CN114808170B - Light-colored sterilization heat storage functional fiber, preparation method thereof and fiber product - Google Patents
Light-colored sterilization heat storage functional fiber, preparation method thereof and fiber product Download PDFInfo
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- CN114808170B CN114808170B CN202110117636.4A CN202110117636A CN114808170B CN 114808170 B CN114808170 B CN 114808170B CN 202110117636 A CN202110117636 A CN 202110117636A CN 114808170 B CN114808170 B CN 114808170B
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- 239000000835 fiber Substances 0.000 title claims abstract description 108
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 46
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000005338 heat storage Methods 0.000 title description 41
- 239000000843 powder Substances 0.000 claims abstract description 59
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 45
- 239000010937 tungsten Substances 0.000 claims abstract description 45
- 239000011148 porous material Substances 0.000 claims abstract description 43
- 239000011941 photocatalyst Substances 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 238000009825 accumulation Methods 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011858 nanopowder Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 29
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- 239000002904 solvent Substances 0.000 claims description 12
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- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
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- 229910052723 transition metal Inorganic materials 0.000 claims description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000906 Bronze Inorganic materials 0.000 description 29
- 239000010974 bronze Substances 0.000 description 29
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- OHUPZDRTZNMIJI-UHFFFAOYSA-N [Cs].[W] Chemical group [Cs].[W] OHUPZDRTZNMIJI-UHFFFAOYSA-N 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
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- 238000007873 sieving Methods 0.000 description 3
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- 238000002834 transmittance Methods 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
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- 239000002923 metal particle Substances 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 241000295644 Staphylococcaceae Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- YENIOYBTCIZCBJ-UHFFFAOYSA-N acetic acid;1-methoxypropan-2-ol Chemical compound CC(O)=O.COCC(C)O YENIOYBTCIZCBJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- D01F1/103—Agents inhibiting growth of microorganisms
-
- 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
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
-
- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
Abstract
The invention relates to a light-colored sterilization and heat accumulation functional fiber, a preparation method thereof and a fiber product, wherein the sterilization and heat accumulation functional fiber consists of sterilization and heat accumulation particles and a high polymer matrix, and the sterilization and heat accumulation particles are obtained by coating compound powder of nano tungsten bronze powder/photocatalyst nano powder with a porous material with a mesoporous pore structure.
Description
Technical Field
The invention relates to a novel functional fiber, a preparation method thereof and a fiber product, in particular to a novel heat-accumulating and sterilizing functional fiber based on a photo-thermal effect, a preparation method thereof and a fiber product.
Background
Along with the continuous development of science and technology and the improvement of human living standard, the requirements of people on clothes are changed continuously, and the novel functional fiber material is required to achieve the heat preservation effect, avoid the serious influence on the comfort of the clothes and simultaneously have the antibacterial effect. The heat accumulating fiber can absorb heat from human body or outside actively and store the heat in the fiber to realize continuous heat release. In the prior research work, the heat storage functional materials are various, and the main stream comprises bamboo charcoal, coffee carbon, graphene, natural minerals, carbide, nitride, metal particles and the like.
For example: chinese patents CN201310392735, CN201410546018, CN201620824033 use bamboo charcoal as a heat storage functional material, while chinese patents CN201320282112, CN201810867861 use coffee charcoal as a heat storage functional material. The carbon heat storage functional material is convenient to prepare and low in cost, but has limited heat storage efficiency, so that the addition amount is large, and the fabric can only be black or coffee, cannot be dyed, and limits the application. The Chinese patent CN201610474260 uses graphene, and has high heat storage efficiency and small addition amount, but still only can be black fiber, and the graphene has high cost and low practicability. Chinese patent CN201910020877 and CN201811206953 use natural mineral functional filler, chinese patent CN201610528052 uses inorganic carbide such as zirconium carbide and silicon carbide, chinese patent CN201710346483 uses titanium nitride, chinese patent CN201210148274 and CN201210151412 disclose that mixed metal particles are used for modifying high polymer fiber to prepare heat accumulating fiber, but the above methods have the defects of large addition amount, large specific gravity of powder, easy enrichment and falling off in the melting process, basically black color, difficult subsequent dyeing and the like.
In summary, in the existing heating fiber process, almost all the heating fibers are black or dark color fibers, and the addition amount of most functional materials is large. Therefore, there is a need to explore a light-colored fiber that stores heat efficiently, which will help to improve the heat storage capacity, mechanical properties, and the applicability of subsequent fabrics.
Alkali tungsten bronze inorganic ceramic materials having a blue color are known. However, the color of the alkali metal tungsten bronze material is darker blue, and compared with a black material, the absorption of visible light is lower, so that the light absorption and heat storage effects are reduced to a certain extent; and the thermal storage fiber has dark blue appearance, and if the thermal storage fiber is directly manufactured, the color is still dark, and the dyeing property is still insufficient, so that the thermal storage fiber needs to be modified by being compounded with other materials. Chinese patent CN201710678395 combines tungsten bronze with tin oxide and titanium nitride, so that the color is deepened to improve the light absorption capacity, and the dyeing property of the product is reduced; chinese patent CN201910647223 directly coats tungsten bronze with carbon, resulting in darker black tungsten bronze. The method only considers the improvement of the heat storage performance of the tungsten bronze composite fiber, but neglects the dyeability of the tungsten bronze composite fiber, so that the application range is limited. Research on the preparation of dyeable high-efficiency heat storage fibers using tungsten bronze is currently blank.
Disclosure of Invention
Aiming at the defects of the existing heat storage fiber, the invention aims to provide a novel tungsten bronze/photocatalyst composite sterilization heat storage functional fiber, so that the preparation of light-colored high-efficiency heat storage fiber is realized, and the product has the characteristics of high-efficiency heat storage function, high-efficiency sterilization function and light color.
In a first aspect, the invention provides a sterilization and heat storage functional fiber, which consists of sterilization and heat storage particles and a high polymer matrix, wherein the sterilization and heat storage particles are obtained by coating compound powder of nano tungsten bronze powder/photocatalyst nano powder with a porous material with a mesoporous pore structure. According to the composition of the invention, after the tungsten bronze powder is compounded with the photocatalyst powder with the catalytic function, the nano inorganic material with mesoporous characteristic is adopted for porous coating modification, so that the ultraviolet light-absorbing and heat-accumulating type ultraviolet light-accumulating fiber has the functions of high-efficiency infrared light absorption and heat accumulation, bacteriostasis and moisture absorption and heat accumulation, and can improve the problem that dark color fibers are difficult to dye.
The content of the sterilizing heat storage particles may be 0.2 to 20wt.% of the fiber.
The photocatalyst nano powder can be at least one of titanium dioxide, doped titanium dioxide, zinc oxide and bismuth vanadate. The particle size of the photocatalyst nano powder can be 5-500 nm.
The nano tungsten bronze powder is provided with M x WO 3 Wherein M can be more than one element of alkali metal element, alkaline earth metal element and transition metal element, and x is more than 0 and less than or equal to 1. The particle size of the nano tungsten bronze powder can be 5-500 nm.
The mass ratio of the photocatalyst nano powder to the nano tungsten bronze powder can be (100:1) - (1:10).
The porous material may have a mesoporous pore structure of 2 to 50nm. The material with the pores of 2-50nm has stronger capability of actively absorbing water vapor in air.
The coating thickness of the porous material may be 0.05 to 5 microns.
The particle size of the sterilization and heat storage particles can be 0.1-10 microns.
The material of the high molecular polymer matrix can be at least one of polyamide, polyethylene terephthalate, polypropylene and polybutylene terephthalate.
The fiber can be one of solid long fiber, solid short fiber and hollow short fiber. The hollow section of the hollow short fiber can be one of a single-hole circle, a single-hole triangle, a four-hole circle or a seven-hole circle.
The appearance color of the sterilization heat storage functional fiber can be white or light blue. The color range of the sterilization and heat storage functional fiber in the form of the invention is characterized by CIE color coordinates, wherein the color coordinates (x, y) are 0.05< x <0.33, and 0.1< y <0.35.
In a second aspect, the present invention provides a fibrous product obtained by processing any one of the above-described heat-sterilization functional fibers. The fiber can be used in various applications such as clothing, living cloth, medical cloth and other fiber products and other industrial fiber materials which are required to have high heat storage performance, effective antibacterial performance and easy dyeing.
In a third aspect, the present invention provides a method for preparing the fiber with sterilization and heat storage functions, which is characterized by comprising: mixing nano tungsten bronze powder with photocatalyst nano powder, and adding a porous material while stirring to obtain mixed powder; preparing slurry after sintering the mixed powder; mixing the slurry with the powder of the high molecular polymer, and heating to volatilize the solvent to obtain a mixture; granulating the mixture to obtain master batches; and spinning and forming the master batch. According to the method, the porous material is coated with the mixed particles of tungsten bronze powder and photocatalyst powder, the particles of the photocatalyst and the tungsten bronze are stirred and mixed to obtain the compound powder, and the compound powder enters the inside of the pores and is fixed in the pores through sintering in the process of mixing with the porous particles.
The spinning forming may include: mixing the master batch and extruding.
The spinning forming may also include: mixing the master batch with the white slices made of the high-molecular polymer, and extruding.
Drawings
FIG. 1 shows the appearance of a light colored functional fiber according to example 1;
FIG. 2 shows an infrared thermographic test of the fiber heat storage capacity of the fibrous article of example 2;
FIG. 3 shows a comparative photo-catalytic bacteriostatic graph of the fabric of example 3;
fig. 4 shows the color range of the heat-accumulative fiber (bluish fiber) obtained in the embodiment of the present invention.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
The present disclosure relates to a light-colored functional fiber and a fiber product (mainly a textile product) thereof, wherein the fiber contains tungsten bronze/photocatalyst nano ceramic powder, and the nano ceramic powder is modified by porous coating, and has the dual functions of moisture absorption, light absorption, heat storage and sterilization. And the fiber can have a light-colored appearance (light blue), and is easy to carry out post-processing such as dyeing. The fiber and the fabric have strong heat storage capacity, can effectively keep warm, and lighten the weight of textiles. The functional fibers and the fabric have different colors from white to light blue along with different addition amounts of the nano functional ceramic powder, but all belong to light colors, so that the functional fibers and the fabric are easy to dye into various dark colors, namely, the functional fibers and the fabric have strong dyeability and wide application range.
Embodiment 1.
The heat-accumulative fiber of embodiment 1 comprises heat-accumulative particles and a polymer matrix, and is made of polymer modified with heat-accumulative particles. The sterilization heat storage particles are obtained by coating compound powder of nano tungsten bronze powder/photocatalyst nano powder by porous materials with mesoporous pore structures. The compound powder can be positioned (adsorbed) on the surface of the porous material and in the pore canal structure. For example, the porous material has mesopores and macropores exceeding 1 μm, has a large surface area in the pore canal, is easy to adsorb powder materials, and is also adsorbed on the surface.
The tungsten bronze powder has M x WO 3 Wherein M can be alkali metal such as lithium, sodium, potassium, rubidium, cesium, alkaline earth metal such as beryllium, magnesium, calcium, strontium, barium, radium, transition metal element, etc. in the periodic table, x is more than 0 and less than or equal to 1. The preferable element M is Cs, li, na, K, rb, which can make tungsten oxide blue, and more preferable is Cs, and further improves infrared absorption efficiency. In this embodiment, the tungsten bronze powder preferably has a high visible light transmittance (more than 70%) and is easy to prepare a light-colored composite material. In a preferred embodiment, the tungsten bronze powder is cesium tungsten bronze Cs 0.32 WO 3 Can further absorb ultraviolet light, infrared light, heat with high efficiency, e.g. Cs 0.32 WO 3 The powder is directly spread into a film (spread out, and the optical property (transmittance) of the powder is directly tested), so that the visible light transmittance exceeds 70%, the near infrared absorptivity is as high as 95%, and the ultraviolet absorptivity is as high as 99%. The grain size (grain diameter) of the tungsten bronze powder can be 5-500 nm. In this embodiment, the tungsten bronze powder can be inserted into the pores (gaps between porous layers) of the porous material during mixing of the compound powder and the porous material, which will be described later.
The photocatalyst nano powder can be at least one of titanium dioxide, doped titanium dioxide, zinc oxide and bismuth vanadate. Preferably, titanium dioxide photocatalysts doped with silver, iron and the like are used, specific metal ions are doped, the photocatalytic sterilization capability can be effectively improved, and the doping amount can be 0.5% -5%. The particle size of the photocatalyst nano powder can be 5-500 nm. In this embodiment, the photocatalyst nano-powder can be inserted into the pores (gaps of the porous layer) of the porous material during mixing of the compound powder and the porous material, which will be described later. The photocatalyst nano powder can play a role of photocatalysis, and after absorbing the energy of sunlight or other light sources, electrons on the surfaces of particles are activated to leave the original orbit, and positive holes are generated. The escaped electrons have strong reducibility, the holes have strong oxidability, and the electrons and the holes respectively react with water vapor in the air to generate active oxygen and hydroxyl free radicals, so that bacteria are oxidized and decomposed into carbon dioxide and water, and the effects of sterilization and bacteriostasis are achieved. The sterilization characteristic of the photocatalyst has strong stability, and can sterilize for a long time; is nontoxic and harmless, has no harm to human body contact, and is suitable for underwear. Meanwhile, the photocatalyst nano powder is white or nearly white, and can be compounded with tungsten bronze to improve the deep blue of the tungsten bronze. In the tungsten bronze/photocatalyst compound powder, the compound mass ratio of the tungsten bronze to the photocatalyst can be 100:1-1:10. When the compounding mass ratio of the two is more than 100:1, the dark color can be restrained and the color is beyond the CIE color coordinate range. When the compounding mass ratio of the two is below 1:10, the influence of the heat storage effect can be restrained.
In the sterilization heat storage particles, the compound powder of nano tungsten bronze powder/photocatalyst nano powder is coated by a porous coating layer formed by porous materials with mesoporous pore structures. For example, the porous coating composition may be from at least one of nano-hydroxyapatite, nano-zeolite, sepiolite, diatomaceous earth. The thickness of the porous layer (coating thickness of the porous material) may be 0.05 to 5 μm. The porous layer is a mesoporous material and contains a large number of mesoporous pore structures with the diameter of 2-50nm, and the porous layer has excellent moisture absorption characteristics, can absorb moisture in the environment in functional fiber application, realizes moisture absorption and heat accumulation, is matched with tungsten bronze to realize the functions of light absorption and moisture absorption and heat accumulation, and the moisture absorption effect can be cooperated with the light absorption and heat accumulation of the tungsten bronze to play a better heat accumulation effect and greatly improve the heat accumulation capacity. In addition, the porous layer has a large surface area, so that the porous layer has good adhesion to small molecules such as bacteria and fungi, attracts the bacteria and fungi to move towards the photocatalyst of the fiber, and promotes sterilization. Thereby, the use of a porous layer promotes the sterilization of the fibers. In addition, the porous layer is used as a coating layer of the compound powder, so that tungsten bronze/photocatalyst particles are not in direct contact with the high-molecular polymer in the fiber in practice, the damage of tungsten bronze and photocatalyst nano particles to a high-molecular polymer matrix is greatly reduced, the problem that the compound powder is incompatible with the high-molecular polymer is avoided, and the service life of the fiber is further prolonged. In addition, the use of the porous layer further reduces the specific gravity of the tungsten bronze in the composite structure and improves the deep blue color of the tungsten bronze.
The content of the sterilizing heat storage particles can account for 0.2 to 20 weight percent of the whole fiber. The content of the high molecular polymer can be 80 to 99.8 percent of the weight of the fiber. The appearance of the fiber with the sterilization and heat storage functions can be white or light blue, and the color of the fiber can gradually transition from white to light blue along with the increase of the dosage of the tungsten bronze/photocatalyst compound powder, and the fiber belongs to light color.
The particle size of the bactericidal heat storage particles of the present disclosure may be 0.1 to 10 microns. Tungsten bronze (general formula M) x WO 3 ) After the powder is compounded with the photocatalyst powder with the catalytic effect, the nano inorganic material with mesoporous characteristic is adopted for porous coating modification, so that the photocatalyst powder has the advantages of high-efficiency infrared absorption function, antibacterial effect, excellent light absorption and heat storage effect and moisture absorption effect. In addition, the tungsten bronze/photocatalyst nano ceramic powder can be prevented from directly contacting with the matrix, so that a protection effect is achieved.
The sterilization and heat accumulation functional fiber can be solid long fiber, solid short fiber and hollow short fiber. The hollow section of the hollow short fiber can be in a shape which can be realized in the prior art, such as a single-hole round shape, a single-hole triangle shape, a four-hole round shape or a seven-hole round shape. The hollow structure is further beneficial to the exertion of the heat storage effect. The color range of the bluish fiber of this embodiment is characterized using CIE color coordinates, color coordinates (x, y), where 0.05< x <0.33,0.1< y <0.35 (bluish color range shown in fig. 4).
The fiber can be further woven to obtain the light-colored sterilization heat storage fabric, and the fabric is formed by blending the fiber or the fiber with common textile materials such as cotton, hemp, silk and other high polymer fibers. The blending mass ratio of the sterilization and heat storage functional fiber to common textile materials such as cotton, hemp, silk and other high polymer fibers is not particularly limited, and can be common blending mass ratio in the field.
The following illustrates a method for preparing the sterilization and heat accumulation functional fiber disclosed in the present disclosure.
Firstly, mixing nano tungsten bronze powder with photocatalyst nano powder, and adding a porous material while stirring to obtain mixed powder. In some embodiments, tungsten bronze and photocatalyst nano powder can be accurately weighed according to the proportion, and then fed into a mixer to be mixed uniformly, so as to obtain compound powder, and then the porous material is added while mixing the powder. The mass ratio of the compound powder to the porous material can be 1: (1.9-20). The porous material feedstock may have a size between 0.1 and 10 microns.
And then, sintering the mixed powder to prepare slurry. In some embodiments, the mixed powder may be poured into a rotary atmosphere furnace, sintered in a nitrogen-hydrogen mixer atmosphere, and heated while rotating at a speed of 10-100 rpm for 1-6 hours at 150-300 ℃. In some embodiments, the sintered powder, the dispersing aid and the solvent can be mixed according to the proportion: dispersing auxiliary agent: the solvent=1:0.1-0.8:3-10, and the mixture is transferred into a sand mill, and ball milling with the diameter of 0.3 mm or less is used for fully grinding until uniform and stable nano color paste is obtained. The solvent can be at least one of water, ethyl acetate, xylene, acetone, ethanol, isopropanol and propylene glycol methyl ether acetate.
Then, the slurry is mixed with a powder of a high molecular polymer and heated to volatilize the solvent, thereby obtaining a mixture. In some embodiments, the nano color paste and the high polymer powder can be weighed according to the proportion, and then are put into a mixer, and are mixed while being heated until the solvent is fully volatilized, so as to obtain the mixture. The high molecular polymer (powder) as the material of the high molecular polymer matrix can be common chemical fiber preparation materials such as polyamide, polyethylene terephthalate, polypropylene, polybutylene terephthalate and the like. The slurry and the powder of the high molecular polymer may be mixed in an amount of (0.1 to 0.5): (0.5 to 0.9) and heating to volatilize the solvent. When the color paste prepared from the powder in the process is mixed with the high-molecular polymer powder, the viscosity is moderate, the color paste can be uniformly mixed, and the materials can be easily taken out from a mixer.
Then, the mixture is granulated to obtain master batch, and the master batch is subjected to spinning molding. In some embodiments, the blend may be pelletized by an extruder at a melting temperature of 250-300 ℃ to obtain a functional plastic masterbatch.
Spin forming may include: mixing the master batch and extruding. Spin forming may also include: mixing the master batch with the white slices made of the high-molecular polymer, and extruding. The functional master batch and the blank high-molecular polymer master batch can be mixed for integrally drawing wires. In some embodiments, the functional plastic master batch and the high-molecular polymer of the same material can be sliced, so that the functional plastic master batch: bai Qiepian =1:0 to 5, extruding filaments or short filaments in a fiber extruder or obtaining hollow short filaments by using a hollow template. The fibres obtained can be woven on a loom to the corresponding fabric.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below;
in the examples described below, reagents, materials and apparatus used, unless otherwise specified, are conventional reagents, conventional materials and conventional apparatus, which are commercially available, and the reagents involved are also synthetically obtainable by conventional synthetic methods.
Example 1
A) Weighing cesium tungsten bronze Cs with particle size of 50nm 0.32 WO 3 5 kg of powder, 2 kg of photocatalyst silver-doped titanium dioxide powder with the particle size of 20nm, feeding the powder into a stirring machine, uniformly mixing for 30min, slowly adding 20 kg of nano hydroxyapatite while stirring, and continuously stirring for 30min;
b) Pouring the mixed powder into a rotary atmosphere furnace, continuously introducing nitrogen and hydrogen mixed gas (the hydrogen accounts for 28 percent in the mixed gas), keeping the rotating speed of 20 revolutions per minute, and sintering at 300 ℃ for 3 hours to obtain composite powder, and sieving the composite powder by a 200-mesh sieve to remove large particles generated during sintering;
c) Weighing 10 kg of composite powder, using BYK company to provide 5 kg of wetting dispersant auxiliary agent and 40 kg of dimethylbenzene, fully and uniformly mixing, and then filling into a sand mill for grinding to obtain dispersed color paste;
d) Putting the dispersion color paste and 190 kg of Polyamide (PA) high polymer powder into a mixer, heating to 90 ℃ and continuously stirring and mixing for 10 hours until the solvent is fully volatilized to obtain a mixture;
e) Granulating the mixture by an extruder, and obtaining functional plastic master batches at a melting temperature of 280 ℃;
f) Weighing 100 kg of functional plastic master batches, mixing, loading into a fiber extruder, and extruding hollow short fibers by using a round hollow short fiber template to obtain 5D38 PA hollow short fibers;
the fiber appearance photograph obtained is shown in fig. 1, and is shown as a light blue color as a whole, and is indicated by color coordinates (0.17,0.11).
Example 2
A) Weighing cesium tungsten bronze Cs with particle size of 50nm 0.32 WO 3 10 kg of powder and 20nm of photocatalyst silver-doped titanium dioxide TiO 2 1 kg of powder is fed into a mixer to be mixed uniformly for 30min, then 30 kg of nano zeolite is slowly added while mixing, and the mixing is continued for 30min;
b) Pouring the mixed powder into a rotary atmosphere furnace, continuously introducing nitrogen and hydrogen mixed gas (the hydrogen accounts for 28 percent in the mixed gas), keeping the rotating speed of 20 revolutions per minute, and sintering at 300 ℃ for 3 hours to obtain composite powder, and sieving the composite powder by a 200-mesh sieve to remove large particles generated during sintering;
c) Weighing 10 kg of composite powder, using 3 kg of special auxiliary agent (nano dispersing agent) provided by Shanghai exemplary chemical company, and 40 kg of solvent propylene glycol methyl ether acetic acid, fully and uniformly mixing, and then filling into a sand mill for grinding to obtain dispersed color paste;
d) Putting the dispersion color paste and 190 kg of polyethylene terephthalate (PET) high polymer powder into a mixer, heating to 90 ℃ and continuously stirring and mixing for 10 hours until the solvent is fully volatilized to obtain a mixture;
e) Granulating the mixture by an extruder, and obtaining functional plastic master batches at a melting temperature of 280 ℃;
f) Weighing 100 kg of functional plastic master batch and 200 kg of PET white slice, mixing, extruding filaments in a fiber extruder, adopting a coiling machine to coil at 3200 m/min to obtain 125D/72F low-stretch filaments, and finally performing friction type extension false twisting to prepare 75D/72F PET filament fibers;
g) The resulting fibers were woven into a face fabric on a loom and tested to appear bluish in color with a color coordinate of about (0.15,0.25). Fig. 2 shows the fiber heat storage capacity infrared thermal image test (heat storage effect) of the fiber product of example 2, after irradiation with an infrared lamp for 1min, the infrared irradiation was removed, and the infrared thermal image was photographed with an infrared thermal imager, and the result showed that: compared with common cotton fiber, the fiber surface temperature of the invention can be obviously raised to 75 ℃, and the radiation can only be raised to 29 ℃ under the same condition, so that the heating effect is quite obvious.
The obtained fabric photo and the thermal imager photo after 1 minute of irradiation in sunlight are shown in fig. 2, and the thermal imager photo in the image shows that the temperature of the fabric is obviously higher than the outside temperature, thereby proving the heat storage capability.
Example 3
A) Weighing cesium tungsten bronze Cs with particle size of 50nm 0.32 WO 3 1 kg of powder, 10 kg of photocatalyst silver-doped titanium dioxide powder with the particle size of 20nm, feeding the powder into a stirring machine, uniformly mixing for 30min, slowly adding 20 kg of nano hydroxyapatite while stirring, and continuously stirring for 30min;
b) Pouring the mixed powder into a rotary atmosphere furnace, continuously introducing nitrogen and hydrogen mixed gas (the hydrogen accounts for 28 percent in the mixed gas), keeping the rotating speed of 20 revolutions per minute, and sintering at 300 ℃ for 3 hours to obtain composite powder, and sieving the composite powder by a 200-mesh sieve to remove large particles generated during sintering;
c) Weighing 10 kg of composite powder, using BYK company to provide 5 kg of wetting dispersant auxiliary agent and 40 kg of dimethylbenzene, fully and uniformly mixing, and then filling into a sand mill for grinding to obtain dispersed color paste;
d) Putting the dispersion color paste and 190 kg of Polyamide (PA) high polymer powder into a mixer, heating to 90 ℃ and continuously stirring and mixing for 10 hours until the solvent is fully volatilized to obtain a mixture;
e) Granulating the mixture by an extruder, and obtaining functional plastic master batches at a melting temperature of 280 ℃;
f) Preparing the obtained functional master batch into filaments and weaving the filaments into fabrics;
the whole fabric is nearly bluish white, the color coordinates are about (0.28,0.32), bacterial colonies (white staphylococci) are cultured on the fabric, and then the light is irradiated for 1h, so that the photocatalyst sterilization is promoted. The sterilization effect before and after illumination is shown in fig. 3. It can be seen that almost all the colonies are killed, demonstrating the bactericidal capacity of the product.
Comparative example 1:
a composite fiber without porous material was prepared in the same manner as in example 1.
The fiber prepared in comparative example 1 was not resistant to ultraviolet light. After 1h of ultraviolet ageing, obvious fiber embrittlement occurs, which greatly reduces the service life of the product.
Claims (9)
1. The sterilization and heat accumulation functional fiber is characterized by comprising sterilization and heat accumulation particles and a high polymer matrix, wherein the sterilization and heat accumulation particles are nano tungsten bronze powder/photocatalyst nano powder compound powder and are obtained by coating a porous material with a mesoporous pore structure;
the photocatalyst nano powder is silver-doped titanium dioxide; the mass ratio of the photocatalyst nano powder to the nano tungsten bronze powder is (10:1) - (1:10);
the porous material with the mesoporous pore structure is nano hydroxyapatite or nano zeolite, the pore diameter of the macropores exceeds 1 mu m, and the pore diameter of the mesopores is 2-50 nm.
2. The heat and sterilization functional fiber according to claim 1, wherein the content of the heat and sterilization particles is 0.2 to 20wt.% of the heat and sterilization functional fiber.
3. According toThe sterilization and heat accumulation functional fiber as set forth in claim 1, wherein said nano tungsten bronze powder has M x WO 3 Wherein M is more than one element selected from alkali metal element, alkaline earth metal element and transition metal element, and x is more than 0 and less than or equal to 1.
4. The sterilization and heat accumulation functional fiber according to claim 1, wherein the coating thickness of the porous material with a mesoporous pore structure is 0.05-5 microns.
5. The heat and sterilization functional fiber according to claim 1, wherein the high molecular polymer matrix is at least one of polyamide, polyethylene terephthalate, polypropylene and polybutylene terephthalate.
6. The sterilization and heat accumulation functional fiber according to claim 1, wherein the sterilization and heat accumulation functional fiber is one of a solid long fiber, a solid short fiber and a hollow short fiber.
7. A fiber product, characterized in that the fiber product is processed by the sterilization and heat accumulation functional fiber in claim 1.
8. A method for preparing the sterilization and heat accumulation functional fiber as claimed in claim 1, which is characterized by comprising the following steps:
mixing nano tungsten bronze powder with photocatalyst nano powder, and adding a porous material with a mesoporous pore structure while stirring to obtain mixed powder;
preparing slurry after sintering the mixed powder;
mixing the slurry with the powder of the high molecular polymer matrix, and heating to volatilize the solvent to obtain a mixture;
granulating the mixture to obtain master batches; and
and spinning and forming the master batch.
9. The method of preparing according to claim 8, wherein the spinning forming comprises: mixing the master batch with the white slices made of the high-molecular polymer, and extruding.
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