗粒。
  10. 根据权利要求9所述的制备方法，其中，所述基底材料包括基底材料1和基底材料2，优选的，所述基底材料1和所述基底材料2是相同的基底材料或者不同的基底材料。
  11. 根据权利要求10所述的制备方法，其中，所述第一无机微纳颗粒和所述基底材料1混合形成第一微纳颗粒和基底材料纺丝原液；优选的，以所述第一无机微纳颗粒为1重量份计，所述基底材料1为1-49重量份，优选为1.5-4重量份，进一步优选为2.33-3重量份；
    优选的，所述第二无机微纳颗粒和所述基底材料2混合形成第二微纳颗粒和基底材料纺丝原液，优选的，所述第二无机微纳颗粒为0或者以所述第二无机微纳颗粒为1重量份计，所述基底材料2为4-49重量份，优选为9-19重量份，进一步优选为10-12.5重量份。
  12. 根据权利要求11所述的制备方法，其中，以在第一微纳颗粒和基底材料在纺丝原液所占的质量百分比计，所述第一无机微纳颗粒和基底材料1为1-70％，优选为20-40％；
    优选的，以在第二微纳颗粒和基底材料在纺丝原液所占的质量百分比计，所述第二无机微纳颗粒和基材材料2为1-70％，优选为20-40％。
  13. 根据权利要求1-12中任一项所述的制备方法，其中，所述干湿法纺丝包括下述步骤：
    将所述微纳颗粒和基底材料纺丝原液送至纺丝装置中，然后从纺丝装置中喷丝头的喷丝孔中喷出得到喷出液；
    喷出液经过空气层进入到凝固浴中形成初生纤维；
    将初生纤维进行水洗、拉伸形成辐射制冷纤维。
  14. 根据权利要求1-13中任一项所述的制备方法，其中，所述微纳颗粒和基底材料纺丝原液的粘度为50-400Pa·s，优选为300Pa·s。
  15. 一种辐射制冷纤维，其通过权利要求1-14中任一项所述的制备方法制备得到。
  16. 根据权利要求15所述的辐射制冷纤维，所述辐射制冷纤维的结构为圆形结构、皮芯结构、中空结构、人字型结构、十字型结构、并列型结构、放射型结构、海岛型结构中的至少一种。
  17. 一种辐射制冷织物，其是将权利要求1-14中任一项所述的制备方法制备得到的辐射制冷纤维或者权利要求15-16中任一项所述的辐射制冷纤维进行编织得到。
  18. 根据权利要求17所述的辐射制冷织物，其中，所述辐射制冷织物在太阳光波段的平均反射率大于等于0.9，优选为0.9-0.95。
  19. 根据权利要求17所述的辐射制冷织物，其中，所述辐射制冷织物在8-13μm波段的平均发射率大于等于0.9，优选为0.90-0.95。
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