CN116905118A - Preparation method of functional fiber - Google Patents
Preparation method of functional fiber Download PDFInfo
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- CN116905118A CN116905118A CN202310673976.4A CN202310673976A CN116905118A CN 116905118 A CN116905118 A CN 116905118A CN 202310673976 A CN202310673976 A CN 202310673976A CN 116905118 A CN116905118 A CN 116905118A
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- 239000000835 fiber Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000004332 silver Substances 0.000 claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 42
- 239000012510 hollow fiber Substances 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000009987 spinning Methods 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 33
- -1 silver ions Chemical class 0.000 claims abstract description 31
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 27
- 239000004814 polyurethane Substances 0.000 claims abstract description 27
- 239000002121 nanofiber Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 125000002091 cationic group Chemical group 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000009503 electrostatic coating Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 77
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- 229920001661 Chitosan Polymers 0.000 claims description 24
- 229920000858 Cyclodextrin Polymers 0.000 claims description 22
- 229960004853 betadex Drugs 0.000 claims description 22
- 239000001116 FEMA 4028 Substances 0.000 claims description 19
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 19
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002166 wet spinning Methods 0.000 claims description 11
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical group [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001523 electrospinning Methods 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 37
- 230000006750 UV protection Effects 0.000 abstract description 26
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 14
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 239000004744 fabric Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000012792 core layer Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000004753 textile Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 230000009881 electrostatic interaction Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920006052 Chinlon® Polymers 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- 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
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
Abstract
The application discloses a preparation method of functional fibers, which comprises the following steps: mixing polyurethane, a cationic functional solvent and a dispersing agent, and then spinning by using a coaxial needle to obtain the hollow fiber; injecting graphene oxide into the hollow cavity of the hollow fiber to obtain a composite fiber; preparing spinning solution containing silver ions, carrying out electrostatic spinning, and coating the formed nano fiber containing the silver ions on the composite fiber to obtain the functional fiber; the preparation of the silver ion containing nanofibers is performed in synchronization with the application of the silver ion containing nanofibers to the surface of the composite fibers. According to the preparation method of the functional fiber with the ultraviolet resistance and the antibacterial performance, the graphene oxide is injected into the polyurethane hollow fiber, the hollow fiber is coated with the nano fiber containing silver ions, and the composite fiber shows the long-term and efficient antibacterial performance through the adsorption and in-situ reduction principle of the graphene oxide on Ag+.
Description
The application relates to a functional fiber with ultraviolet resistance and antibacterial performance, which is applied for 25 days 11 in 2022, 2022114887142 and is prepared by the preparation method and application thereof.
Technical Field
The application belongs to the technical field of functional fibers and textiles, and particularly relates to a preparation method of functional fibers with ultraviolet resistance and antibacterial property.
Background
Graphene oxide is a derivative of graphene, and oxygen-containing polar groups such as hydroxyl, carboxyl and the like are introduced, so that the graphene oxide has stronger reaction activity and better water solubility. The graphene oxide can absorb ultraviolet light, and can reflect ultraviolet light due to the sheet structure, so that the ultraviolet light protective performance of the fabric is positively achieved, the sharp edge of the sheet structure has a physical cutting effect on bacteria, and meanwhile, the graphene oxide also has a mechanical wrapping effect, so that the bacteria can not absorb external nutrition, and the aim of bacteriostasis is achieved.
At present, in the research of anti-ultraviolet and antibacterial functional fibers, as disclosed in patent CN111155318A, a preparation method of an antibacterial and ultraviolet resistant fabric is disclosed, mixed solutions such as anion microcapsule solution, softener and the like are adopted to pretreat yarns, and then weaving is performed, so that the antibacterial and ultraviolet resistant effects are achieved, but the use amount of the mixed solutions in the dipping process is relatively large, and the performance durability is insufficient. Patent CN114806096a discloses an ultraviolet-resistant master batch for polyester fiber, a preparation method, ultraviolet-resistant polyester fiber and fabric, wherein the ultraviolet-resistant polyester fiber is obtained by spinning after melt blending polyester and the ultraviolet-resistant master batch, and the high-temperature melting of the melt spinning has high requirements on the spinning temperature, so that the performance is reduced; patent CN112921428A discloses an antibacterial fiber and an antibacterial textile thereof, wherein inorganic particles containing antibacterial components are loaded on the surface of the fiber, so that a certain antibacterial effect can be achieved, but the problem of surface particle falling is easily caused; patent CN112342634a discloses a preparation method of an antibacterial nano cellulose fiber, which comprises the steps of preparing a mixed solution and acid bath spinning, but has complex process and strict spinning condition.
Disclosure of Invention
In view of the above, in order to overcome the defects of the prior art, the application aims to provide a preparation method of functional fibers with ultraviolet resistance and antibacterial performance, and the prepared functional fibers have lasting ultraviolet resistance and antibacterial performance.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a preparation method of functional fiber with ultraviolet resistance and antibacterial property comprises the following steps:
injecting graphene oxide into the hollow cavity of the hollow fiber to obtain a composite fiber;
and covering the nanofiber containing silver ions on the surface of the composite fiber to form a coating for coating, so as to obtain the functional fiber.
According to some preferred embodiments of the application, the graphene oxide accounts for 0.5-3% of the composite fiber by mass.
According to some preferred embodiments of the application, the nano-fiber containing silver ions is obtained by using an electrostatic spinning process for spinning solution containing silver ions.
In some embodiments of the present application, the preparation of the nanofibers containing silver ions and the coating of the nanofibers onto the surface of the composite fibers are performed simultaneously, i.e., silver-loaded chitosan (CS-Ag) and beta-cyclodextrin are prepared as an electrostatic spinning solution, and then the formed nanofibers are coated into the composite fibers and wound and collected by electrostatic spinning of a needle head, thereby obtaining the functional fibers.
According to some preferred embodiments of the application, the silver ion-containing spinning solution contains silver-loaded chitosan and beta-cyclodextrin. Beta-cyclodextrin can interact with certain groups in chitosan through non-covalent bonds, so that efficient adsorption is achieved. Wherein the mass ratio of the silver nitrate to the chitosan to the beta-cyclodextrin is 0.1:1.5-2.5:0.8-1.2; in some embodiments preferably 0.1:2:1.
according to some preferred embodiments of the present application, the spinning solution containing silver ions is prepared by the following method: dissolving chitosan in a formic acid/acetone solution with the mass ratio of 7:3 to obtain a mixed solution, and dispersing a silver nitrate solution into the mixed solution to obtain a solution A; and dissolving the beta-cyclodextrin in a dimethylformamide solvent to obtain a solution B, and finally uniformly mixing the solution A and the solution B to obtain the spinning solution containing silver ions.
According to some preferred embodiments of the application, the silver nitrate accounts for 3-5% of the weight of the silver-loaded chitosan and the beta-cyclodextrin.
According to some preferred embodiments of the application, the parameters of the electrospinning process are: the injection speed of the solution is 1.5-2.5mL/h, the receiving distance is 18-22cm, the voltage is 25-35kV, and the ambient temperature is 23-25 ℃. In some embodiments, the solution injection rate is preferably 2mL/h, the receiving distance is 20cm, the voltage is 30kV, and the ambient temperature is 24 ℃.
According to some preferred embodiments of the application, the hollow fiber is prepared by: and (3) mixing polyurethane with a cationic functional solvent, and spinning by using a coaxial needle to obtain the hollow fiber, wherein the diameter of the prepared hollow fiber (shell layer) is 300-500 mu m, and the diameter of a hollow cavity is 100-400 mu m. Because the graphene oxide material has larger specific surface area and more and regular holes, and has rich oxygen-containing functional groups, the graphene oxide material is combined with the cationic functional solvent through hydrogen bond acting force, so that the GO injected from the core layer is easier to attach to the shell TPU.
The TPU selected by the shell layer of the functional fiber is of a porous structure, on one hand, part of graphene oxide can move through micropores of the shell layer of the TPU, and on the other hand, the interlayer thickness between the shell layer TPU and the core layer GO (the penetration depth of the core layer into the GO) is controlled to be 50-100um, so that the ultraviolet resistance of the graphene oxide of the core layer cannot be influenced. And graphene oxide of the core layer and external Ag+ substances can be combined after being contacted with each other through electrostatic interaction.
According to some preferred embodiments of the application, the cationic functional solvent is 2, 3-epoxypropyltrimethylammonium chloride (GTA) and/or 3-chloro-2-hydroxypropyl trimethylammonium chloride (CHPTAC).
According to some preferred embodiments of the application, the mass ratio of polyurethane to cationic functional solvent is 6-10:2, preferably 8:2.
According to some preferred embodiments of the application, a dispersing agent is further added to the spinning solution, wherein the dispersing agent is Dimethylformamide (DMF). Dimethylformamide (DMF) is used as an organic solvent for dissolving polyurethane, and the mass fraction of polyurethane in the spinning solution finally prepared is 18-25%.
In some embodiments, the hollow fiber prepared by wet spinning specifically comprises the following steps: firstly, mixing polyurethane (TPU) with a cationic functional solvent, adding a dispersing agent dimethylformamide, and stirring for 24 hours at room temperature by using a magnetic stirrer until the TPU is completely dissolved to obtain spinning solution; spinning by using a coaxial needle, and collecting the formed hollow fiber in deionized water; finally, washing and drying to remove redundant impurities; hollow fibers are obtained. Wherein deionized water is used for washing, and the drying temperature is 60 ℃.
According to some preferred embodiments of the application, the injecting is to select a 10mL injector to absorb the graphene oxide solution, select a 25G bevel-mouth needle as an injecting needle, and inject the graphene oxide solution into the hollow fiber to prepare the composite fiber.
The application also provides the functional fiber which is prepared by the preparation method and has the anti-ultraviolet and antibacterial properties.
The application also provides application of the functional fiber with the ultraviolet resistance and the antibacterial property in textiles. Specifically, the functional fiber prepared by the method is combined and twisted to form yarn, and is woven with nylon yarn and the like into fabrics with different structures, such as plain weave, twill weave and satin weave.
The basic principle of the application is as follows:
(1) According to the application, graphene oxide GO is injected into the polyurethane hollow fiber, silver ions are compounded on the surface through electrostatic spinning, and the prepared functional fiber shows long-term and efficient antibacterial performance mainly by utilizing the adsorption and in-situ reduction principle of the graphene oxide to Ag+. On the one hand, GO is taken as a macromolecule with negative charge, and the positively charged Ag+ is captured through the strong electrostatic interaction between an oxygen-containing group and Ag+ to assemble GO-Ag+ macromolecule salt; on the other hand, GO acts as a reducing agent, reducing ag+ to nano silver particles (AgNPs) through its surface active functional groups.
(2) According to the application, coaxial wet spinning and opposite-spraying electrostatic spinning are combined, firstly, a shell layer is treated by adding a cationic functional solvent in the wet spinning process, so that GO injected into a core layer is easier to attach to realize ultraviolet resistance; secondly, the nano fiber formed by spray electrostatic spinning can be endowed with antibacterial performance; finally, through interaction of GO and Ag+ in electrostatic spinning, interlayer close combination is realized, and long-term antibacterial property can be maintained.
Due to the adoption of the technical scheme, compared with the prior art, the application has the following advantages: according to the preparation method of the functional fiber with the ultraviolet resistance and the antibacterial property, the graphene oxide is injected into the polyurethane hollow fiber, the hollow fiber is coated with the nano fiber containing silver ions, and the prepared functional fiber shows the ultraviolet resistance and the antibacterial property with high efficiency for a long time through the adsorption and in-situ reduction principle of the graphene oxide on Ag+.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a functional fiber prepared in a preferred embodiment of the present application;
in the attached drawings, 1, shell TPU; 2. a core layer GO; 3. a nanofiber; 101. silver ions; 102. and (3) oxidizing graphene.
Detailed Description
In order to make the technical solution of the present application better understood by those skilled in the art, the technical solution of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
The application mainly combines wet spinning and electrostatic spinning technology to form composite fiber, and realizes high-efficiency ultraviolet resistance and antibacterial performance by controlling interaction of graphene oxide GO and silver ions, and simultaneously can meet the performance requirements on mechanical strength. The coaxial polyurethane@graphene oxide (GO) hollow fiber is prepared through wet spinning, and then the hollow fiber is coated and coated by using a counter-spraying electrostatic spinning silver-loaded chitosan (CS-Ag) @beta-cyclodextrin fiber, so that the functional fiber is obtained. The functional fiber can be twisted and compounded with other yarns to be woven into fabrics with different structures, and the functional cloth is obtained.
Specifically, the preparation method of the fiber with the ultraviolet resistance and antibacterial function comprises the following steps:
step 1, preparation of hollow fiber
Firstly, polyurethane (TPU) is mixed with a cation functionalized solvent, and a dispersing agent dimethylformamide is added, and the mixture is stirred for 24 hours at room temperature by using a magnetic stirrer until the TPU is completely dissolved, so as to obtain spinning solution.
And spinning by using a coaxial needle, and collecting the formed hollow fibers in deionized water.
Finally, the excess impurities were removed by washing with deionized water and dried at 60 ℃. The diameter of the prepared hollow fiber (shell layer) is 300-500 mu m, and the diameter of the hollow cavity is 100-400 mu m.
The cation functionalized solvent can be selected from 2, 3-epoxypropyl trimethyl ammonium chloride (GTA) or 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (CHPTAC).
Step 2, preparation of composite fiber
And (3) injecting a proper amount of Graphene Oxide (GO) solution into the hollow part of the polyurethane hollow fiber treated by cationic functionalization in the step (1). The mass ratio of the Graphene Oxide (GO) in the composite fiber is 0.5-3%. Specifically, a 10mL syringe is selected to absorb the graphene oxide solution, a 25G bevel-mouth needle is selected as a perfusion needle, and the graphene oxide solution is injected into the hollow fiber to prepare the composite fiber.
Step 3, nanofiber coating
Firstly, preparing spinning solution containing silver ions, and then carrying out electrostatic spinning on a needle head to coat the formed nanofiber onto the composite fiber formed in the step 2, and carrying out winding and collection.
The spinning solution containing silver ions is prepared by the following method: dissolving chitosan in a formic acid/acetone solution with the mass ratio of 7:3 to obtain a mixed solution, and dispersing a silver nitrate solution into the mixed solution to obtain a solution A; and dissolving the beta-cyclodextrin in a dimethylformamide solvent to obtain a solution B, and finally uniformly mixing the solution A and the solution B to obtain the spinning solution containing silver ions.
The mass ratio of the silver nitrate in the silver-loaded chitosan and the beta-cyclodextrin is 3-5%. The injection speed of the electrostatic spinning solution is set to be 2mL/h, the receiving distance is 20cm, the voltage is 30kV, and the environmental temperature is controlled to be 23-25 ℃.
Example 1
The preparation method of the fiber with the ultraviolet resistance and the antibacterial function comprises the following steps:
step 1, preparation of hollow fiber
Firstly, mixing polyurethane (TPU) with cationic functional solvent 2, 3-epoxypropyl trimethyl ammonium chloride (GTA) (the mass ratio is 8:2), adding dispersant dimethylformamide, and stirring for 24 hours at room temperature by using a magnetic stirrer until the TPU is completely dissolved, thus obtaining spinning solution.
And spinning by using a coaxial needle, and collecting the formed hollow fibers in deionized water.
Finally, the excess impurities were removed by washing with deionized water and dried at 60 ℃. The diameter of the prepared hollow fiber (shell layer) is 400 mu m, and the diameter of the hollow cavity is 300 mu m.
Step 2, preparation of composite fiber
And (3) injecting a proper amount of Graphene Oxide (GO) solution into the hollow part of the polyurethane hollow fiber treated by cationic functionalization in the step (1). The mass ratio of the Graphene Oxide (GO) in the composite fiber is 0.8%. Graphene oxide in this example was purchased from Ann Ji-Kai-chemical, brand A60007, particle size: 1-5 μm.
Step 3, nanofiber coating
Firstly, preparing spinning solution containing silver ions, and then carrying out electrostatic spinning on a needle head to coat the formed nanofiber onto the composite fiber formed in the step 2, and carrying out winding and collection.
The spinning solution containing silver ions is prepared by the following method: dissolving chitosan in a formic acid/acetone solution with the mass ratio of 7:3 to obtain a mixed solution, and dispersing a silver nitrate solution into the mixed solution to obtain a solution A; and dissolving the beta-cyclodextrin in a dimethylformamide solvent to obtain a solution B, and finally uniformly mixing the solution A and the solution B to obtain the spinning solution containing silver ions.
The mass ratio of the silver nitrate in the silver-loaded chitosan and the beta-cyclodextrin is 3 percent. The injection speed of the electrostatic spinning solution is set to 2mL/h, the receiving distance is 20cm, the voltage is 30kV, and the environmental temperature is controlled to be 23 ℃.
Example 2
The preparation method of the fiber with the ultraviolet resistance and the antibacterial function comprises the following steps:
step 1, preparation of hollow fiber
Firstly, polyurethane (TPU) is mixed with a cationic functional solvent of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (CHPTAC), and a dispersing agent of dimethylformamide is added, and the mixture is stirred for 24 hours at room temperature by a magnetic stirrer until the TPU is completely dissolved, so as to obtain spinning solution.
And spinning by using a coaxial needle, and collecting the formed hollow fibers in deionized water.
Finally, the excess impurities were removed by washing with deionized water and dried at 60 ℃.
Step 2, preparation of composite fiber
And (3) injecting a proper amount of Graphene Oxide (GO) solution into the hollow part of the polyurethane hollow fiber treated by cationic functionalization in the step (1). The mass ratio of the Graphene Oxide (GO) in the composite fiber is 1.2%.
Step 3, nanofiber coating
Firstly, preparing silver-loaded chitosan (CS-Ag) and beta-cyclodextrin as electrostatic spinning solution, and then carrying out electrostatic spinning on a needle head, coating the formed nanofiber on the composite fiber formed in the step 2, and carrying out winding and collection.
The mass ratio of the silver nitrate in the silver-loaded chitosan and the beta-cyclodextrin is 4 percent. The injection speed of the electrostatic spinning solution is set to 2mL/h, the receiving distance is 20cm, the voltage is 30kV, and the environmental temperature is controlled to 25 ℃.
Example 3
The preparation method of the fiber with the ultraviolet resistance and the antibacterial function comprises the following steps:
step 1, preparation of hollow fiber
Firstly, polyurethane (TPU) is mixed with a cationic functional solvent of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (CHPTAC), and a dispersing agent of dimethylformamide is added, and the mixture is stirred for 24 hours at room temperature by a magnetic stirrer until the TPU is completely dissolved, so as to obtain spinning solution.
And spinning by using a coaxial needle, and collecting the formed hollow fibers in deionized water.
Finally, the excess impurities were removed by washing with deionized water and dried at 60 ℃.
Step 2, preparation of composite fiber
And (3) injecting a proper amount of Graphene Oxide (GO) solution into the hollow part of the polyurethane hollow fiber treated by cationic functionalization in the step (1). The mass ratio of the Graphene Oxide (GO) in the composite fiber is 2.5%.
Step 3, nanofiber coating
Firstly, preparing silver-loaded chitosan (CS-Ag) and beta-cyclodextrin as electrostatic spinning solution, and then carrying out electrostatic spinning on a needle head, coating the formed nanofiber on the composite fiber formed in the step 2, and carrying out winding and collection.
The mass ratio of the silver nitrate in the silver-loaded chitosan and the beta-cyclodextrin is 5 percent. The injection speed of the electrostatic spinning solution is set to 2mL/h, the receiving distance is 20cm, the voltage is 30kV, and the environmental temperature is controlled to 25 ℃.
Example 4 fabrics
The functional fibers prepared in the above embodiments are combined and twisted to form yarns, and are compounded with nylon yarns and the like to be woven into fabrics with different structures, such as plain fabrics, twill fabrics, satin fabrics and the like.
Comparative example 1
The fiber preparation in this comparative example includes the following steps:
polyurethane (TPU) was mixed with cationic functionalized solvent 2, 3-epoxypropyltrimethylammonium chloride (GTA) (mixing ratio 8:2), and dispersant Dimethylformamide (DMF) was added, and after stirring 24h at room temperature using a magnetic stirrer until TPU was completely dissolved, 0.8wt% GO was added to prepare a mixed solution, designated solution 1.
Preparing silver-carrying chitosan (CS-Ag) and beta-cyclodextrin solution, wherein the content of the silver nitrate solution in the preparation of silver-carrying chitosan (CS-Ag) @ beta-cyclodextrin fiber is 3wt%, and the silver nitrate solution is marked as solution 2.
And respectively immersing the polyester fabric into the solution 1 and the solution 2, and performing drying post-treatment.
The raw materials used were substantially the same as in example 1.
Comparative example 2
The difference between this comparative example and example 1 is that the electrospinning coating in step 3 was changed to a silver nitrate solution directly mixed with GO and injected into the core layer of the hollow fiber, and the other steps and parameters were basically the same as in example 1.
Testing and results
The fibers or the prepared fabrics prepared in the above examples and comparative examples were subjected to ultraviolet ray resistance and antibacterial property tests. Wherein, ultraviolet resistance: referring to GB/T18830-2009 evaluation of ultraviolet resistance of textiles, an ultraviolet protection factor (UPF value) and ultraviolet transmittance are tested by using an ultraviolet resistance tester and an ultraviolet visible spectrophotometer of the textiles; antibacterial properties: reference GB/T20944.3-2008, evaluation of antimicrobial properties of textiles section 3: testing by an oscillation method; mechanical property test: and testing by a universal material tester according to FZ/T50006-2013 and FZ/T50007-2012, wherein the clamping distance of the test sample is 50mm, the stretching rate is 500mm/min, the testing temperature is room temperature, and each group of samples is tested for 20 times, and the average value is obtained. The test results are shown in table 1:
table 1 test results
From the data in table 1, it can be seen that the method of combining wet spinning with electrostatic spinning adopted in the examples and the interaction principle between GO and silver ions are combined, and the ultraviolet resistance, antibacterial performance and mechanical properties of examples 1-3 are obviously improved compared with comparative examples 1 and 2 due to the adsorption and in-situ reduction between materials in the spinning process. The fiber fabric is treated by the dipping method adopted in the comparative example 1, the material consumption is large, and the ultraviolet resistance and the antibacterial performance are obviously inferior to those of the functional fiber in the examples; in comparative example 2, no electrospinning coating was used, silver ions and GO were both present in the hollow fiber core, and the performance was also poor.
The application relates to a preparation method of fiber with ultraviolet resistance and antibacterial function, which comprises the following steps: firstly, preparing coaxial polyurethane@graphene oxide (GO) hollow fibers by wet spinning, wherein a shell polyurethane is added with a cationic functional solvent to realize the GO efficient adsorption of core injection; secondly, coating and coating the hollow fiber by using a counter-spraying electrostatic spinning silver-loaded chitosan (CS-Ag) @ beta-cyclodextrin fiber; finally, the coated composite fiber yarns can be woven into fabrics with different structures. The application combines the wet spinning technology and the electrostatic spinning technology to form the functional fiber, thereby controlling the interaction of GO and silver ions, realizing high-efficiency ultraviolet resistance and antibacterial performance, meeting the performance requirements on mechanical strength and the like, having less raw material consumption, saving production cost, simple operation and realizing continuous production.
Compared with the prior art, the application has the following beneficial effects:
(1) According to the application, GO is injected into the polyurethane hollow fiber, silver ions are compounded on the surface through electrostatic spinning, and the composite fiber is enabled to show long-term and efficient antibacterial performance mainly by utilizing the adsorption and in-situ reduction principle of graphene oxide on Ag+. On the one hand, GO is taken as a macromolecule with negative charge, and the positively charged Ag+ is captured through the strong electrostatic interaction between an oxygen-containing group and Ag+ to assemble GO-Ag+ macromolecule salt; on the other hand, GO acts as a reducing agent, reducing ag+ to nano silver particles (AgNPs) through its surface active functional groups. As shown in fig. 1.
(2) According to the application, coaxial wet spinning and opposite-spraying electrostatic spinning are combined, firstly, a shell TPU is treated by adding a cationic functional solvent in the wet spinning process, so that GO injected into a core layer is easier to attach, and ultraviolet resistance is realized; secondly, the nano fiber formed by spray electrostatic spinning can be endowed with antibacterial performance; finally, through interaction of GO and Ag+ in electrostatic spinning, interlayer close combination is realized, and long-term antibacterial property can be maintained.
(3) The composite fiber yarn formed by the application can be combined with common yarns such as chinlon to be set into different tissue structures, so that the requirements of ultraviolet resistance and antibacterial property and mechanical property can be met. In addition, the dosage in the preparation process of the composite fiber is small, the structure is simple, and the continuous production can be realized.
The above embodiments are provided to illustrate the technical concept and features of the present application and are intended to enable those skilled in the art to understand the content of the present application and implement the same, and are not intended to limit the scope of the present application. All equivalent changes or modifications made in accordance with the spirit of the present application should be construed to be included in the scope of the present application.
Claims (12)
1. The preparation method of the functional fiber is characterized by comprising the following steps:
mixing polyurethane, a cationic functional solvent and a dispersing agent, and spinning by using a coaxial needle to obtain a hollow fiber;
injecting graphene oxide into the hollow cavity of the hollow fiber to obtain a composite fiber;
preparing spinning solution containing silver ions, carrying out electrostatic spinning, and coating the formed nano fiber containing the silver ions on the composite fiber to obtain the functional fiber;
the preparation of the nano-fiber containing silver ions is carried out synchronously with the coating of the nano-fiber on the surface of the composite fiber; the graphene oxide is used for reducing silver ions in the nanofiber.
2. The method according to claim 1, wherein the functional fiber has a shell layer, and the graphene oxide is movable through micropores of the shell layer.
3. The preparation method according to claim 1, wherein the cationic functional solvent is 2, 3-epoxypropyl trimethyl ammonium chloride and/or 3-chloro-2-hydroxypropyl trimethyl ammonium chloride; the dispersing agent is dimethylformamide.
4. A method according to claim 1 or 3, wherein the mass ratio of polyurethane to cationic functional solvent is 6-10:2.
5. the method according to claim 4, wherein the mass fraction of polyurethane in the spinning solution for preparing the hollow fiber is 18 to 25%.
6. A method of preparing as claimed in claim 1 or 3, wherein the hollow fibres are prepared by wet spinning, comprising the steps of: mixing polyurethane with a cationic functional solvent, adding a dispersing agent, and stirring at room temperature until the polyurethane is completely dissolved to obtain spinning solution; spinning with a coaxial needle, collecting the formed fibers in water; and washing and drying to obtain the hollow fiber.
7. The preparation method according to claim 1, wherein the graphene oxide accounts for 0.5-3% of the composite fiber by mass.
8. The preparation method according to claim 1, wherein the spinning solution containing silver ions contains silver-loaded chitosan and beta-cyclodextrin; the silver-loaded chitosan is prepared from silver nitrate and chitosan; the mass ratio of the silver nitrate in the silver-loaded chitosan and the beta-cyclodextrin is 3-5%.
9. The preparation method according to claim 8, wherein the mass ratio of the silver nitrate, the chitosan and the beta-cyclodextrin is 0.1:1.5-2.5:0.8-1.2.
10. The preparation method according to claim 1 or 8, wherein the spinning solution containing silver ions is prepared by the following method: dissolving chitosan in formic acid and/or acetone to obtain a mixed solution, and dispersing silver nitrate into the mixed solution to obtain a solution A; dissolving beta-cyclodextrin in dimethylformamide to obtain a solution B; and uniformly mixing the solution A and the solution B to obtain the spinning solution containing silver ions.
11. The method according to claim 1, wherein the parameters of the electrospinning process are: the injection speed of the solution is 1.5-2.5mL/h, the receiving distance is 18-22cm, and the voltage is 25-35kV.
12. The preparation method according to claim 1, wherein the injecting is to suck the graphene oxide solution by using an injector and inject the graphene oxide solution into a hollow cavity of the hollow fiber to prepare the composite fiber.
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