WO2021203867A1

WO2021203867A1 - Radiative cooling fiber and preparation method for fabric thereof

Info

Publication number: WO2021203867A1
Application number: PCT/CN2021/078388
Authority: WO
Inventors: 陶光明; 曾少宁
Original assignee: 华中科技大学
Priority date: 2020-04-05
Filing date: 2021-03-01
Publication date: 2021-10-14
Also published as: CN111455483A

Abstract

A radiative cooling fiber and a preparation method for a fabric thereof, the method comprising: mixing inorganic micro-nano particles and a polymer substrate material according to a predetermined weight ratio so as to obtain a composite material masterbatch; and molding by compounding and extruding the composite material masterbatch in a spinning assembly, and obtaining a radiative cooling fiber after winding. In the present invention, high-concentration inorganic micro-nano particles are introduced into a polymer fiber by using a melt composite spinning method, by precisely regulating the size of the micro-nano particles and the internal composite structure of the fiber, the fiber has a high mechanical strength and weaving performance while having an excellent daytime radiative cooling performance, obtaining a radiative cooling fabric suitable for cooling the surface of the human skin; in addition present invention also has the advantages of large-scale mass preparation, low costs, and high production efficiency.

Description

一种辐射制冷纤维及其织物的制备方法Radiant refrigeration fiber and preparation method of its fabric

技术领域Technical field

本发明涉及一种辐射制冷领域，特别是涉及一种辐射制冷纤维及其织物的制备方法。The invention relates to the field of radiant refrigeration, in particular to a preparation method of a radiant refrigeration fiber and its fabric.

背景技术Background technique

能源是人类生存的重要基础，推动着社会的发展和进步。巨大的能源消耗在产生经济损失的同时，也带来温室气体的过度排放，导致严峻的气候问题，使高温等极端天气更加剧烈和频繁。由此产生的空间供热和制冷需求成为现在住宅和商业能源消耗的主要部分，对人类可持续发展构成巨大挑战。面对巨大的能源消耗和高温所带来的健康和经济的威胁。个人热管理作为一种只向个体及其局部环境提供加热或冷却的技术，正在逐渐成为一种个性化的高效解决方案。在实现无源热调节性能的同时，减少人类对空调等低能效冷却方法的依赖，有效降低整个建筑的降温成本，更加节能经济地满足个性化热舒适需求。Energy is an important foundation for human survival and promotes the development and progress of society. While huge energy consumption produces economic losses, it also brings excessive emissions of greenhouse gases, leading to severe climate problems, and making extreme weather such as high temperatures more intense and frequent. The resulting demand for space heating and cooling has become the main part of residential and commercial energy consumption, posing a huge challenge to the sustainable development of mankind. Face the health and economic threats brought by huge energy consumption and high temperature. As a technology that only provides heating or cooling to individuals and their local environment, personal thermal management is gradually becoming a personalized and efficient solution. While achieving passive thermal regulation performance, it reduces human dependence on inefficient cooling methods such as air conditioners, effectively reduces the cooling cost of the entire building, and meets the needs of personalized thermal comfort in a more energy-efficient and economical manner.

随着制冷技术的迅速发展，基于智能降温材料的零能耗辐射制冷技术应运而生。辐射制冷技术通过材料的选择和结构的设计，使物体在太阳辐射(0.3μm-2.5μm)波长范围实现高反射率，极大阻挡人体通过太阳辐射的热量输入。并且同时利用在人体辐射波段高发射率或透明的材料，将自身热量以电磁波的形式通过“大气窗口”排放到温度接近绝对零度的外部太空，达到自身冷却的目的，有效地实现了零能耗降温。尽管辐射制冷已逐渐成为研究热点，但现有的技术方法要应用于人体降温织物仍具有一定的局限性。With the rapid development of refrigeration technology, zero-energy radiant refrigeration technology based on intelligent cooling materials has emerged. The radiant refrigeration technology enables objects to achieve high reflectivity in the solar radiation (0.3μm-2.5μm) wavelength range through the selection of materials and the design of the structure, which greatly blocks the human body's heat input through solar radiation. At the same time, it uses materials with high emissivity or transparency in the human body's radiation band to discharge its own heat in the form of electromagnetic waves through the "atmospheric window" to the outer space where the temperature is close to absolute zero, achieving the purpose of self-cooling and effectively achieving zero energy consumption. Cool down. Although radiant refrigeration has gradually become a research hotspot, the existing technical methods still have certain limitations when applied to human body cooling fabrics.

美国哥伦比亚大学Yuan Yang教授团队基于相位反转的方法，利用P(VdF-HFP)/丙酮/水混合溶液制备了具有5μm的微孔和50nm-500nm的纳米孔的分级多孔聚合物涂层用于辐射制冷。由于微纳米孔可以有效地散射太阳辐射，且P(VdF-HFP)涂层在8μm-13μm范围内存在多个吸收峰能有效地辐射热量，所以厚度约300μm的涂层实现了96％的高太阳光反射率和97％的高热发射率，在阳光下测试被动辐射制冷性能可使温度下降约6℃，产生约96W m ^-2的冷却功率。 Based on the phase reversal method, the team of Professor Yuan Yang of Columbia University in the United States prepared a hierarchical porous polymer coating with 5μm micropores and 50nm-500nm nanopores using a P(VdF-HFP)/acetone/water mixed solution. Radiant cooling. Because the micro-nanopores can effectively scatter solar radiation, and the P(VdF-HFP) coating has multiple absorption peaks in the range of 8μm-13μm, which can effectively radiate heat, the coating with a thickness of about 300μm achieves a height of 96%. Sunlight reflectivity and 97% high heat emissivity, testing passive radiant cooling performance under sunlight can reduce the temperature by about 6°C and produce a cooling power of ^{about 96W m -2.}

另一种辐射制冷涂层，如中国专利CN 110628325 A所公开的，包括反射隔热层以及罩面保护层，反射隔热层由耐高温基材、耐高温辐射制冷颜料以及其他助剂构成，保护层包括二氧化钛溶胶以及硅溶胶，此发明制备的涂层对可见光以及红外光具有大于80％的反射率，并在大气窗口波段具有大于80％的红外发射率，且对紫外线起到阻隔作用，能够在温度为-40℃-500℃的环境中长期使用。尽管涂层材料具有辐射制冷性能，能够为物体提供散热和抗紫外的保护作用，但其不具备可穿戴性，无法用于人体的局部降温。Another type of radiant refrigeration coating, as disclosed in Chinese Patent CN 110628325 A, includes a reflective heat insulation layer and a cover protective layer. The reflective heat insulation layer is composed of a high temperature resistant substrate, a high temperature resistant radiant cooling pigment and other additives. The protective layer includes titanium dioxide sol and silica sol. The coating prepared by this invention has a reflectivity of more than 80% for visible light and infrared light, and has an infrared emissivity of more than 80% in the atmospheric window band, and has a blocking effect on ultraviolet rays. It can be used for a long time in an environment with a temperature of -40℃-500℃. Although the coating material has radiant cooling properties and can provide heat dissipation and anti-ultraviolet protection for objects, it is not wearable and cannot be used for local cooling of the human body.

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8μm-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。薄膜态的辐射制冷材料又，如中国专利CN 109968769 A所公开的，也被应用于生产生活，将微米颗粒和聚合物溶液混合，通过挤压的方式制备薄膜作为日光反射层，将微纳粉末和荧光剂混合物喷涂制备紫外吸收荧光粗糙层，此方法制备的薄膜的太阳光能量平均反射率达到97％，大气窗口平均辐射率达到95％。但此方法步骤复杂，无法一步成型，且制备的薄膜柔性差，无法用于人体降温，仅适用于工业领域。而另一种添加二氧化钛空心球的高分子辐射制冷薄膜，例如中国专利CN109705819A，则是将二氧化钛空心球与偏氟乙烯和六氟丙烯的共聚物混合均匀后涂布制备，实现8μm-13μm范围的高发射率和太阳光辐射波段的高反射率。虽然以上薄膜材料具有有效的降温辐射制冷性能，但是其缺乏透气性和舒适性，且方法无法大规模生产，不适用于人体降温。 A team from the University of Colorado in the United States has prepared a random glass-polymer hybrid metamaterial. The transparent polymer methylpentene is embedded with randomly distributed resonance dielectric SiO ₂ microspheres and a silver film is used as a backing. The prepared 200nm silver The 50μm thick metamaterial backed by the coating can reflect about 96% of solar radiation, has a high emissivity of more than 93% between 8μm and 13μm, and can generate a radiant cooling power of ^{more than 100W m -2 under direct sunlight.} The thin-film radiant refrigeration material, as disclosed in Chinese Patent CN 109968769 A, is also used in production and life. Micron particles and polymer solution are mixed, and the film is prepared by extrusion as the solar reflective layer, and the micro-nano powder Spraying with a fluorescent agent mixture to prepare an ultraviolet absorbing fluorescent rough layer, the average solar energy reflectance of the film prepared by this method reaches 97%, and the average radiance of the atmospheric window reaches 95%. However, this method has complicated steps, cannot be formed in one step, and the prepared film has poor flexibility, cannot be used for human body cooling, and is only suitable for industrial fields. Another type of polymer radiant refrigeration film with titanium dioxide hollow spheres, such as Chinese patent CN109705819A, is prepared by uniformly mixing titanium dioxide hollow spheres with a copolymer of vinylidene fluoride and hexafluoropropylene and coating to achieve a range of 8μm-13μm High emissivity and high reflectivity in the solar radiation band. Although the above film materials have effective cooling and radiant cooling performance, they lack air permeability and comfort, and the method cannot be mass-produced, and is not suitable for human body cooling.

相较于薄膜态，纤维态的辐射制冷材料，例如中国专利CN110042564A所公开的，其所具备的透气透湿特性和柔性更适合人体热管理，将单分散性好的高发射的辐射粒子SiO ₂微球均匀分散在聚合物，例如PE、PA6、PMMA和PVDF溶液中，通过静电纺丝得到纤维膜，具备给人体皮肤表面辐射降温的能力，但此方法生产效率低，工艺复杂，设备成本高，而且生产的纤维强度低，无法用于人体辐射制冷织物。 Compared with the film state, the fibrous radiant refrigeration material, such as disclosed in Chinese Patent CN110042564A, has the air and moisture permeability characteristics and flexibility that are more suitable for human thermal management. It combines the SiO _{2 radiant particles with good monodispersity and high emission.} The microspheres are uniformly dispersed in polymers, such as PE, PA6, PMMA and PVDF solutions, and the fibrous membrane is obtained by electrostatic spinning, which has the ability to radiate and cool the human skin surface, but this method has low production efficiency, complex process and high equipment cost , And the produced fiber has low strength and cannot be used for human body radiant cooling fabrics.

熔融纺丝的方法可以实现大批量纤维的快速制备，工艺简单且生产效率高。如中国专利CN102677218A，其利用熔融纺丝法制备的抗紫外聚苯硫醚纤维内含90％-99.9％的聚苯硫醚树脂和0.01％-10％光稳定剂，具有较高的紫外光稳定性能和光稳定性能持续时间。如中国专利CN103668538B所公开的方案，将抗紫外型母粒，例如纳米二氧化钛1％-5％，纳米氮化钛1％-5％及生物质聚酯，和生物质聚酯切片进行熔融纺丝还可制备具有抗紫外功效的生物质聚酯纤维。但以上利用熔融纺丝法制备的纤维，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。The melt-spinning method can realize the rapid preparation of large batches of fibers, the process is simple and the production efficiency is high. For example, Chinese patent CN102677218A, its UV resistant polyphenylene sulfide fiber prepared by melt spinning method contains 90%-99.9% polyphenylene sulfide resin and 0.01%-10% light stabilizer, which has high UV light stability Performance and light stability can last for a long time. As disclosed in the Chinese patent CN103668538B, the anti-ultraviolet masterbatch, such as nano-titanium dioxide 1%-5%, nano-titanium nitride 1%-5% and biomass polyester, and biomass polyester chips are melt-spinned It can also prepare biomass polyester fiber with anti-ultraviolet effect. However, the above-mentioned fibers prepared by the melt spinning method are limited to anti-ultraviolet function, cannot regulate solar radiation and human thermal radiation, and cannot be used for personal thermal management.

中国专利CN110685031A所公开的，利用熔融纺丝的方法将粒径为1μm-20μm、质量分数为1％-17％的功能填料，例如SiO ₂、SiC、TiO ₂、CaCO ₃、BaSO ₄、Si ₃N ₄、ZnO、Al ₂O ₃、Fe ₂O ₃、ZrO ₂或玉石粉体，与基体材料，例如聚丙烯、聚乙烯醇、聚氯乙烯、聚氨酯、聚酯、聚乙烯、聚酰胺、聚甲基丙烯酸甲酯、聚偏氟乙烯或聚丙烯腈，混合可制备辐射制冷纤维，进一步编织可得到的辐射制冷面料对太阳辐射波段具有大于60％的反射率，在人体热辐射波段具有大于80％的发射率，良好的降温效果可用于制备有降温需求的纺织品。但此方法未能精确调控功能填料的粒径范围且掺杂在纤维内部的功能填料质量分数低，在太阳辐射波段反射率低，因此日间辐射性能差；另一方面，此发明未能实现对于纤维内部的结构控制，限制其辐射制冷效果和力学性能。 Chinese patent CN110685031A discloses that functional fillers with a particle size of 1μm-20μm and a mass fraction of 1%-17%, such as SiO ₂ , SiC, TiO ₂ , CaCO ₃ , BaSO ₄ , and Si _{3 are made by melt spinning method.} N ₄ , ZnO, Al ₂ O ₃ , Fe ₂ O ₃ , ZrO ₂ or jade powder, and matrix materials, such as polypropylene, polyvinyl alcohol, polyvinyl chloride, polyurethane, polyester, polyethylene, polyamide, poly Methyl methacrylate, polyvinylidene fluoride or polyacrylonitrile can be mixed to prepare radiant refrigeration fiber. The radiant refrigeration fabric obtained by further weaving has a reflectivity of more than 60% for the solar radiation band and more than 80% for the heat radiation band of the human body. % Emissivity and good cooling effect can be used to prepare textiles that require cooling. However, this method fails to precisely control the particle size range of the functional filler and the mass fraction of the functional filler doped inside the fiber is low, and the reflectivity in the solar radiation band is low, so the daytime radiation performance is poor; on the other hand, this invention has not been realized. For the control of the internal structure of the fiber, the radiant cooling effect and mechanical properties are limited.

综上所述，现有辐射制冷材料存在以下缺点：(1)多为涂层或薄膜态，透气性和舒适性不足无法用于人体皮肤降温；(2)静电纺丝等方法工艺复杂、成本高；(3)现有利用熔融纺丝法制备的复合纤维日间辐射制冷效果较差。所以，现缺乏利用熔融复合纺丝方法引入高浓度无机微纳颗粒制备辐射制冷纤维的技术，并通过精确调控微纳颗粒尺寸和纤维内部复合结构，使纤维在具备优异的辐射制冷性能的同时兼具高机械强度和可编织性能，从而制备适用于人体皮肤降温的高舒适性织物，并实现大规模批量制备，具有成本低、生产效率高的优点。To sum up, the existing radiant refrigeration materials have the following shortcomings: (1) Most of them are in the form of coatings or films, and the air permeability and comfort are not enough to be used for human skin cooling; (2) Electrospinning and other methods are complicated and cost-effective. High; (3) The existing composite fiber prepared by melt spinning has a poor daytime radiant refrigeration effect. Therefore, there is currently a lack of technology for preparing radiant refrigeration fibers by introducing high-concentration inorganic micro-nano particles by the melt composite spinning method, and by accurately adjusting the size of the micro-nano particles and the internal composite structure of the fiber, the fiber has excellent radiant refrigeration performance and at the same time. It has high mechanical strength and knitability, so as to prepare high-comfort fabrics suitable for human skin cooling, and realize large-scale batch preparation, and has the advantages of low cost and high production efficiency.

发明内容Summary of the invention

有鉴于此，本发明所要解决的技术问题是提供一种辐射制冷纤维及其织物的批量制备方法，能够利用熔融复合纺丝引入高浓度微纳颗粒，并且能够精确调控微纳颗粒的尺寸和纤维结构。In view of this, the technical problem to be solved by the present invention is to provide a batch preparation method of radiant refrigeration fiber and its fabric, which can introduce high-concentration micro-nano particles by melt composite spinning, and can precisely control the size and fiber of micro-nano particles. structure.

为了解决上述问题，本发明主要提供如下技术方案：In order to solve the above-mentioned problems, the present invention mainly provides the following technical solutions:

一种辐射制冷纤维的制备方法，包括：A preparation method of radiant refrigeration fiber, including:

将无机微纳颗粒和聚合物基底材料按照预定的重量比例混合，制得复合材料母粒；Mixing the inorganic micro-nano particles and the polymer base material according to a predetermined weight ratio to prepare a composite material masterbatch;

将复合材料母粒在纺丝组件中复合挤出成型，经卷绕后得到辐射制冷纤维。The composite material masterbatch is compounded and extruded in the spinning assembly, and the radiant refrigerating fiber is obtained after winding.

优选的，所述将无机微纳颗粒和聚合物基底材料按照预定的重量比例混合，制得复合材料母粒，包括，Preferably, the mixing of the inorganic micro-nano particles and the polymer base material according to a predetermined weight ratio to prepare a composite material masterbatch includes:

将第一无机微纳颗粒和第一聚合物基底材料按照预定的第一重量比例混合均匀，制得第一复合材料母粒，将第二无机微纳颗粒和第二聚合物基底材料按照预定的第二重量比例混合均匀，制得第二复合材料母粒；The first inorganic micro-nano particles and the first polymer base material are mixed uniformly according to a predetermined first weight ratio to prepare a first composite material masterbatch, and the second inorganic micro-nano particles and the second polymer base material are mixed according to a predetermined first weight ratio. The second weight ratio is evenly mixed to obtain the second composite material masterbatch;

将复合材料母粒在纺丝组件中挤出成型，经卷绕后得到辐射制冷纤维，包括，将第一复合材料母粒作为第一组分，第二复合材料母粒作为第二组分，在纺丝组件中复合挤出成型，经卷绕后得到辐射制冷纤维。The composite material masterbatch is extruded and formed in the spinning assembly, and the radiant refrigerating fiber is obtained after winding. The first composite material masterbatch is used as the first component, and the second composite material masterbatch is used as the second component. Compound extrusion molding in the spinning assembly, after winding to obtain radiant refrigeration fiber.

优选的，所述第一复合材料母粒中无机微纳颗粒的重量占比为1％-80％，所述第二复合材料母粒中无机微纳颗粒的重量占比为0-20％，并且所述第一复合材料母粒中无机微纳颗粒的重量占比大于等于第二复合材料母粒中无机微纳颗粒的重量占比。Preferably, the weight proportion of the inorganic micro-nano particles in the first composite material masterbatch is 1%-80%, and the weight proportion of the inorganic micro-nano particles in the second composite material masterbatch is 0-20%, And the weight proportion of the inorganic micro-nano particles in the first composite material master particle is greater than or equal to the weight proportion of the inorganic micro-nano particles in the second composite material master particle.

优选的，所述第一聚合物基底材料与所述第二聚合物基底材料，可以相同也可以不同；所述第一无机微纳颗粒与第二无机微纳颗粒，可以相同也可以不同。Preferably, the first polymer base material and the second polymer base material may be the same or different; the first inorganic micro-nano particles and the second inorganic micro-nano particles may be the same or different.

优选的，还包括至少一种第三组分，所述至少一种第三组分与第一、第二组分一起在纺丝组件中复合挤出成型，经卷绕后得到辐射制冷纤维；Preferably, it also includes at least one third component, and the at least one third component, together with the first and second components, are compositely extruded and molded in the spinning assembly, and the radiant refrigeration fiber is obtained after winding;

所述至少一种第三组分为第三无机微纳颗粒和第三聚合物基底材料按照第三重量比例制得的至少一种第三复合材料母粒。The at least one third component is at least one third composite material master particle prepared by third inorganic micro-nano particles and a third polymer base material according to a third weight ratio.

优选的，所述至少一种第三复合材料母粒中无机微纳颗粒的重量占比为1％-80％，并且所述至少一种第三复合材料母粒中无机微纳颗粒的重量占比大于等于第二复合材料母粒中无机微纳颗粒的重量占比。Preferably, the weight of the inorganic micro-nano particles in the at least one third composite material masterbatch is 1%-80%, and the weight of the inorganic micro-nano particles in the at least one third composite material masterbatch is The ratio is greater than or equal to the weight ratio of the inorganic micro-nano particles in the second composite material masterbatch.

优选的，所述聚合物基底材料包括聚甲基丙烯酸甲酯(PMMA)、氟树脂、氟树脂改性的聚甲基丙烯酸甲酯(F-PMMA)、聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)、聚对苯二甲酸乙二酯(PET)、聚偏氟乙烯(PVDF)、聚氯乙烯(PVC)、聚苯乙烯(PS)、聚酯和间苯二甲酸酯磺酸钠共聚物、丙烯酸酯共聚物、聚乙二醇(PEG)、聚对苯二甲酸丙二酯(PTT)、聚偏二氯乙烯树脂(PVDC)、醋酸乙烯酯树脂、聚乙烯醇(PVA)和聚乙烯醇缩乙醛中的一种或一种以上的混合物。Preferably, the polymer base material includes polymethyl methacrylate (PMMA), fluororesin, fluororesin modified polymethyl methacrylate (F-PMMA), polyethylene (PE), polypropylene (PP) ), polyamide (PA), polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polystyrene (PS), polyester and isophthalic acid Sodium sulfonate copolymer, acrylate copolymer, polyethylene glycol (PEG), polytrimethylene terephthalate (PTT), polyvinylidene chloride resin (PVDC), vinyl acetate resin, polyvinyl alcohol (PVA) and a mixture of one or more of polyvinyl acetal.

优选的，所述无机微纳颗粒包括二氧化钛(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)中的一种或一种以上的混合物。 Preferably, the inorganic micro-nano particles include titanium dioxide (TiO ₂ ), silicon dioxide (SiO ₂ ), zinc oxide (ZnO), silicon carbide (SiC), silicon nitride (Si ₃ N ₄ ), zinc sulfide (ZnS ), alumina (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 more than one.

优选的，所述无机微纳颗粒的粒径范围为0.03μm-250μm。Preferably, the particle size of the inorganic micro/nano particles ranges from 0.03 μm to 250 μm.

优选的，所述辐射制冷纤维单丝纤度范围为1D-50D，纤维直径范围0.1mm-1.5mm。Preferably, the monofilament size of the radiant refrigeration fiber is in the range of 1D-50D, and the fiber diameter is in the range of 0.1mm-1.5mm.

优选的，所述辐射制冷纤维包括单一结构、皮芯结构、径向梯度浓度结构、人字形结构、异形凸起结构、橘瓣结构、并列结构、旋转对称方位结构和海岛结构中的至少一种。Preferably, the radiant refrigeration fiber includes at least one of a single structure, a skin-core structure, a radial gradient concentration structure, a herringbone structure, a profiled convex structure, an orange petal structure, a side-by-side structure, a rotationally symmetrical orientation structure, and a sea-island structure .

优选的，所述复合挤出温度为100℃-600℃，卷绕速度为10m/min-6000m/min。Preferably, the composite extrusion temperature is 100°C-600°C, and the winding speed is 10m/min-6000m/min.

一种辐射制冷纤维织物的制备方法，具体包括，将上述辐射制冷纤维，通过针织和/或机织制得到辐射制冷织物。A method for preparing a radiant refrigerating fiber fabric specifically includes knitting and/or weaving the above radiant refrigerating fiber to obtain a radiant refrigerating fabric.

优选的，所述通过针织和/或机织制得辐射制冷织物，具体包括Preferably, the radiant cooling fabric made by knitting and/or weaving specifically includes

将辐射制冷纤维作为经纱和纬纱中的一种，将其他纤维作为经纱和纬纱中的另一种进行编织；The radiant refrigeration fiber is used as one of the warp and weft, and other fibers are used as the other of the warp and weft for weaving;

或者是将辐射制冷纤维作为经纱和纬纱进行编织。Or the radiant refrigeration fiber is woven as warp and weft.

借由上述技术方案，本发明提供的技术方案至少具有下列优点：本发明利用熔融复合纺丝法在聚合物纤维内引入高浓度无机微纳颗粒，通过精确调控微纳颗粒尺寸和纤维内部复合结构，使纤维在具备优异的日间辐射制冷性能的同时兼具高机械强度和可编织性能，得到适用于人体皮肤表面降温的辐射制冷织物，并具有大规模批量制备、成本低、生产效率高的优点。With the above technical solution, the technical solution provided by the present invention has at least the following advantages: the present invention uses the melt composite spinning method to introduce high-concentration inorganic micro-nano particles into the polymer fiber, and precisely regulates the size of the micro-nano particles and the internal composite structure of the fiber. , So that the fiber has excellent daytime radiant cooling performance and high mechanical strength and knitability at the same time, to obtain a radiant cooling fabric suitable for cooling the surface of human skin, and has a large-scale batch preparation, low cost, and high production efficiency. advantage.

本发明的制备方法，通过引入高浓度的无机微纳颗粒掺杂并精确调控颗粒尺寸，最大程度提升辐射制冷性能，制备优异的日夜辐射制冷性能的纤维及织物。In the preparation method of the present invention, by introducing high-concentration inorganic micro-nano particles doping and accurately adjusting the particle size, the radiant refrigeration performance is maximized, and fibers and fabrics with excellent day and night radiant refrigeration performance are prepared.

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、弹性稳定性以及高舒适性。The preparation method of the present invention can design the internal composite structure of the fiber, so that the fiber has excellent radiant refrigeration performance while having good mechanical properties, elastic stability and high comfort.

附图说明Description of the drawings

图1为本发明实施例1、2所制备的辐射制冷纤维的截面示意图。Figure 1 is a schematic cross-sectional view of the radiant refrigeration fiber prepared in Examples 1 and 2 of the present invention.

图2为本发明实施例3所制备的辐射制冷纤维的截面示意图。2 is a schematic cross-sectional view of the radiant refrigeration fiber prepared in Example 3 of the present invention.

图3为本发明实施例4所制备的辐射制冷纤维的截面示意图。3 is a schematic cross-sectional view of the radiant refrigeration fiber prepared in Example 4 of the present invention.

图4为本发明实施例5所制备的辐射制冷纤维的截面示意图。4 is a schematic cross-sectional view of the radiant refrigeration fiber prepared in Example 5 of the present invention.

图5为本发明实施例6所制备的辐射制冷纤维的截面示意图。5 is a schematic cross-sectional view of the radiant refrigeration fiber prepared in Example 6 of the present invention.

图6为本发明实施例7所制备的辐射制冷纤维的截面示意图。6 is a schematic cross-sectional view of the radiant refrigeration fiber prepared in Example 7 of the present invention.

图7为本发明实施例8所制备的辐射制冷纤维的截面示意图。Fig. 7 is a schematic cross-sectional view of a radiant refrigeration fiber prepared in Example 8 of the present invention.

图8为本发明实施例制作复合材料母粒所用的装置的示意图。Fig. 8 is a schematic diagram of an apparatus used for preparing a composite material masterbatch according to an embodiment of the present invention.

图9为本发明实施例的熔融纺丝所用的装置的示意图。Fig. 9 is a schematic diagram of an apparatus for melt spinning according to an embodiment of the present invention.

图10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。Fig. 10 is a schematic diagram of the prepared radiant refrigeration fiber after woven into a fabric according to an embodiment of the present invention.

其中，1为进料口，2为螺杆挤出机，3为熔体挤出口，4为铸带冷却装置，5为铸带牵引盘，6为铸带，7为切粒机，8为母粒出口，9为复合材料母粒料斗，10为纺丝机进料口，11为螺杆挤出机，12为计量泵，13为复合纺丝组件，14为辐射制冷纤维，15为油轮，16为导丝盘，17为卷绕筒，20为第一组分，30为第二组分，40为第三组分。Among them, 1 is the feed port, 2 is the screw extruder, 3 is the melt extrusion port, 4 is the casting belt cooling device, 5 is the casting belt traction disc, 6 is the casting belt, 7 is the pelletizer, and 8 is the mother The pellet outlet, 9 is the composite material master batch hopper, 10 is the spinning machine feed inlet, 11 is the screw extruder, 12 is the metering pump, 13 is the composite spinning component, 14 is the radiant refrigeration fiber, 15 is the tanker, and 16 It is the godet, 17 is the winding drum, 20 is the first component, 30 is the second component, and 40 is the third component.

具体实施方式Detailed ways

下面将参照附图更详细地描述本发明的示例性实施例。虽然附图中显示了本发明的示例性实施例，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。Hereinafter, exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings. Although the drawings show exemplary embodiments of the present invention, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to enable a more thorough understanding of the present invention and to fully convey the scope of the present invention to those skilled in the art.

一种辐射制冷纤维及其织物的批量制备方法，所制备的辐射制冷纤维织物，包括聚合物基底和无机微纳颗粒，所述无机微纳颗粒分散在聚合物基底内，并且所述辐射制冷纤维及其织物，采用熔融纺丝法制得，具体包括以下步骤：A method for batch preparation of radiant refrigeration fiber and its fabric. The prepared radiant refrigeration fiber fabric includes a polymer substrate and inorganic micro-nano particles. The inorganic micro-nano particles are dispersed in the polymer substrate, and the radiant refrigeration fiber Its fabric is made by melt spinning method, which specifically includes the following steps:

101：辐射制冷复合材料母粒的制备，将无机微纳颗粒和聚合物基底材料按照预定的重量比例均匀混合，制得复合材料母粒。101: Preparation of radiant refrigeration composite material masterbatch. The inorganic micro-nano particles and the polymer base material are uniformly mixed according to a predetermined weight ratio to prepare a composite material masterbatch.

102：熔融纺丝得到辐射制冷纤维，将步骤101中得到的复合材料母粒在纺丝组件中挤出成型，经卷绕后得到辐射制冷纤维。102: The radiant refrigerating fiber is obtained by melt spinning, and the composite material masterbatch obtained in step 101 is extruded into a spinning assembly, and the radiant refrigerating fiber is obtained after winding.

103：辐射制冷织物的制备，具体为，通过针织和/或机织工艺将步骤102中得到的辐射制冷纤维编织形成辐射制冷织物。103: Preparation of the radiant cooling fabric, specifically, weaving the radiant cooling fiber obtained in step 102 through a knitting and/or weaving process to form a radiant cooling fabric.

并且优选的，上述步骤101，具体包括，将第一无机微纳颗粒和第一聚合物基底材料按照预定的第一重量比例均匀混合，制得第一复合材料母粒，将第二无机微纳颗粒和第二聚合物基底材料按照预定的第二重量比例均匀混合，制得第二复合材料母粒；And preferably, the above step 101 specifically includes, uniformly mixing the first inorganic micro-nano particles and the first polymer base material according to a predetermined first weight ratio to prepare a first composite material masterbatch, and combining the second inorganic micro-nano particles The particles and the second polymer base material are uniformly mixed according to a predetermined second weight ratio to prepare a second composite material masterbatch;

所述第一复合材料母粒中无机微纳颗粒的重量占比为1-80wt.％，所述第二复合材料母粒中无机微纳颗粒的重量占比为0-20wt.％，并且所述第一复合材料母粒中无机微纳颗粒的重量占比大于等于第二复合材料母粒中无机微纳颗粒的重量占比。The weight percentage of the inorganic micro-nano particles in the first composite material masterbatch is 1-80wt.%, and the weight percentage of the inorganic micro-nano particles in the second composite material masterbatch is 0-20wt.%, and The weight proportion of the inorganic micro-nano particles in the first composite material master particle is greater than or equal to the weight proportion of the inorganic micro-nano particles in the second composite material master particle.

同时该步骤102包括，将步骤101中得到的第一复合材料母粒作为第一组分，第二复合材料母粒作为第二组分，在纺丝组件中复合挤出成型，经卷绕后得到辐射制冷纤维。At the same time, step 102 includes taking the first composite material masterbatch obtained in step 101 as the first component, and the second composite material masterbatch as the second component, in the spinning assembly for composite extrusion molding, and after winding Obtain radiant refrigeration fiber.

上述辐射制冷纤维的第一复合材料母粒和第二复合材料母粒，均为无机微纳颗粒以高浓度与聚合物基底复合以不同的重量比例混合制成，该第一复合材料母粒中的第一聚合物基底材料和第二复合材料母粒中的第二聚合物基底材料，可以相同也可以不同，并且第一重量比例大于等于第二重量比例，使得该制冷纤维中的第一组分可以为高掺杂的复合材料，而第二组分可以是低掺杂或者是零掺杂，可以使得整个辐射制冷纤维保证一定的韧性，易于编织成织物。同样，该第一复合材料母粒的第一无机微纳颗粒和第二复合材料母粒中的第二无机微纳颗粒，可以相同也可以不同，优选的，该第一无机微纳颗粒和第二无机微纳颗粒相同。The first composite material masterbatch and the second composite material masterbatch of the above-mentioned radiant refrigeration fiber are made by mixing inorganic micro-nano particles with high concentration and polymer substrate in different weight ratios. The first composite material masterbatch The first polymer base material and the second polymer base material in the second composite material masterbatch may be the same or different, and the first weight ratio is greater than or equal to the second weight ratio, so that the first group of refrigerating fibers The component can be a highly doped composite material, and the second component can be low-doped or zero-doped, so that the entire radiant refrigeration fiber can ensure a certain toughness and is easy to be woven into a fabric. Similarly, the first inorganic micro-nano particles in the first composite material masterbatch and the second inorganic micro-nano particles in the second composite material masterbatch may be the same or different. Preferably, the first inorganic micro-nano particles and the second inorganic micro-nano particles The two inorganic micro-nano particles are the same.

并且，作为本发明的另一实施方式，该辐射制冷纤维还可以包括至少一种第三组分，该第三组分对应于第三无机微纳颗粒和第三聚合物基底材料按照第三重量比例制得的第三复合材料母粒，所述至少一种第三复合材料母粒中无机微纳颗粒的重量占比为1-80wt.％，并且所述至少一种第三复合材料母粒中无机微纳颗粒的重量占比大于等于第二复合材料母粒中无机微纳颗粒的重量占比。该至少一种第三组分，为至少两种时，该至少两种第三组分中，无机微纳颗粒、无机微纳颗粒的粒径、无机微纳颗粒的质量占比和聚合物基底材料中，至少有一个参数不同。And, as another embodiment of the present invention, the radiant refrigeration fiber may further include at least one third component, the third component corresponding to the third inorganic micro-nano particles and the third polymer base material according to the third weight The third composite material masterbatch prepared by the ratio, the weight proportion of the inorganic micro-nano particles in the at least one third composite material masterbatch is 1-80wt.%, and the at least one third composite material masterbatch The weight proportion of the inorganic micro-nano particles in the second composite material is greater than or equal to the weight proportion of the inorganic micro-nano particles in the second composite material master particle. When the at least one third component is at least two, in the at least two third components, the inorganic micro/nano particles, the particle size of the inorganic micro/nano particles, the mass proportion of the inorganic micro/nano particles, and the polymer substrate Among the materials, at least one parameter is different.

优选的，该步骤103中，可以是用步骤102中得到的辐射制冷纤维来单独进行织物的编织，也可以是用辐射制冷纤维作为纬纱和经纱中的一种，其他纤维作为经纱和纬纱中的另一种，混合编织形成辐射制冷织物。所述其他纤维，可以是涤纶、棉等其他单一面料或者混纺面料的纤维。Preferably, in this step 103, the radiant refrigerating fiber obtained in step 102 can be used to separately weave the fabric, or the radiant refrigerating fiber can be used as one of the weft and warp yarns, and the other fibers can be used as the warp and weft yarns. The other is mixed weaving to form a radiant cooling fabric. The other fibers may be fibers of other single fabrics or blended fabrics such as polyester and cotton.

所述聚合物基底材材料为热塑性树脂，优选的，包括聚甲基丙烯酸甲酯(PMMA)、氟树脂、氟树脂改性的聚甲基丙烯酸甲酯(F-PMMA)、聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)、聚对苯二甲酸乙二酯(PET)、聚偏氟乙烯(PVDF)、聚氯乙烯(PVC)、聚苯乙烯(PS)、聚酯/间苯二甲酸酯磺酸钠共聚物、丙烯酸酯共聚物、聚乙二醇(PEG)、聚对苯二甲酸丙二酯(PTT)、聚偏二氯乙烯树脂(PVDC)、醋酸乙烯酯树脂、聚乙烯醇(PVA)和聚乙烯醇缩乙醛等中的一种或一种以上的混合物。The polymer substrate material is a thermoplastic resin, preferably including polymethyl methacrylate (PMMA), fluororesin, fluororesin-modified polymethyl methacrylate (F-PMMA), polyethylene (PE) , Polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polystyrene (PS), polyester/ Sodium isophthalate sulfonate copolymer, acrylate copolymer, polyethylene glycol (PEG), polytrimethylene terephthalate (PTT), polyvinylidene chloride resin (PVDC), vinyl acetate One or more mixtures of resin, polyvinyl alcohol (PVA) and polyvinyl acetal.

优选的，所述氟树脂改性的聚甲基丙烯酸甲酯(F-PMMA)中，氟树脂与PMMA的质量比范围为1:100-10:1。Preferably, in the fluororesin-modified polymethyl methacrylate (F-PMMA), the mass ratio of fluororesin to PMMA ranges from 1:100 to 10:1.

优选的，所述无机微纳颗粒包括二氧化钛(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)等中的一种或一种以上混合物。优选的，该无机微纳颗粒为TiO ₂。 Preferably, the inorganic micro-nano particles include titanium dioxide (TiO ₂ ), silicon dioxide (SiO ₂ ), zinc oxide (ZnO), silicon carbide (SiC), silicon nitride (Si ₃ N ₄ ), zinc sulfide (ZnS ), alumina (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 ) or a mixture of one or more of them. Preferably, the inorganic micro-nano particles are TiO ₂ .

所述无机微纳颗粒的粒径范围为0.03μm-250μm，优选的，微纳颗粒粒径为0.4μm-1.2μm，进一步优选的，为0.6μm。The particle size of the inorganic micro-nano particles ranges from 0.03 μm to 250 μm, preferably, the particle size of the micro-nano particles is 0.4 μm to 1.2 μm, and more preferably, it is 0.6 μm.

所述辐射制冷纤维，单丝纤度范围为1D-50D，纤维直径范围0.1mm-1.5mm。The radiant refrigeration fiber has a monofilament size ranging from 1D to 50D, and a fiber diameter ranging from 0.1mm to 1.5mm.

当上述第二、第三组分的材料加入至第一组分时，可以得到复合结构的辐射制冷纤维，例如可以为皮芯结构、径向梯度浓度结构、人字形结构、异形凸起结构、橘瓣结构、并列结构、旋转对称方位结构、海岛结构等复合结构中的至少一种。而当第二组分材料与第一组分中的聚合物基底材料相同时，该熔融挤出的辐射制冷纤维仍然为单一结构，只是形状可以根据需要控制。When the materials of the second and third components are added to the first component, a composite structure of radiant refrigeration fiber can be obtained, for example, it can be a sheath-core structure, a radial gradient concentration structure, a herringbone structure, a special-shaped convex structure, At least one of compound structures such as orange petal structure, side-by-side structure, rotationally symmetrical azimuth structure, and sea-island structure. When the second component material is the same as the polymer base material in the first component, the melt-extruded radiant refrigeration fiber still has a single structure, but the shape can be controlled as required.

将复合材料母粒在纺丝组件中挤出成型，经卷绕后得到辐射制冷纤维，具体包括将所述第一、第二组分在纺丝组件中挤出成型，并且该复合挤出成型的温度为100℃-600℃，优选温度范围为150℃-350℃；卷绕速度为10m/min-6000m/min，优选的，卷绕速度为200m/min-500m/min，更加优选的为300m/min。The composite material masterbatch is extruded and formed in the spinning assembly, and the radiant refrigeration fiber is obtained after winding, which specifically includes extruding the first and second components in the spinning assembly, and the composite extrusion molding The temperature is 100°C-600°C, and the preferred temperature range is 150°C-350°C; the winding speed is 10m/min-6000m/min, preferably, the winding speed is 200m/min-500m/min, more preferably 300m/min.

所述制备复合材料母粒的过程，具体包括将无机微纳颗粒和聚合物基底材料的混合材料熔融挤出，水浴切粒后得到辐射制冷复合材料母粒，该熔融挤出的母粒的温度范围优选的，为100℃-600℃，更加优选的，为150℃-350℃。The process of preparing the composite material masterbatch specifically includes melt extruding the mixed material of the inorganic micro-nano particles and the polymer base material, and the radiant refrigeration composite material masterbatch is obtained after pelletizing in a water bath. The temperature of the melt-extruded masterbatch is The preferred range is 100°C to 600°C, and more preferably 150°C to 350°C.

实施例1：Example 1:

该实施例1中，辐射制冷纤维仅包含第一组分，即为单一结构的辐射制冷纤维，其截面如图1所示，该辐射制冷纤维的聚合物基底为聚乙烯(PE)，掺杂的无机微纳颗粒为TiO ₂，TiO ₂颗粒的粒径为600nm，重量占比为50wt.％。 In this embodiment 1, the radiant refrigeration fiber only contains the first component, which is a single-structure radiant refrigeration fiber. The cross section of the radiant refrigeration fiber is shown in Figure 1. The inorganic micro-nano particles are TiO ₂ , _{the particle size of the TiO 2} particles is 600 nm, and the weight percentage is 50 wt.%.

具体步骤为：The specific steps are:

101，辐射制冷复合材料母粒的制备；101. Preparation of radiant refrigeration composite material masterbatch;

利用如图8所示的装置，将1200g聚乙烯(PE)颗粒粉碎至粉末状，加入1200g于100℃真空烘箱中烘干24h的TiO ₂颗粒混合均匀。将混合材料通过双螺杆挤出机在260℃，4MPa压力下挤出熔体铸带。将铸带通过常温水浴进行凝固，导引铸带穿过引导轮至切片机，将固化的熔体铸带切成PE和TiO ₂、TiO ₂的重量占比为50％的复合材料母粒。 Using the device shown in Figure 8, 1200g of polyethylene (PE) particles were crushed to powder form, and 1200g of TiO ₂ particles dried in a vacuum oven at 100°C for 24 hours were added and mixed uniformly. The mixed material was extruded into the melt cast belt through a twin-screw extruder at 260° C. and a pressure of 4 MPa. The casting belt is solidified in a water bath at room temperature, and the casting belt is guided through the guide wheel to the slicer, and the solidified melt casting belt is cut into composite material master particles with a weight ratio of _{PE, TiO 2} , and TiO _{2 of 50%.}

102，熔融纺丝制备辐射制冷纤维；102. Prepare radiant refrigeration fiber by melt spinning;

利用如图9所示的装置，将PE和TiO ₂复合材料母粒于75℃真空烘箱中干燥24h。将干燥完成后的复合材料母粒填入熔融纺丝机料斗中，调整熔融纺丝机各区的温度，例如：螺杆各区温度分为四个区，分别为235℃、260℃、275℃和275℃，计量泵温度为275℃，纺丝组件温度为280℃。在螺杆转速为20Hz、稳定螺杆压力为5.6MPa条件下，进行熔融复合纺丝制备纤维，并通过300m/min的卷绕速度收丝落筒，由此得到均匀掺杂50wt.％二氧化钛颗粒的辐射制冷纤维。 Using the device shown in Figure 9, the PE and TiO ₂ composite masterbatch was dried in a vacuum oven at 75°C for 24 hours. Fill the dried composite masterbatch into the hopper of the melt spinning machine, adjust the temperature of each zone of the melt spinning machine, for example: the temperature of each zone of the screw is divided into four zones, respectively 235℃, 260℃, 275℃ and 275 ℃, the temperature of the metering pump is 275℃, and the temperature of the spinning assembly is 280℃. Under the conditions of a screw speed of 20 Hz and a stable screw pressure of 5.6 MPa, the fiber was prepared by melt composite spinning, and the yarn was taken up and doffed at a winding speed of 300 m/min, thereby obtaining radiation uniformly doped with 50 wt.% titanium dioxide particles. Refrigeration fiber.

(3)辐射制冷织物的制备；(3) Preparation of radiant cooling fabric;

将得到的辐射制冷纤维作为纬纱，并且取合适长度和根数的辐射制冷纤维穿过梭织机的综眼和筘齿，整齐排列于综框中作为经纱，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。如图10所示。The obtained radiant refrigerating fiber is used as weft yarn, and the radiant refrigerating fiber of suitable length and number is passed through the heddle eyelet and reed teeth of the shuttle loom, and they are neatly arranged in the heald frame as warp yarn to avoid excessive friction. , Adjust the warp yarn of the winding roller to make the tension even and moderately tight; according to the changing law of the warp and weft, the opening mechanism is used to drive the upper and lower warp yarns in order to form the shed channel; the fiber is wound on the shuttle as the weft, and the shuttle is alternately passed through the shed. The channel is woven, coordinated with other mechanisms on the loom to adjust the arrangement density of the weft yarn, and the fabric is wound and drawn on the cloth roll, thereby obtaining a radiant cooling fabric uniformly doped with 50wt.% titanium dioxide particles. As shown in Figure 10.

实施例2：Example 2:

如图1所示，该实施例也为单一结构的辐射制冷纤维，该辐射制冷纤维的聚合物基底为聚合物材料聚丙烯(PP)，掺杂的无机微纳颗粒为TiO ₂，TiO ₂颗粒的粒径为600nm，重量比例为20wt.％。该辐射制冷纤维在制作时包含两个组分，第一组分和第二组分的聚合物基底材料和无机微纳颗粒相同，并且重量占比也相同。 As shown in Figure 1, this embodiment is also a single-structure radiant refrigeration fiber. The polymer substrate of the radiant refrigeration fiber is polypropylene (PP), a polymer material, and the doped inorganic micro-nano particles are TiO ₂ and TiO ₂ particles. The particle size is 600nm, and the weight ratio is 20wt.%. The radiant refrigeration fiber contains two components during production, the polymer base material of the first component and the second component are the same as the inorganic micro-nano particles, and the weight ratio is also the same.

具体制作方法为：The specific production method is:

101，辐射制冷复合材料母粒的制备：101. Preparation of radiant refrigeration composite material masterbatch:

将1200g聚丙烯(PP)颗粒粉碎至粉末状，加入300g于100℃真空烘箱中烘干24h的TiO ₂颗粒混合均匀。将混合材料通过双螺杆挤出机在260℃，4MPa压力下挤出熔体铸带。将铸带通过水浴进行凝固，导引铸带穿过引导轮至切粒机，将固化的熔体铸带切成PP和TiO ₂、TiO ₂的重量占比为20％的复合材料母粒。 1200g of polypropylene (PP) particles were crushed to powder, and 300g of TiO ₂ particles dried in a vacuum oven at 100°C for 24 hours were added and mixed uniformly. The mixed material was extruded into the melt cast belt through a twin-screw extruder at 260° C. and a pressure of 4 MPa. The cast belt is solidified through a water bath, and the cast belt is guided through a guide wheel to a pelletizer, and the solidified melt cast belt is cut into composite master particles with a weight ratio of _{PP, TiO 2} and TiO _{2 of 20%.}

102，熔融复合纺丝制备辐射制冷纤维：102. Preparation of radiant refrigeration fiber by melt composite spinning:

将PP和TiO ₂的复合材料母粒于75℃真空烘箱中干燥24h。将干燥完成后的PP@TiO ₂(20wt.％)复合材料母粒等分，分别作为第一组分和第二组分，填入熔融纺丝机的两个料斗中，调整熔融纺丝机各区的温度和螺杆转速，稳定螺杆压力，熔融复合纺丝制备得到单一结构辐射制冷纤维，并通过300m/min的卷绕速度收丝落筒，由此得到均匀掺杂20wt.％二氧化钛颗粒的单一结构辐射制冷纤维。 The composite masterbatch of PP and TiO ₂ was dried in a vacuum oven at 75°C for 24 hours. Divide the dried PP@TiO ₂ (20wt.%) composite masterbatch into equal parts as the first component and the second component, and fill them into the two hoppers of the melt spinning machine to adjust the melt spinning machine The temperature and screw speed of each zone, stabilize the screw pressure, melt composite spinning to prepare a single-structure radiant refrigeration fiber, and take up and doffing at a winding speed of 300m/min, thereby obtaining a single uniformly doped 20wt.% titanium dioxide particle Structure radiant refrigeration fiber.

103，辐射制冷织物的制备：103. Preparation of radiant cooling fabric:

将得到的辐射制冷纤维作为纬纱，取合适长度和根数的辐射制冷纤维穿过梭织机的综眼和筘齿，整齐排列于综框中作为经纱，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。Use the obtained radiant refrigerating fiber as the weft yarn, and take the radiant refrigerated fiber of suitable length and number to pass through the heddle eyelet and reed teeth of the shuttle loom, and neatly arrange them in the heald frame as the warp yarn, in order to avoid excessive friction and wear the fiber. Adjust the warp yarn of the winding roller to make the tension even and moderately tight; according to the changing law of warp and weft interweaving, the opening mechanism is used to drive the upper and lower warp yarns in order to form the shed channel; the fiber is wound on the shuttle as the weft yarn, and the shuttle is alternately passed through the shed channel. Perform weaving, adjust the arrangement density of weft yarns in coordination with other mechanisms on the loom, and wind and draw off the fabric on a cloth roll, thereby obtaining a radiant cooling fabric uniformly doped with 20wt.% titanium dioxide particles.

实施例3：Example 3:

如图2所示，该实施例制得的辐射制冷纤维为皮芯结构，即包含两种组分，第一组分20和第二组分30，第一组分20的聚合物基底材料为氟树脂与聚甲基丙烯酸甲酯的复合材料(F-PMMA)，掺杂的无机微纳颗粒为TiO ₂，并且微纳颗粒TiO ₂的粒径为600nm，第一重量比例为60wt.％。该第二组分30中的聚合物基底材料为F-PMMA，微纳颗粒为零掺杂。 As shown in Figure 2, the radiant refrigeration fiber prepared in this embodiment has a sheath-core structure, that is, contains two components, a first component 20 and a second component 30. The polymer base material of the first component 20 is The composite material of fluororesin and polymethyl methacrylate (F-PMMA), the doped inorganic micro-nano particles are TiO ₂ , and the particle size of the micro-nano particles TiO ₂ is 600 nm, and the first weight ratio is 60 wt.%. The polymer base material in the second component 30 is F-PMMA, and the micro/nano particles are zero-doped.

具体的制备方法包括：The specific preparation method includes:

101，辐射制冷复合材料母粒的制备101. Preparation of radiant refrigeration composite material masterbatch

将10g氟树脂颗粒与1000g PMMA颗粒粉碎至粉末状，加入1515g TiO ₂颗粒混合均匀，该TiO ₂颗粒先于100℃真空烘箱中烘干24h。将混合材料通过双螺杆挤出机在260℃，4MPa压力下挤出熔体铸带。将铸带通过常温水浴进行凝固，导引铸带穿过引导轮至切片机，将固化的熔体铸带切片得到F-PMMA(1:100)和TiO ₂(60wt.％)复合材料母粒，即第一复合材料母粒。 10g of fluororesin particles and 1000g of PMMA particles were crushed to powder, and 1515g of TiO ₂ particles were added and mixed uniformly. The TiO ₂ particles were first dried in a vacuum oven at 100°C for 24 hours. The mixed material was extruded into the melt cast belt through a twin-screw extruder at 260° C. and a pressure of 4 MPa. The casting belt is solidified in a water bath at room temperature, and the casting belt is guided through the guide wheel to the slicer, and the solidified melt casting belt is sliced to obtain F-PMMA (1:100) and TiO ₂ (60wt.%) composite masterbatch , The first composite material masterbatch.

同理，混合氟树脂颗粒与PMMA颗粒粉碎至粉末状，制得F-PMMA复合材料母粒，即第二复合材料母粒。In the same way, the mixed fluororesin particles and PMMA particles are pulverized to a powder form to prepare the F-PMMA composite masterbatch, that is, the second composite masterbatch.

将F-PMMA和TiO ₂(60wt.％)的复合材料母粒于75℃真空烘箱中干燥24h。将干燥完成后的复合材料母粒和F-PMMA复合材料母粒分别填入熔融纺丝机料斗中，调整熔融纺丝机各区的温度和螺杆转速，稳定螺杆压力，熔融复合纺丝制备得到皮芯结构辐射制冷纤维，并通过300m/min的卷绕速度收丝落筒，由此得到芯层均匀掺杂60wt.％二氧化钛颗粒的皮芯结构辐射制冷纤维。该第一组分作为芯层，第二组分作为包层。 The composite masterbatch of F-PMMA and TiO ₂ (60 wt.%) was dried in a vacuum oven at 75° C. for 24 hours. Fill the dried composite material masterbatch and F-PMMA composite material masterbatch into the hopper of the melt spinning machine respectively, adjust the temperature and screw speed of each zone of the melt spinning machine, stabilize the screw pressure, and prepare the skin by melt composite spinning. The core structure radiant refrigeration fiber is taken up and doffed at a winding speed of 300 m/min, thereby obtaining a core-sheath structure radiant refrigeration fiber with a core layer uniformly doped with 60 wt.% titanium dioxide particles. The first component serves as the core layer, and the second component serves as the cladding layer.

103，辐射制冷织物的制备步骤与实施例1相同，由此得到纤维的芯层均匀掺杂为60wt.％二氧化钛颗粒的皮芯结构辐射制冷织物。103. The preparation steps of the radiant cooling fabric are the same as in Example 1, thereby obtaining a skin-core radiant cooling fabric in which the core layer of the fiber is uniformly doped with 60 wt.% titanium dioxide particles.

实施例4Example 4

如图3所示，该辐射制冷纤维的横截面为浓度，即微纳颗粒的重量浓度沿径向递减的形式。该纤维包括第一组分20、第二组分30和第三组分40。第一组分、第二组分和第三组分的聚合物基底材料均为氟树脂与聚甲基丙烯酸甲酯的复合材料(F-PMMA)，掺杂的无机微纳颗粒均为TiO ₂，粒径为600nm。第一组分中的微纳颗粒的重量占比为80％。第三组分中的微纳颗粒的重量占比为60％，第二组分中微纳颗粒无掺杂，即重量占比为0。该第一组分20、第三组分40和第二组分30依次从内向外设置，进而形成微纳颗粒的重量占比沿径向递减。 As shown in Fig. 3, the cross-section of the radiant refrigeration fiber is in the form of concentration, that is, the weight concentration of micro-nano particles decreases in the radial direction. The fiber includes a first component 20, a second component 30, and a third component 40. The polymer base materials of the first component, the second component and the third component are all composite materials of fluororesin and polymethyl methacrylate (F-PMMA), and the doped inorganic micro-nano particles are all TiO ₂ , The particle size is 600nm. The weight ratio of the micro-nano particles in the first component is 80%. The weight ratio of the micro/nano particles in the third component is 60%, and the weight ratio of the micro/nano particles in the second component is zero. The first component 20, the third component 40 and the second component 30 are sequentially arranged from the inside to the outside, and the weight ratio of the micro/nano particles formed decreases in the radial direction.

该实施例中的辐射制冷纤维的制备方法，包括：The preparation method of radiant refrigeration fiber in this embodiment includes:

将10g氟树脂颗粒与1000g PMMA颗粒粉碎至粉末状，加入4040g TiO ₂颗粒混合均匀，该TiO ₂于100℃真空烘箱中烘干24h。将混合材料通过双螺杆挤出机在260℃，4MPa压力下挤出熔体铸带，将铸带通过常温水浴进行凝固，导引铸带穿过引导轮至切片机，将固化的熔体铸带切片得到F-PMMA(1:100)和TiO ₂(80wt.％)复合材料母粒，即第一复合材料母粒。 10g of fluororesin particles and 1000g of PMMA particles were pulverized to powder, 4040g of TiO ₂ particles were added and mixed uniformly, and the TiO ₂ was dried in a vacuum oven at 100°C for 24 hours. The mixed material is extruded through a twin-screw extruder at 260°C and a pressure of 4MPa to extrude the melt casting belt, the casting belt is solidified in a water bath at room temperature, and the casting belt is guided through the guide wheel to the slicer, and the solidified melt is cast Tape slices to obtain F-PMMA (1:100) and TiO ₂ (80wt.%) composite masterbatch, that is, the first composite masterbatch.

并且同理，制备出F-PMMA(1:100)和TiO ₂(60wt.％)复合材料母粒，即第三复合材料母粒，以及同理，制备出F-PMMA复合材料母粒，即第二复合材料母粒。 In the same way, F-PMMA (1:100) and TiO ₂ (60wt.%) composite material masterbatch was prepared, namely the third composite material masterbatch, and in the same way, F-PMMA composite material masterbatch was prepared, namely The second composite material masterbatch.

102，熔融复合纺丝制备辐射制冷纤维；102. Preparation of radiant refrigeration fiber by melt composite spinning;

将步骤101中制得的三种复合材料母粒于75℃真空烘箱中干燥24h。将干燥完成后的F-PMMA和TiO ₂(80wt.％)复合材料母粒、F-PMMA和TiO ₂(60wt.％)复合材料母粒和F-PMMA复合材料母粒分别填入熔融纺丝机料斗中，调整熔融纺丝机各区的温度和螺杆转速，稳定螺杆压力，熔融复合纺丝制备得到径向梯度浓度结构辐射制冷纤维，并通过300m/min的卷绕速度收丝落筒，由此得到最内部芯层均匀掺杂80wt.％二氧化钛颗粒、中间层均匀掺杂60wt.％二氧化钛颗粒的径向梯度浓度结构辐射制冷纤维。 The three composite masterbatches prepared in step 101 were dried in a vacuum oven at 75° C. for 24 hours. Fill the dried F-PMMA and TiO ₂ (80wt.%) composite masterbatch, F-PMMA and TiO ₂ (60wt.%) composite masterbatch and F-PMMA composite masterbatch into the melt-spinning respectively In the machine hopper, adjust the temperature and screw speed of each zone of the melt spinning machine, stabilize the screw pressure, melt composite spinning to prepare the radial gradient concentration structure radiant refrigeration fiber, and take up the doffing at a winding speed of 300m/min. In this way, a radial gradient concentration structure radiant refrigeration fiber is obtained in which the innermost core layer is uniformly doped with 80 wt.% titanium dioxide particles, and the intermediate layer is uniformly doped with 60 wt.% titanium dioxide particles.

103，辐射制冷织物的制备；103. Preparation of radiant cooling fabrics;

将得到的辐射制冷纤维作为纬纱，取合适长度和根数的其他纤维穿过梭织机的综眼和筘齿，整齐排列于综框中作为经纱，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，由此得到掺杂二氧化钛颗粒的辐射制冷织物。上述其他纤维，可以是涤纶、棉等其他面料的纤维，可以根据需要来进行选取。Use the obtained radiant refrigerated fiber as the weft yarn, take other fibers of appropriate length and number to pass through the heddle eyelet and reed teeth of the shuttle loom, and arrange them neatly in the heald frame as the warp yarn. In order to avoid excessive friction and wear the fibers, adjust The warp yarn of the winding roller makes the tension uniform and the tension is moderate; according to the changing law of the warp and weft interweaving, the opening mechanism is used to drive the upper and lower warp yarns in order to form the shed channel; the fiber is wound on the shuttle as the weft yarn, and the shuttle is alternately reciprocated through the shed channel. Weaving, coordinate with other mechanisms on the loom to adjust the arrangement density of weft yarns, and wind and draw off the fabric on a cloth roll, thereby obtaining a radiant cooling fabric doped with titanium dioxide particles. The above-mentioned other fibers may be fibers of other fabrics such as polyester, cotton, etc., and can be selected according to needs.

取实施例1、2、3和4中的复合材料辐射制冷纤维分别进行力学性能对比，表1所示。在同等外界条件下，实施例3的皮芯结构纤维和实施例4的径向梯度浓度结构复合纤维的断裂强度远高于实施例1和2的单一结构复合纤维的断裂强度。这是由于通过熔融复合纺丝法制备的复合纤维皮层大大加强了纤维的力学性能。由于掺杂浓度的影响，实施例1和2所制备的单一结构的织物相较于实施例3皮芯结构和实施例4径向梯度浓度结构的辐射制冷纤维在太阳辐射的反射率较低。说明通过熔融复合纺丝法调节掺杂微纳颗粒浓度和纤维内部结构，可以在保证辐射性能的同时具有良好的机械强度，适用于制作成人体表面降温的织物。Take the composite radiant refrigeration fibers in Examples 1, 2, 3 and 4 to compare their mechanical properties, as shown in Table 1. Under the same external conditions, the breaking strength of the sheath-core structure fiber of Example 3 and the radial gradient concentration structure composite fiber of Example 4 is much higher than that of the single structure composite fiber of Examples 1 and 2. This is because the composite fiber skin layer prepared by the melt composite spinning method greatly strengthens the mechanical properties of the fiber. Due to the influence of the doping concentration, the single-structure fabric prepared in Examples 1 and 2 has lower solar radiation reflectivity than the radiant refrigeration fiber with the sheath-core structure in Example 3 and the radial gradient concentration structure in Example 4. It shows that adjusting the concentration of doped micro-nano particles and the internal structure of the fiber by the melt composite spinning method can ensure the radiation performance while having good mechanical strength, which is suitable for making fabrics that cool the surface of the human body.

表1Table 1

实施例Example	纤维结构Fiber structure	纤维内部最高微纳颗粒掺杂浓度The highest micro-nano particle doping concentration inside the fiber
实施例1Example 1	单一结构Single structure	20wt.％20wt.%
实施例2Example 2	单一结构Single structure	50wt.％50wt.%
实施例3Example 3	皮芯结构Skin core structure	60wt.％60wt.%
实施例4Example 4	径向梯度浓度结构Radial gradient concentration structure	80wt.％80wt.%

实施例5：Example 5:

该实施例中的纤维，为横截面为异性结构的辐射制冷纤维，如图4所示，该辐射制冷纤维包括第一组分20和第二组分30，第一组分20位于中心为芯层，第二组分30位于外侧为包层，该包层包括在芯层外侧沿周向均匀分布的突起。第一组分20中的聚合物基底材料为聚酰胺(PA)，其中掺杂的无机微纳颗粒为TiO ₂，平均粒径约600nm，TiO ₂掺杂浓度为50wt.％。该第二组分30的聚合物基底材料为氟树脂与聚甲基丙烯酸甲酯的复合材料(F-PMMA)，无机微纳颗粒为的质量比例为0，即零掺杂。 The fiber in this embodiment is a radiant refrigeration fiber with a heterogeneous cross-section. As shown in Figure 4, the radiant refrigeration fiber includes a first component 20 and a second component 30. The first component 20 is located in the center as the core. The second component 30 is located on the outer side as a cladding layer, and the cladding layer includes protrusions uniformly distributed along the circumferential direction on the outer side of the core layer. The polymer base material in the first component 20 is polyamide (PA), wherein the doped inorganic micro-nano particles are TiO ₂ with an average particle size of about 600 nm, and the _{doping concentration of TiO 2} is 50 wt.%. The polymer base material of the second component 30 is a composite material of fluororesin and polymethyl methacrylate (F-PMMA), and the mass ratio of the inorganic micro-nano particles is 0, that is, zero doping.

该辐射制冷纤维及其织物的制备方法，包括：The preparation method of the radiant refrigeration fiber and its fabric includes:

将1200g聚酰胺(PA)颗粒粉碎至粉末状，加入1200g于100℃真空烘箱中烘干24h的TiO ₂颗粒混合均匀。将混合材料通过双螺杆挤出机在260℃，4MPa压力下挤出熔体铸带。将铸带通过常温水浴进行凝固，导引铸带穿过引导轮至切片机，将固化的熔体铸带切成PA和TiO ₂(50wt.％)复合材料母粒，即第一复合材料母粒。将1000g氟树脂颗粒与100g PMMA颗粒粉碎至粉末状，将混合材料通过双螺杆挤出机在260℃，4MPa压力下挤出熔体铸带。将铸带通过常温水浴进行凝固，导引铸带穿过引导轮至切片机，将固化的熔体铸带切片得到F-PMMA(10:1)复合材料母粒，即第二复合材料母粒。 1200g of polyamide (PA) particles were crushed to powder, and 1200g of TiO ₂ particles dried in a vacuum oven at 100°C for 24 hours were added and mixed uniformly. The mixed material was extruded into the melt cast belt through a twin-screw extruder at 260° C. and a pressure of 4 MPa. The casting belt is solidified in a water bath at room temperature, and the casting belt is guided through the guide wheel to the slicer, and the solidified melt casting belt is cut into PA and TiO ₂ (50wt.%) composite masterbatch, that is, the first composite masterbatch grain. 1000g of fluororesin particles and 100g of PMMA particles were crushed to powder, and the mixed material was extruded into a melt cast belt at 260°C and 4MPa pressure through a twin-screw extruder. The casting belt is solidified in a water bath at room temperature, and the casting belt is guided through the guide wheel to the slicer, and the solidified melt casting belt is sliced to obtain the F-PMMA (10:1) composite masterbatch, that is, the second composite masterbatch .

将PA、TiO ₂(50wt.％)和F-PMMA复合材料母粒于75℃真空烘箱中干燥24h。将干燥完成后的PA和TiO ₂(50wt.％)复合材料母粒、F-PMMA复合材料母粒分别填入熔融纺丝机料斗中，调整熔融纺丝机各区的温度和螺杆转速，稳定螺杆压力，熔融复合纺丝制备得到异形结构辐射制冷纤维，并通过300m/min的卷绕速度收丝落筒，由此得到芯层均匀掺杂50wt.％二氧化钛颗粒、外层为弧形凸起的异形结构辐射制冷纤维。 The PA, TiO ₂ (50wt.%) and F-PMMA composite masterbatch were dried in a vacuum oven at 75°C for 24 hours. Fill the dried PA and TiO ₂ (50wt.%) composite masterbatch and F-PMMA composite masterbatch into the hopper of the melt spinning machine respectively, adjust the temperature and screw speed of each zone of the melt spinning machine to stabilize the screw Pressure, melt composite spinning to prepare radiant refrigeration fiber with special-shaped structure, and take-up and doffing at a winding speed of 300m/min, thereby obtaining a core layer that is uniformly doped with 50wt.% titanium dioxide particles and the outer layer is arc-shaped convex Irregular structure radiant refrigeration fiber.

(3)辐射制冷织物的制备步骤与实施例1相同，由此得到芯层均匀掺杂50wt.％二氧化钛颗粒、外层为弧形凸起的异形结构辐射制冷织物。(3) The preparation steps of the radiant cooling fabric are the same as in Example 1, thereby obtaining a special-shaped radiant cooling fabric with a core layer uniformly doped with 50 wt.% titanium dioxide particles and an outer layer with arc-shaped protrusions.

实施例1和实施例5的复合材料辐射制冷纤维进行对比，由于实施例5中得到的辐射制冷纤维外有若干凸起的异形结构，使纤维表面具有凹槽，与实施例1的圆形结构辐射制冷纤维相比，具有较大的表面积，因此能够增强纤维吸湿排汗性能。且由于氟树脂的改性，使纤维更具有柔韧性。所以通过熔融复合纺丝调控纤维内部结构，可以在维持其辐射制冷性能的同时，增强舒适性。The composite radiant refrigeration fiber of Example 1 and Example 5 is compared. Because the radiant refrigeration fiber obtained in Example 5 has a number of convex shaped structures outside, the fiber surface has grooves, which is similar to the circular structure of Example 1. Compared with radiant refrigeration fiber, it has a larger surface area, so it can enhance the moisture absorption and perspiration performance of the fiber. And because of the modification of fluororesin, the fiber is more flexible. Therefore, the internal structure of the fiber can be controlled by melt composite spinning, which can enhance the comfort while maintaining its radiant cooling performance.

实施例6：Example 6:

如图5所示，该实施例中制备的辐射制冷纤维的截面，为圆形，包括第一组分20和第二组分30，并且第一组分20和第二组分30的形状分别为圆形中的半圆。该第一组分20中的聚合物基底材料为聚对苯二甲酸丙二酯(PTT)，第一组分20中的无机微纳颗粒为TiO ₂，其质量比例为50wt.％；该第二组分30中的聚合物基底材料为聚对苯二甲酸乙二酯(PET)，该第二组分30中的无机微纳颗粒的质量比例为0，即零掺杂。 As shown in Figure 5, the cross-section of the radiant refrigeration fiber prepared in this embodiment is circular, including a first component 20 and a second component 30, and the shapes of the first component 20 and the second component 30 are respectively It is a semicircle in a circle. The polymer base material in the first component 20 is polytrimethylene terephthalate (PTT), the inorganic micro-nano particles in the first component 20 are TiO ₂ , and the mass ratio is 50 wt.%; The polymer base material in the second component 30 is polyethylene terephthalate (PET), and the mass ratio of the inorganic micro-nano particles in the second component 30 is 0, that is, zero doping.

该辐射制冷纤维的制备方法，包括以下步骤：The preparation method of the radiant refrigeration fiber includes the following steps:

将1200g聚对苯二甲酸丙二酯(PTT)颗粒粉碎至粉末状，加入1200g于120℃真空烘箱中烘干24h的TiO ₂颗粒混合均匀。将混合材料通过双螺杆挤出机在290℃，6MPa压力下挤出熔体铸带。将铸带通过常温水浴进行凝固，导引铸带穿过引导轮至切片机，将固化的熔体铸带切成PTT和TiO ₂(50wt.％)的复合材料母粒。 1200 g of polytrimethylene terephthalate (PTT) particles were crushed to powder, and 1200 g of TiO ₂ particles dried in a vacuum oven at 120° C. for 24 hours were added and mixed uniformly. The mixed material was extruded into the melt-cast belt through a twin-screw extruder at 290°C and a pressure of 6 MPa. The cast strip is solidified in a water bath at room temperature, and the cast strip is guided through the guide wheel to the slicer, and the solidified melt cast strip is cut into _{composite master batches of PTT and TiO 2} (50 wt.%).

同理制得PET母粒。In the same way, a PET masterbatch was prepared.

将PTT和TiO ₂(50wt.％)复合材料母粒于120℃真空烘箱中干燥24h。将干燥完成后的PTT和TiO ₂(50wt.％)复合材料母粒、PET母粒分别填入熔融纺丝机料斗中，调整熔融纺丝机各区的温度和螺杆转速，稳定螺杆压力，熔融复合纺丝制备得到并列结构辐射制冷纤维，并通过300m/min的卷绕速度收丝落筒，由此得到一半为聚对苯二甲酸乙二酯 (PET)、一半均匀掺杂50wt.％二氧化钛颗粒的聚对苯二甲酸丙二酯(PTT)的并列结构辐射制冷纤维。 The PTT and TiO ₂ (50wt.%) composite masterbatch was dried in a vacuum oven at 120°C for 24 hours. Fill the dried PTT and TiO ₂ (50wt.%) composite material masterbatch and PET masterbatch into the hopper of the melt spinning machine respectively, adjust the temperature and screw speed of each zone of the melt spinning machine, stabilize the screw pressure, and melt compound The side-by-side radiant refrigeration fiber is prepared by spinning, and the yarn is taken up and doffed at a winding speed of 300m/min, thereby obtaining half of polyethylene terephthalate (PET) and half uniformly doped with 50wt.% titanium dioxide particles Polytrimethylene terephthalate (PTT) side-by-side structure radiant refrigeration fiber.

103，辐射制冷织物的制备步骤与实施例1相同，由此得到一半为聚对苯二甲酸乙二酯(PET)、一半掺杂50wt.％二氧化钛颗粒的聚对苯二甲酸丙二酯(PTT)的并列结构辐射制冷织物。103. The preparation steps of the radiant refrigeration fabric are the same as in Example 1, thereby obtaining half of the polyethylene terephthalate (PET) and half of the polytrimethylene terephthalate (PTT) doped with 50wt.% titanium dioxide particles. ) Radiant cooling fabric with side-by-side structure.

取实施例2和6的复合材料辐射制冷纤维进行对比。实施例6所制备的辐射制冷是一半为聚对苯二甲酸乙二酯(PET)、一半均匀掺杂50wt.％二氧化钛颗粒的聚对苯二甲酸丙二酯(PTT)的并列结构纤维，由于双组分不同的取向和结晶结构，二者之间存在热收缩率差异，受热后两组分收缩应力不同而产生异收缩效应导致整根纤维自发地产生扭转，由此纤维具有不同程度的伸缩性和弹性。与实施例2的圆形结构辐射制冷纤维相比，这种并列结构纤维及其织物在具有优异辐射制冷性能的同时，具备良好的卷曲稳定性。所以通过熔融复合纺丝调控纤维内部结构，可以在维持其辐射制冷性能的同时，极大增强舒适性。Take the composite radiant refrigeration fiber of Examples 2 and 6 for comparison. The radiant refrigeration prepared in Example 6 is a side-by-side structure fiber of half polyethylene terephthalate (PET) and half polyethylene terephthalate (PTT) uniformly doped with 50wt.% titanium dioxide particles. The two components have different orientations and crystalline structures, and there is a difference in thermal shrinkage between the two components. After the two components are heated, the shrinkage stress of the two components is different and the different shrinkage effect results in the spontaneous twist of the entire fiber, and the fiber has different degrees of expansion and contraction. Sex and flexibility. Compared with the circular structure radiant refrigeration fiber of Example 2, this side-by-side structure fiber and its fabric have excellent radiant refrigeration performance and good crimp stability. Therefore, the internal structure of the fiber can be controlled by melt composite spinning, which can greatly enhance the comfort while maintaining its radiant cooling performance.

实施例7：Example 7:

如图6所示，为一种截面为橘瓣结构的辐射制冷纤维，该辐射制冷纤维包括两种组分，第一组分20的聚合物基底材料为尼龙6(PA6)，掺杂的无机微纳颗粒为TiO ₂，平均粒径约600nm，在PA6内的掺杂浓度为50wt.％。第二组分30的聚合物基底材料为聚对苯二甲酸丙二酯(PTT)，无机微纳颗粒为零掺杂。 As shown in Figure 6, it is a radiant refrigeration fiber with an orange petal structure in cross section. The radiant refrigeration fiber includes two components. The polymer base material of the first component 20 is nylon 6 (PA6), doped with inorganic The micro-nano particles are TiO ₂ with an average particle size of about 600 nm, and the doping concentration in PA6 is 50 wt.%. The polymer base material of the second component 30 is polytrimethylene terephthalate (PTT), and the inorganic micro-nano particles are zero-doped.

该辐射制冷纤维的制备方法为：The preparation method of the radiant refrigeration fiber is:

将1200g尼龙6(PA6)颗粒粉碎至粉末状，加入1200g TiO ₂颗粒混合均匀，该TiO ₂颗粒先于120℃真空烘箱中烘干24h。将混合材料通过双螺杆挤出机在270℃，4MPa压力下挤出熔体铸带。将铸带通过常温水浴进行凝固，导引铸带穿过引导轮至切片机，将固化的熔体铸带切成PA6和TiO ₂(50wt.％)复合材料母粒。 1200g nylon 6 (PA6) particles were crushed to powder, and 1200g TiO ₂ particles were added and mixed uniformly. The TiO ₂ particles were first dried in a vacuum oven at 120°C for 24 hours. The mixed material was extruded into the melt cast belt through a twin-screw extruder at 270° C. and a pressure of 4 MPa. The cast belt is solidified in a water bath at room temperature, and the cast belt is guided through the guide wheel to the slicer, and the solidified melt cast belt is cut into PA6 and TiO ₂ (50wt.%) composite masterbatch.

(2)熔融复合纺丝制备辐射制冷纤维：(2) Melt composite spinning to prepare radiant refrigeration fiber:

将PA6和TiO ₂(50wt.％)复合材料母粒于120℃真空烘箱中干燥24h。将干燥完成后的PA6和TiO ₂(50wt.％)复合材料母粒和PTT母粒分别填入熔融纺丝机料斗中，调整熔融纺丝机各区的温度和螺杆转速，稳定螺杆压力，熔融复合纺丝制备得到橘瓣结构辐射制冷纤维，并通过300m/min的卷绕速度收丝落筒，由此得到掺杂50wt.％二氧化钛颗粒的橘瓣结构辐射制冷纤维。 The PA6 and TiO ₂ (50wt.%) composite masterbatch was dried in a vacuum oven at 120°C for 24 hours. Fill the dried PA6 and TiO ₂ (50wt.%) composite masterbatch and PTT masterbatch into the hopper of the melt spinning machine respectively, adjust the temperature and screw speed of each zone of the melt spinning machine, stabilize the screw pressure, and melt compound The orange petal structure radiant refrigeration fiber is prepared by spinning, and the yarn is taken up and doffed at a winding speed of 300 m/min, thereby obtaining an orange petal structure radiant refrigeration fiber doped with 50 wt.% titanium dioxide particles.

(3)辐射制冷织物的制备步骤与实施例1相同，由此得到掺杂二氧化钛颗粒的橘瓣结构辐射制冷织物。(3) The preparation steps of the radiant refrigeration fabric are the same as in Example 1, thereby obtaining an orange petal structure radiant refrigeration fabric doped with titanium dioxide particles.

实施例8：Example 8:

如图7所示，该辐射制冷纤维的截面为海岛状，其中的第一组分20的聚合物基底材料为聚对苯二甲酸乙二酯(PET)，其内掺杂的无机微纳颗粒为TiO ₂，平均粒径为600nm，在PET内的掺杂浓度为50wt.％。第二组分30的聚合物基底材料为聚苯乙烯(PS)，无机微纳颗粒为零掺杂。 As shown in Figure 7, the cross-section of the radiant refrigeration fiber is sea-island-shaped, and the polymer base material of the first component 20 is polyethylene terephthalate (PET), and inorganic micro-nano particles doped therein It is TiO ₂ , the average particle size is 600nm, and the doping concentration in the PET is 50wt.%. The polymer base material of the second component 30 is polystyrene (PS), and the inorganic micro-nano particles are zero-doped.

该纤维的制备方法，包括The preparation method of the fiber includes

将1200g聚对苯二甲酸乙二酯(PET)颗粒粉碎至粉末状，加入1200g TiO ₂颗粒混合均匀，该TiO ₂颗粒先于120℃真空烘箱中烘干24h。将混合材料通过双螺杆挤出机在280℃，4MPa压力下挤出熔体铸带。将铸带通过常温水浴进行凝固，导引铸带穿过引导轮至切片机，将固化的熔体铸带切成PET和TiO ₂(50wt.％)复合材料母粒。 1200g of polyethylene terephthalate (PET) particles were crushed to powder, and 1200g of TiO ₂ particles were added and mixed uniformly. The TiO ₂ particles were first dried in a vacuum oven at 120°C for 24 hours. The mixed material was extruded into the melt cast belt through a twin-screw extruder at 280° C. and a pressure of 4 MPa. The casting belt is solidified in a water bath at room temperature, and the casting belt is guided through the guide wheel to the slicer, and the solidified melt casting belt is cut into PET and TiO ₂ (50wt.%) composite masterbatch.

将PET和TiO ₂(50wt.％)复合材料母粒于120℃真空烘箱中干燥24h。将干燥完成后的PET和TiO ₂(50wt.％)复合材料母粒、聚苯乙烯(PS)母粒分别填入熔融纺丝机料斗中，调整熔融纺丝机各区的温度和螺杆转速，稳定螺杆压力，熔融复合纺丝制备得到海岛结构辐射制冷纤维，并通过300m/min的卷绕速度收丝落筒，由此得到掺杂50wt.％二氧化钛颗粒的海岛结构辐射制冷纤维。 The PET and TiO ₂ (50wt.%) composite masterbatch was dried in a vacuum oven at 120°C for 24 hours. Fill the dried PET and TiO ₂ (50wt.%) composite material masterbatch and polystyrene (PS) masterbatch into the hopper of the melt spinning machine respectively, and adjust the temperature and screw speed of each zone of the melt spinning machine to stabilize The sea-island structure radiant refrigeration fiber is prepared by screw pressure and melt composite spinning, and the sea-island structure radiant refrigeration fiber is obtained by taking up the yarn at a winding speed of 300 m/min.

(3)辐射制冷织物的制备步骤与实施例1相同，由此得到掺杂50wt.％二氧化钛颗粒的海岛结构辐射制冷织物。(3) The preparation steps of the radiant refrigeration fabric are the same as in Example 1, thereby obtaining a sea-island structure radiant refrigeration fabric doped with 50 wt.% titanium dioxide particles.

取实施例2、7、8的复合材料辐射制冷纤维进行对比。实施例7和实施例8所制备的辐射制冷纤维具有良好的制冷性能和机械强度。并且可以通过化学试剂溶解、物理剥离、机械处理等方法得到超细纤维，相比较实施例2所制备的单一结构辐射制冷纤维，超细纤维所制备的织物在具有优异辐射制冷性能的同时，具有更高的柔软度和舒适性。且将实施例8制备的海岛结构纤维的岛组分去除还可以得到多孔性中空纤维，富有弹性。所以通过熔融复合纺丝调控纤维内部结构，可以在维持其辐射制冷性能的同时，使织物光泽柔和，大大提高穿戴舒适度，可织制适用于人体皮肤降温的高级纺丝织物。Take the composite radiant refrigeration fiber of Examples 2, 7, and 8 for comparison. The radiant refrigeration fiber prepared in Example 7 and Example 8 has good refrigeration performance and mechanical strength. In addition, ultrafine fibers can be obtained by chemical reagent dissolution, physical peeling, mechanical treatment and other methods. Compared with the single-structure radiant refrigeration fiber prepared in Example 2, the fabric prepared by the ultrafine fiber has excellent radiant refrigeration performance while having excellent radiant refrigeration performance. Higher softness and comfort. In addition, removing the island component of the sea-island structure fiber prepared in Example 8 can also obtain a porous hollow fiber, which is rich in elasticity. Therefore, by adjusting the internal structure of the fiber by melt composite spinning, the radiant cooling performance can be maintained while the fabric is softened and the wearing comfort is greatly improved. It can weave high-grade spun fabric suitable for cooling the human skin.

还需要说明的是，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、商品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、商品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括……”限定的要素，并不排除在包括要素的过程、方法、商品或者设备中还存在另外的相同要素。It should also be noted that the terms "include", "include" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, commodity or equipment including a series of elements not only includes those elements, but also includes Other elements that are not explicitly listed, or also include elements inherent to such processes, methods, commodities, or equipment. If there are no more restrictions, the elements defined by the sentence "including..." do not exclude the existence of other identical elements in the process, method, commodity, or equipment that includes the elements.

以上仅为本申请的实施例而已，并不用于限制本申请。对于本领域技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原理之内所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。The above are only examples of the application, and are not used to limit the application. For those skilled in the art, this application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of this application shall be included in the scope of the claims of this application.

Claims

一种辐射制冷纤维的制备方法，包括：A preparation method of radiant refrigeration fiber, including:

将无机微纳颗粒和聚合物基底材料按照预定的重量比例混合，制得复合材料母粒；Mixing the inorganic micro-nano particles and the polymer base material according to a predetermined weight ratio to prepare a composite material masterbatch;

将复合材料母粒在纺丝组件中复合挤出成型，经卷绕后得到辐射制冷纤维。The composite material masterbatch is compounded and extruded in the spinning assembly, and the radiant refrigerating fiber is obtained after winding.
如权利要求1所述的辐射制冷纤维的制备方法，其特征在于：所述将无机微纳颗粒和聚合物基底材料按照预定的重量比例混合，制得复合材料母粒，包括，The method for preparing a radiant refrigeration fiber according to claim 1, characterized in that: said mixing the inorganic micro-nano particles and the polymer base material in a predetermined weight ratio to prepare a composite material masterbatch, comprising:

将第一无机微纳颗粒和第一聚合物基底材料按照预定的第一重量比例混合均匀，制得第一复合材料母粒，将第二无机微纳颗粒和第二聚合物基底材料按照预定的第二重量比例混合均匀，制得第二复合材料母粒；The first inorganic micro-nano particles and the first polymer base material are mixed uniformly according to a predetermined first weight ratio to prepare a first composite material masterbatch, and the second inorganic micro-nano particles and the second polymer base material are mixed according to a predetermined first weight ratio. The second weight ratio is evenly mixed to obtain the second composite material masterbatch;

将复合材料母粒在纺丝组件中挤出成型，经卷绕后得到辐射制冷纤维，包括，将所述第一复合材料母粒作为第一组分，所述第二复合材料母粒作为第二组分，在纺丝组件中复合挤出成型，经卷绕后得到辐射制冷纤维。The composite material masterbatch is extruded and formed in the spinning assembly, and the radiant refrigeration fiber is obtained after winding. The two components are compounded and extruded in the spinning assembly, and the radiant refrigeration fiber is obtained after winding.
如权利要求2所述的辐射制冷纤维的制备方法，其特征在于：所述第一复合材料母粒中无机微纳颗粒的重量占比为1％-80％，所述第二复合材料母粒中无机微纳颗粒的重量占比为0-20％，并且所述第一复合材料母粒中无机微纳颗粒的重量占比大于等于第二复合材料母粒中无机微纳颗粒的重量占比。The method for preparing a radiant refrigeration fiber according to claim 2, wherein the weight ratio of the inorganic micro-nano particles in the first composite material masterbatch is 1%-80%, and the second composite material masterbatch The weight ratio of the inorganic micro/nano particles in the first composite material master particle is 0-20%, and the weight ratio of the inorganic micro/nano particles in the first composite material master particle is greater than or equal to the weight ratio of the inorganic micro/nano particles in the second composite material master particle .
如权利要求3所述的辐射制冷纤维的制备方法，其特征在于：所述第一聚合物基底材料与所述第二聚合物基底材料，可以相同也可以不同；所述第一无机微纳颗粒与第二无机微纳颗粒，可以相同也可以不同。The method for preparing a radiant refrigeration fiber according to claim 3, wherein: the first polymer base material and the second polymer base material may be the same or different; the first inorganic micro-nano particles It can be the same as or different from the second inorganic micro-nano particles.
如权利要求2所述的辐射制冷纤维的制备方法，其特征在于：还包括至少一种第三组分，所述至少一种第三组分与第一、第二组分一起在纺丝组件中复合挤出成型，经卷绕后得到辐射制冷纤维；The method for preparing radiant refrigeration fiber according to claim 2, characterized in that it further comprises at least one third component, and the at least one third component is combined with the first and second components in the spinning assembly Middle composite extrusion molding, radiant refrigeration fiber is obtained after winding;

所述至少一种第三组分为第三无机微纳颗粒和第三聚合物基底材料按照第三重量比例制得的至少一种第三复合材料母粒。The at least one third component is at least one third composite material master particle prepared by third inorganic micro-nano particles and a third polymer base material according to a third weight ratio.
如权利要求5所述的辐射制冷纤维的制备方法，其特征在于：所述至少一种第三复合材料母粒中无机微纳颗粒的重量占比为1％-80％，并且所述至少一种第三复合材料母粒中无机微纳颗粒的重量占比大于等于第二复合材料母粒中无机微纳颗粒的重量占比。The method for preparing a radiant refrigeration fiber according to claim 5, wherein the weight proportion of the inorganic micro-nano particles in the at least one third composite material masterbatch is 1%-80%, and the at least one The weight proportion of the inorganic micro-nano particles in the third composite material masterbatch is greater than or equal to the weight proportion of the inorganic micro-nano particles in the second composite material masterbatch.
如权利要求1-6中任一项所述的辐射制冷纤维的制备方法，其特征在于：所述聚合物基底材料包括聚甲基丙烯酸甲酯(PMMA)、氟树脂、聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)、聚对苯二甲酸乙二酯(PET)、聚氯乙烯(PVC)、聚苯乙烯(PS)、聚酯和间苯二甲酸酯磺酸钠共聚物、丙烯酸酯共聚物、聚乙二醇(PEG)、聚对苯二甲酸丙二酯(PTT)、聚偏二氯乙烯树脂(PVDC)、醋酸乙烯酯树脂、聚乙烯醇(PVA)和聚乙烯醇缩乙醛中的一种或一种以上的混合物。The method for preparing a radiant refrigeration fiber according to any one of claims 1-6, wherein the polymer base material includes polymethylmethacrylate (PMMA), fluororesin, polyethylene (PE), Polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polystyrene (PS), polyester and sodium isophthalate sulfonate Copolymers, acrylate copolymers, polyethylene glycol (PEG), polytrimethylene terephthalate (PTT), polyvinylidene chloride resin (PVDC), vinyl acetate resin, polyvinyl alcohol (PVA) and One or more mixtures of polyvinyl acetal.
如权利要求1-6中任一项所述的辐射制冷纤维的制备方法，其特征在于：所述无机微纳颗粒包括二氧化钛(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)中的一种或一种以上的混合物。 The method for preparing a radiant refrigeration fiber according to any one of claims 1 to 6, wherein the inorganic micro-nano particles include titanium dioxide (TiO ₂ ), silicon dioxide (SiO ₂ ), zinc oxide (ZnO) , Silicon carbide (SiC), silicon nitride (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 ) or a mixture of more than one.
如权利要求1-6中任一项所述的辐射制冷纤维的制备方法，其特征在于：所述无机微纳颗粒的粒径范围为0.03μm-250μm。The method for preparing a radiant refrigeration fiber according to any one of claims 1 to 6, wherein the particle size of the inorganic micro-nano particles ranges from 0.03 μm to 250 μm.
如权利要求1-6中任一项所述的辐射制冷纤维的制备方法，其特征在于：所述辐射制冷纤维单丝纤度范围为1D-50D，纤维直径范围0.1mm-1.5mm。The method for preparing a radiant refrigeration fiber according to any one of claims 1 to 6, wherein the radiant refrigeration fiber monofilament size ranges from 1D to 50D, and the fiber diameter ranges from 0.1mm to 1.5mm.
如权利要求1-6中任一项所述的辐射制冷纤维的制备方法，其特征在于：所述辐射制冷纤维包括单一结构、皮芯结构、径向梯度浓度结构、人字形结构、异形凸起结构、橘瓣结构、并列结构、旋转对称方位结构和海岛结构中的至少一种。The method for preparing a radiant refrigeration fiber according to any one of claims 1 to 6, wherein the radiant refrigeration fiber includes a single structure, a skin-core structure, a radial gradient concentration structure, a herringbone structure, and a special-shaped protrusion. At least one of structure, orange petal structure, side-by-side structure, rotationally symmetric azimuth structure, and sea-island structure.
如权利要求1-6中任一项所述的辐射制冷纤维的制备方法，其特征在于：所述复合挤出温度为100℃-600℃，卷绕速度为10m/min-6000m/min。The method for preparing a radiant refrigeration fiber according to any one of claims 1-6, wherein the composite extrusion temperature is 100°C-600°C, and the winding speed is 10m/min-6000m/min.
一种辐射制冷纤维织物的制备方法，具体包括，将上述权利要求1-12中得到的辐射制冷纤维，通过针织和/或机织制得到辐射制冷织物。A preparation method of a radiant refrigeration fiber fabric, specifically comprising: knitting and/or weaving the radiant refrigeration fiber obtained in the above claims 1-12 to obtain a radiant refrigeration fabric.
如权利要求13所述的辐射制冷纤维织物的制备方法，其特征在于：所述通过针织和/或机织制得辐射制冷织物，具体包括The method for preparing a radiant cooling fiber fabric according to claim 13, wherein the radiant cooling fabric obtained by knitting and/or weaving specifically comprises

将辐射制冷纤维作为经纱和纬纱中的一种，将其他纤维作为经纱和纬纱中的另一种进行编织；The radiant refrigeration fiber is used as one of the warp and weft, and other fibers are used as the other of the warp and weft for weaving;

或者是将辐射制冷纤维作为经纱和纬纱进行编织。Or the radiant refrigeration fiber is woven as warp and weft.