CN117418327A - Antibacterial and antiviral fiber and preparation method and application thereof - Google Patents
Antibacterial and antiviral fiber and preparation method and application thereof Download PDFInfo
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- CN117418327A CN117418327A CN202311531238.2A CN202311531238A CN117418327A CN 117418327 A CN117418327 A CN 117418327A CN 202311531238 A CN202311531238 A CN 202311531238A CN 117418327 A CN117418327 A CN 117418327A
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- antibacterial
- resin
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 121
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 107
- 239000000835 fiber Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 82
- 229920005989 resin Polymers 0.000 claims abstract description 79
- 239000011347 resin Substances 0.000 claims abstract description 79
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 54
- 150000002357 guanidines Chemical class 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000007791 liquid phase Substances 0.000 claims abstract description 30
- 238000002074 melt spinning Methods 0.000 claims abstract description 29
- 125000002091 cationic group Chemical group 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 238000001291 vacuum drying Methods 0.000 claims abstract description 18
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000003242 anti bacterial agent Substances 0.000 claims description 40
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- -1 polyhexamethylene guanidine hydrochloride Polymers 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 239000004952 Polyamide Substances 0.000 claims description 18
- 229920002647 polyamide Polymers 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 7
- 230000000845 anti-microbial effect Effects 0.000 claims description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 6
- 239000004626 polylactic acid Substances 0.000 claims description 6
- GHXZTYHSJHQHIJ-UHFFFAOYSA-N Chlorhexidine Chemical class C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 GHXZTYHSJHQHIJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 4
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004599 antimicrobial Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- CPLASELWOOUNGW-UHFFFAOYSA-N benzyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1=CC=CC=C1 CPLASELWOOUNGW-UHFFFAOYSA-N 0.000 claims 1
- GQVVQDJHRQBZNG-UHFFFAOYSA-N benzyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CC1=CC=CC=C1 GQVVQDJHRQBZNG-UHFFFAOYSA-N 0.000 claims 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims 1
- 239000004753 textile Substances 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000002421 anti-septic effect Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229960000686 benzalkonium chloride Drugs 0.000 description 7
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229920002413 Polyhexanide Polymers 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920013716 polyethylene resin Polymers 0.000 description 4
- 239000002952 polymeric resin Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229960003333 chlorhexidine gluconate Drugs 0.000 description 3
- YZIYKJHYYHPJIB-UUPCJSQJSA-N chlorhexidine gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.C1=CC(Cl)=CC=C1NC(=N)NC(=N)NCCCCCCNC(=N)NC(=N)NC1=CC=C(Cl)C=C1 YZIYKJHYYHPJIB-UUPCJSQJSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229940127554 medical product Drugs 0.000 description 2
- KEBCVCDJOYEDJL-UHFFFAOYSA-N n'-[3-[3-aminopropyl(dimethoxy)silyl]oxypropyl]ethane-1,2-diamine Chemical compound NCCC[Si](OC)(OC)OCCCNCCN KEBCVCDJOYEDJL-UHFFFAOYSA-N 0.000 description 2
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 206010069767 H1N1 influenza Diseases 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- AKGZDINYLOSBTE-UHFFFAOYSA-N [(e)-n'-(diaminomethylideneamino)carbamimidoyl]azanium;chloride Chemical compound Cl.NC(=N)NN=C(N)N AKGZDINYLOSBTE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229960002233 benzalkonium bromide Drugs 0.000 description 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FNXLCIKXHOPCKH-UHFFFAOYSA-N bromamine Chemical class BrN FNXLCIKXHOPCKH-UHFFFAOYSA-N 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960003260 chlorhexidine Drugs 0.000 description 1
- 229960002152 chlorhexidine acetate Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 201000010740 swine influenza Diseases 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- 241000712461 unidentified influenza virus Species 0.000 description 1
- 238000004804 winding Methods 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
The application discloses an antibacterial and antiviral fiber, a preparation method and application thereof, and belongs to the technical field of functionalized textiles. The preparation method comprises the following steps: mixing polymer guanidine salt and cationic antiseptic in organic solvent to form organic composite component liquid phase, and mixing the organic composite component liquid phase with TiO 2 Mixing and vacuum drying to form organic-TiO 2 After compounding the functional components, a first resin, an aminosilane coupling agent and an organic-TiO 2 Blending and granulating the composite functional components to form functional master batches, and finally melting the second resin and the functional master batchesAnd (5) melt spinning to obtain the antibacterial and antiviral fiber. The preparation method can not only endow the fiber with excellent antiviral property and good appearance quality, but also greatly improve the antibacterial property of the fiber.
Description
Technical Field
The application belongs to the technical field of functionalized textiles, and particularly relates to an antibacterial and antiviral fiber, a preparation method and application thereof.
Background
The preparation of the antibacterial and antiviral functional modified fiber by compounding antibacterial and antiviral functional ingredients with a polymer matrix is one of effective methods for realizing functional antibacterial and antiviral functions of fiber materials. Wherein, in order to improve the antibacterial and antiviral effects of the functional ingredients, the related technology can be compounded by antibacterial and antiviral combinations of different types/mechanisms.
For example, the prior art with application publication number CN 115323522A discloses a preparation method of an antibacterial polyamide fiber, which discloses that acid etched tourmaline is dispersed in a guanidine group-containing organic polymer antibacterial agent solution, then mixed with benzotriazole powder and introduced with metal ions to prepare an antibacterial composite powder, and finally an antibacterial polyamide master batch is prepared and melt-spun with polyamide resin, so that the antibacterial polyamide fiber can last be antibacterial in an environment containing a large amount of anions.
However, this prior art has the following problems in practical applications: firstly, the modification process is long, the operation is complex, the cost is high, and the industrial production is not facilitated; secondly, the modified fiber product has no antiviral effect; thirdly, the average antibacterial property of the modified fiber product is poor.
Disclosure of Invention
The application discloses an antibacterial and antiviral fiber, a preparation method and application thereof, and aims to solve the technical problems that the modification process of the conventional antibacterial and functional fiber is long, the operation is complex, the cost is high and the product does not have an antiviral function.
In order to achieve the above purpose, the technical scheme of the application is as follows:
a first aspect of the present application provides a method of preparing an antibacterial and antiviral fiber, the method comprising:
mixing the high molecular guanidine salt and the cationic antibacterial agent in an organic solvent to form an organic composite component liquid phase;
the organic composite component liquid phase and TiO 2 After mixing, vacuum drying to form organic-TiO 2 A composite functional component;
combining a first polyamide resin, an aminosilane coupling agent, and the organic-TiO 2 Blending and granulating the composite functional components to form functional master batches;
melt spinning the second resin and the functionalized master batch to obtain antibacterial and antiviral polyamide fibers;
wherein the first resin is the same as or different from the second resin.
With reference to the first aspect, preferably, the method further includes:
immersing the antibacterial and antiviral fiber formed by melt spinning into an aqueous solution containing alcohol for surface treatment, and drying the surface treated product.
In combination with the first aspect, preferably, the polymer guanidine salt is one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene guanidine hydrochloride and polyhexamethylene guanidine phosphate.
Preferably in combination with the first aspect, the cationic antibacterial agent is one or more of quaternary ammonium salt antibacterial agent, chlorhexidine salt antibacterial agent and halamine salt antibacterial agent.
In combination with the first aspect, preferably, the aminosilane coupling agent is one of aminopropyl triethoxysilane, aminopropyl trimethoxysilane, aminopropyl methyldimethoxysilane, aminopropyl triethoxysilane, aminopropyl methyldiethoxysilane, phenylaminomethyl triethoxysilane, phenylaminomethyl trimethoxysilane, and aminoethylaminoethyl aminopropyl trimethoxysilane.
Preferably, in combination with the first aspect, the resin is one or more of polyamide, polyethylene, polypropylene, polyester, polylactic acid, polyurethane, polyimide and polyphenylene sulfide resin.
With the first aspect is preferablyThe organic-TiO 2 The mass ratio of the composite functional component to the first resin is 5-60:100.
with reference to the first aspect, preferably, the mass ratio of the functionalized masterbatch to the second resin is 5-25:100.
a second aspect of the present application provides an antimicrobial antiviral fiber made by the method of the first aspect.
A third aspect of the present application provides the use of an antibacterial and antiviral fiber according to the second aspect for the manufacture of an antibacterial and antiviral fiber product.
Compared with the prior art, the advantages or beneficial effects of the embodiment of the application at least comprise:
the preparation method provided by the first aspect of the application can enable the organic-TiO to be prepared 2 The composite functional components are uniformly and stably dispersed in the resin for a long time, so that the resin has high-efficiency and durable antibacterial and antiviral functions. Wherein the polymer guanidine salt, the cationic antibacterial agent and the TiO are used for preparing the composite material 2 Compound preparation of organic-TiO 2 The functional components are compounded, and an aminosilane coupling agent is introduced during blending granulation of the functional master batch and the resin, so that the polymer guanidine salt, the cationic antibacterial agent and the TiO can be realized on one hand 2 The antibacterial and antiviral properties of the composite functional components are greatly improved by generating a sufficient synergistic effect; on the other hand, the components can be mutually connected, the defects of the performances and mechanisms of the components are effectively overcome, and the antibacterial and antiviral durability and the drug resistance of the composite functional component are greatly improved; the third aspect can firmly combine the composite functional component with the resin surface, so that not only can the combination stability of the composite functional component and the resin be greatly improved, but also the dispersibility of the composite functional component on the resin surface and in the resin can be improved; the fourth aspect simplifies the modification process, simultaneously solves the problem of yellowing of the organic composite component in the spinning process to a great extent, and obviously improves the appearance quality of the antibacterial and antiviral fiber finished product.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the description of the embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments described in the present application, and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
Fig. 1 is an overall external view of an antibacterial and antiviral fiber αmpu1 provided in the embodiment of the present application;
fig. 2 is a cross-sectional SEM view of fig. 1, wherein fig. 2A is a longitudinal-sectional SEM view of fig. 1, and fig. 2B is a cross-sectional SEM view of fig. 1.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It will be apparent that the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
In the following description of the present embodiment, the term "and/or" is used to describe an association relationship of association objects, which means that three relationships may exist, for example, a and/or B may mean: a alone, B alone and both a and B. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the following description of the present embodiments, the term "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c" may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood by those skilled in the art that, in the following description of the embodiments of the present application, the sequence number does not mean that the sequence of execution is not sequential, and some or all of the steps may be executed in parallel or sequentially, and the execution sequence of each process should be determined by its functions and inherent logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application in the examples and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
All materials and/or reagents in the examples of the present application are commercially available or prepared according to conventional methods well known to those skilled in the art, e.g., various resins, polymeric guanidine salts, cationic antibacterial agents, tiO 2 And aminosilane coupling agents, etc. are commercially available.
In a first aspect, an embodiment of the present application provides an antibacterial and antiviral fiber, and a preparation method of the embodiment of the present application includes:
mixing the high molecular guanidine salt and the cationic antibacterial agent in an organic solvent to form an organic composite component liquid phase;
the organic composite component liquid phase and TiO 2 After mixing, vacuum drying to form organic-TiO 2 A composite functional component;
combining a first resin, an aminosilane coupling agent, and the organic-TiO 2 Blending and granulating the composite functional components to form functional master batches;
melt spinning the second resin and the functionalized master batch to obtain antibacterial and antiviral fibers;
wherein the first resin is the same as or different from the second resin.
Note that the first resin and the second resin in the embodiments of the present application are the same or different, and refer to the same or different material types of the first resin and the second resin, for example, when the first resin is the polyamide 46, the second resin may be the polyamide 46, or may be a polyamide resin of other common types such as the polyamide 56, the polyamide 66, and the like.
Of course, the first resin may be other common resins such as polylactic acid, polyester, polypropylene, polyethylene, polyphenylene sulfide, etc., and the corresponding second resin may be other common resins such as polylactic acid, polyester, polypropylene, polyethylene, polyphenylene sulfide, etc., and specific types of the first resin and the second resin are not particularly limited in the embodiment of the present application.
It should be noted that, the organic solvent in the embodiment of the application is ethanol with the volume concentration of less than 85% preferably, so that the polymer guanidine salt can be uniformly and stably dispersed in the ethanol solvent, the uniformity of mixing the cationic antibacterial agent and the polymer guanidine salt is improved, and the problem of poor heat resistance of the cationic antibacterial agent is effectively solved.
The vacuum drying in the embodiment of the present application is preferably two-stage drying under vacuum. Specifically:
the temperature of the first stage drying is preferably 65-78 ℃, the time is 0.5-4 h, and the pressure is 0.02-0.1Mpa;
the temperature of the second stage drying is preferably 80-120deg.C, the time is 0.5-2h, and the pressure is 0.02-0.1Mpa;
the pressure of the first stage drying and the pressure of the second stage drying are the same or different.
The first-stage vacuum drying is performed to reduce the boiling point of the organic solvent, so that most of the organic solvent in the liquid phase can be efficiently and safely evaporated; the second stage of vacuum drying can sufficiently remove the organic-TiO 2 The water in the composite functional component can avoid the problem that the high molecular guanidine salt is unfavorable for subsequent spinning due to higher viscosity of the material caused by water absorption, and greatly improves the processability of the modified fiber.
It should be noted that, in the examples of the present application, blending granulation and melt spinning are carried out according to the general process requirements in the related art, unless otherwise specified, for example, blending granulation may be carried out using a twin screw extruder under the process conditions of 260±2 ℃ and pelletization; the melt spinning may be performed using a melt spinning machine under process conditions of a temperature of 280.+ -. 10 ℃ and a winding speed of 4000-5000 m/min.
In view of the above, the preparation method of the present application comprises the steps of reacting a polymerAfter guanidine salt and cationic antibacterial agent are compounded into an organic composite component liquid phase in an organic solvent, the organic composite component liquid phase is mixed with TiO 2 Mixing and vacuum drying to obtain organic-TiO 2 The composite functional components greatly improve the antibacterial and antiviral performance of the functional ingredients and improve the appearance quality of the antibacterial and antiviral fiber finished product, and specifically:
the high molecular guanidine salt and the cationic antibacterial agent are compounded in the organic solvent, so that the uniformity of mixing the cationic antibacterial agent and the high molecular guanidine salt is obviously improved, and the defect of poor heat resistance of a single cationic antibacterial agent is effectively overcome;
by liquid phase of organic composite component and TiO 2 Mixing and two-stage vacuum drying to prepare organic-TiO 2 On the one hand, tiO can be used as the composite functional component 2 The repulsive effect of the surface electrical property in the liquid phase promotes the stable, uniform and staggered distribution of the high-molecular guanidine salt on the surface of the cationic antibacterial agent, which is beneficial to further improving the heat resistance of the cationic antibacterial agent; on the other hand by introducing TiO 2 The antibacterial mechanism is expanded, so that the antibacterial and antiviral effects are synergistically enhanced, the problem that the antibacterial performance of the cationic antibacterial agent is reduced or even fails in an environment containing a large amount of anions can be effectively solved, and the antibacterial and antiviral effects can be effectively and permanently exerted in the environment containing a large amount of anions; in a third aspect, tiO may be used 2 The yellowing organic component which is dyed white and is initiated by heating effectively improves the appearance quality of the functionalized master batch and the modified fiber finished product; fourth aspect may utilize TiO 2 The water absorption property in the air promotes the hydrolysis of the high molecular guanidine salt and the cationic antibacterial agent, so that the composite antibacterial and antiviral system runs continuously and efficiently, and the antibacterial efficiency is improved.
Meanwhile, the embodiment of the application can combine organic functional groups and TiO on the surface of the resin by introducing the aminosilane when preparing the functionalized master batch 2 Thereby further improving the organic-TiO 2 The dispersion performance of the composite functional component on the surface and in the resin.
In addition, the examples of the present application use resin chips as polymersMatrix with organic-TiO containing high molecular guanidine salt 2 The composite functional components are compounded, and the polymer resin and the polymer guanidine salt have the same organic functional groups, so that the polymer resin and the polymer guanidine salt can be well fused in the melting process, the success rate of melt spinning can be improved, the surface and the section of a modified fiber finished product can be smooth and flat, and the appearance quality of the modified fiber can be improved.
In a specific embodiment, the preparation method of the embodiment of the application preferably includes:
immersing the antibacterial and antiviral fiber formed by melt spinning into an aqueous solution containing alcohol for surface treatment, and drying the surface treated product. Wherein the alcohol-containing aqueous solution is one or more of methanol, ethanol, propanol and butanol.
According to the embodiment of the application, the antibacterial and antiviral fiber formed by melt spinning is immersed in the alcohol-containing aqueous solution for surface treatment, so that not only can silane groups grafted on the surface of the antibacterial and antiviral fiber be hydrolyzed to form a stable membranous structure, but also the silane groups can be inhibited from condensation precipitation, so that the film forming efficiency and the stability of the membranous structure are greatly improved, and the organic-TiO is effectively solved 2 The composite functional component is easy to be influenced by external anion environment to fail, so that the modified fiber has lasting and efficient antibacterial and antiviral functions.
In a specific embodiment, the polymer guanidine salt used in the embodiment of the present application is preferably one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanidine hydrochloride and polyhexamethylene guanidine phosphate. The polymer guanidine salts are efficient, nontoxic and easy to prepare, and the antibacterial active ingredients of the polymer guanidine salts are guanidine groups, so that the effect cannot be influenced when the polymer guanidine salts are used in combination, and the polymer guanidine salts can be used in a plurality of modes.
In a specific embodiment, the cationic antibacterial agent in the embodiment of the present application is one or more of a quaternary ammonium salt antibacterial agent, a chlorhexidine salt antibacterial agent, or a halamine salt antibacterial agent, for example, the quaternary ammonium salt antibacterial agent may be benzalkonium chloride; the chlorhexidine salt antibacterial agent can be chlorhexidine acetate, chlorhexidine gluconate, etc.; the halamine salt antibacterial agent can be trichloroisocyanuric acid, 5-dimethyl hydantoin, etc. The cationic antibacterial agents have the characteristics of high efficiency, low toxicity and difficult influence by pH value change, are hydrolyzed cationic systems with high polymer guanidine salts, and can not influence the antibacterial effect mutually after being compounded, and meanwhile, a new antibacterial system is introduced, so that the antibacterial range, the efficiency and the drug resistance of the compound antibacterial system are greatly enhanced.
In a specific embodiment, the aminosilane coupling agent of the embodiments herein is preferably one of aminopropyl triethoxysilane, aminopropyl trimethoxysilane, aminopropyl methyldimethoxysilane, aminopropyl triethoxysilane, aminopropyl methyldiethoxysilane, anilinomethyl triethoxysilane, anilinomethyl trimethoxysilane, aminoethylaminoethyl aminopropyl trimethoxysilane. Wherein the aminosilane coupling agents can combine with resin and organic functional groups and inorganic TiO on the surface of the sheet 2 Thereby further improving the organic-TiO 2 The dispersion performance of the composite functional component on the surface and in the resin.
In a specific embodiment, the first resin and the second resin are the same or different and are one or more of polyamide, polyethylene, polypropylene, polyester, polylactic acid, polyurethane, polyimide and polyphenylene sulfide resin. The polymer resins have organic functional groups which are the same as or have affinity to polymer guanidine salt, so that the polymer resins can be well compatible in the processes of blending granulation and melt spinning, the fiber surface and the section are smooth and flat, the success rate of melt spinning is greatly improved, and the fiber can be widely applied to spinning, military, environmental protection, medical and health and construction.
In particular embodiments, the organic-TiO of the examples of this application 2 The mass ratio of the composite functional component to the first resin is preferably 5-60:100. wherein, the organic-TiO 2 The mass ratio of the composite functional component to the first resin is lower than 5:100, in order to achieve the ideal antibacterial and antiviral effects, the addition amount of the functionalized master batch is usually increased during melt spinning, so that the spinning continuity is greatly influenced; organic-TiO 2 The mass ratio of the composite functional component to the first resin is higher than 60:100 then easily results in a pelletization processThe pressure of the equipment components is too large, which is not beneficial to industrial production. Thus, embodiments of the present application preferably use organic-TiO 2 The mass ratio of the composite functional component to the first resin is 5-60:100, thereby improving the granulation performance under the condition of achieving ideal antibacterial and antiviral effects.
In a specific embodiment, the mass ratio of the functionalized masterbatch to the second resin in the embodiment of the application is preferably 5-25:100. wherein, the mass ratio of the functionalized master batch to the second resin is lower than 5:100, the prepared modified fiber has weak antibacterial and antiviral effects, and is difficult to achieve ideal antibacterial and antiviral effects; the mass ratio of the functionalized master batch to the second resin is higher than 25:100, the equipment components of the spinning process are prone to excessive pressure, affecting fiber spinnability. Therefore, the mass ratio of the functionalized masterbatch to the second resin is preferably 5-25:100, thereby improving spinning performance under the condition of achieving better antibacterial and antiviral effects.
In a second aspect, embodiments of the present application also provide an antimicrobial antiviral fiber made by the method of the first aspect.
Wherein the preparation method based on the first aspect can enable the macromolecular guanidine salt, the cationic antibacterial agent and the TiO 2 The full synergistic effect is generated, and the appearance quality of the antibacterial and antiviral fiber finished product can be improved. Therefore, the antibacterial and antiviral fiber prepared by the embodiment of the application has excellent antibacterial and antiviral performance and excellent appearance quality.
The test results of the examples show that the antibacterial and antiviral fibers have the antibacterial rates of more than 99% on escherichia coli, staphylococcus aureus and candida albicans; the antiviral rate to H1N1 influenza virus is more than 99.9%; and the surface and the section of the antibacterial and antiviral fiber are smooth and flat.
In a third aspect, embodiments of the present application further provide for the use of the antimicrobial and antiviral fibers described above based on the antimicrobial and antiviral properties of the antimicrobial and antiviral fibers described above and the effect of improving the appearance quality of the modified fibers. In particular to application of the antibacterial and antiviral fiber in the embodiment of the application as raw materials in manufacturing daily products including textile products, environment-friendly products, medical products, building products and the like. Based on the characteristics and effects of the antibacterial and antiviral fiber, daily products such as textile products, environment-friendly products, medical products, building products and the like prepared by using the antibacterial and antiviral fiber have excellent antibacterial and antiviral properties and good appearance quality.
The technical scheme of the present application will be further described in conjunction with specific embodiments.
Example 1
The embodiment provides a preparation method of an antibacterial and antiviral fiber alpha MPU1, which specifically comprises the following steps:
s101: after 100g of polyhexamethylene monoguanidine hydrochloride and 100g of benzalkonium chloride are dissolved in 100mL of ethanol with a concentration of 75% v, the mixture is fully stirred to obtain an organic composite component liquid phase;
s102: liquid phase of organic composite component and TiO 2 The mass ratio is 2:1, and carrying out two-stage vacuum drying with vacuum pressure of 0.1Mpa, wherein the temperature of the first-stage drying is 75 ℃ and the time is 2h; the second stage of drying is carried out at 100 ℃ for 1h to obtain the organic-TiO 2 A composite functional component;
s103: organic-TiO 2 The mass ratio of the composite functional component to the polyamide 56 resin to the aminopropyl triethoxysilane is 11.5:100:6, blending and granulating in proportion to obtain functional master batches;
s104: under the protection of nitrogen, after melt spinning is carried out on the functionalized master batch and the polyamide 56 resin according to the mass ratio of 10:100, the melt spinning is immediately immersed into ethanol water solution with the concentration of 5% v for surface treatment, and after the treatment is finished, the antibacterial and antiviral fiber alpha MPU1 is obtained.
Example 2
The embodiment provides a preparation method of an antibacterial and antiviral fiber alpha MPU2, which specifically comprises the following steps:
s201: after 30.2g of polyhexamethylene biguanide hydrochloride, 20.3g of polyhexamethylene guanidine hydrochloride and 40.3g of benzalkonium chloride were dissolved in 150mL of ethanol with a concentration of 65% v, the mixture was thoroughly stirred to obtain an organic composite component liquid phase;
s202: liquid phase of organic composite component and TiO 2 The mass ratio is 4:1, and then carrying out two-stage vacuum drying, wherein the temperature of the first-stage drying is 65 ℃, the time is 0.5h, and the pressure is 0.02Mpa; the second stage of drying is carried out at 90 ℃ for 0.1h under 0.1Mpa to obtain the organic-TiO 2 composite functional component;
s203: blending and granulating the organic-TiO 2 composite functional component and polylactic resin and aminopropyl triethoxysilane according to the mass ratio of 5:100:6 to obtain a functional master batch;
s204: under the protection of nitrogen, after melt spinning is carried out on the functionalized master batch and the polylactic acid resin according to the mass ratio of 25:100, the melt spinning is immediately immersed into 5% v methanol aqueous solution for surface treatment, and after the treatment is finished, the antibacterial and antiviral fiber alpha MPU2 is obtained.
Example 3
The embodiment provides a preparation method of an antibacterial and antiviral fiber alpha MPU3, which specifically comprises the following steps:
s301: after 45.5g of polyhexamethylene biguanide hydrochloride, 37.6g of benzalkonium chloride and 22.4g of chlorhexidine gluconate were dissolved in 120mL of ethanol with a concentration of 85% v, the mixture was sufficiently stirred to obtain an organic composite component liquid phase;
s302: liquid phase of organic composite component and TiO 2 The mass ratio is 5:1, and carrying out two-stage vacuum drying with vacuum pressure of 0.05Mpa, wherein the temperature of the first-stage drying is 72 ℃ and the time is 2h; the second stage of drying is carried out at the temperature of 80 ℃ for 2 hours to obtain the organic-TiO 2 composite functional component;
s303: blending and granulating the organic-TiO 2 composite functional component and polypropylene resin and aminopropyl methyl dimethoxy silane according to the mass ratio of 20:100:6 to obtain a functional master batch;
s304: under the protection of nitrogen, after melt spinning is carried out on the functionalized master batch and the polypropylene resin according to the mass ratio of 10:100, the master batch and the polypropylene resin are immediately immersed into ethanol water solution with the concentration of 5% v for surface treatment, and after the treatment is finished, the master batch and the polypropylene resin are dried, thus obtaining the antibacterial and antiviral fiber alpha MPU3.
Example 4
The embodiment provides a preparation method of an antibacterial and antiviral fiber alpha MPU4, which specifically comprises the following steps:
s401: after dissolving 55.2g of polyhexamethylene guanidine phosphate, 26.5g of chlorhexidine citrate and 35.5g of chloramine salt in 300mL of ethanol with concentration of 80% v, stirring thoroughly to obtain an organic composite component liquid phase;
s402: liquid phase of organic composite component and TiO 2 The mass ratio is 5:2, performing two-stage vacuum drying, wherein the temperature of the first-stage drying is 78 ℃, the time is 3 hours, and the pressure is 0.1Mpa; the second stage of drying is carried out at 120 ℃ for 1.5 hours under 0.04Mpa to obtain an organic-TiO 2 composite functional component;
s403: blending and granulating the organic-TiO 2 composite functional component and polyester resin and aminopropyl triethoxysilane according to the mass ratio of 20:100:6 to obtain a functional master batch;
s404: under the protection of nitrogen, after melt spinning is carried out on the functionalized polyester master batch and the polyester resin according to the mass ratio of 10:100, the polyester master batch and the polyester resin are immediately immersed into 5% v ethanol aqueous solution for surface treatment, and after the treatment is finished, the antibacterial and antiviral fiber alpha MPU4 is obtained.
Example 5
The embodiment provides a preparation method of an antibacterial and antiviral fiber alpha MPU5, which specifically comprises the following steps:
s501: after 48.5g of polyhexamethylene guanidine phosphate, 30.5g of polyhexamethylene biguanide hydrochloride and 60.2g of chloramine salt were dissolved in 200mL of ethanol with a concentration of 70% v, the mixture was thoroughly stirred to obtain an organic composite component liquid phase;
s502: liquid phase of organic composite component and TiO 2 The mass ratio is 2:1, and then carrying out two-stage vacuum drying, wherein the temperature of the first-stage drying is 70 ℃, the time is 1h, and the pressure is 0.04Mpa; the second stage of drying is carried out at 100 ℃ for 0.5h under 0.08Mpa to obtain the organic-TiO 2 composite functional component;
s503: blending and granulating the organic-TiO 2 composite functional component and polyethylene resin and aminopropyl methyl diethoxy silane according to the mass ratio of 10:100:6 to obtain a functional master batch;
s504: under the protection of nitrogen, after melt spinning is carried out on the functionalized master batch and the polyethylene resin according to the mass ratio of 5:100, the master batch and the polyethylene resin are immersed into a propanol aqueous solution with the concentration of 5% v for surface treatment, and after the treatment is finished, the master batch and the polyethylene resin are dried, thus obtaining the antibacterial and antiviral fiber alpha MPU5.
Example 6
The embodiment provides a preparation method of an antibacterial and antiviral fiber alpha MPU6, which specifically comprises the following steps:
s601: after 35.5g of polyhexamethylene guanidine phosphate, 15.5g of polyhexamethylene guanidine hydrochloride, 5g of polyhexamethylene biguanide hydrochloride, 10.9g of bromamine salt, 12.5g of benzalkonium bromide and 15.3g of chlorhexidine gluconate were dissolved in 180mL of ethanol with a concentration of 75% v, the mixture was thoroughly stirred to obtain an organic composite component liquid phase;
s602: liquid phase of organic composite component and TiO 2 The mass ratio is 10:3, carrying out two-stage vacuum drying, wherein the temperature of the first-stage drying is 68 ℃, the time is 4 hours, and the pressure is 0.08Mpa; the second stage of drying is carried out at 110 ℃ for 0.8h under 0.02Mpa to obtain an organic-TiO 2 composite functional component;
s603: blending and granulating the organic-TiO 2 composite functional component and polyphenylene sulfide resin and phenylaminomethyl triethoxysilane according to the mass ratio of 15:100:6 to obtain a functional master batch;
s604: under the protection of nitrogen, after melt spinning is carried out on the functionalized master batch and the polyphenylene sulfide 6 resin according to the mass ratio of 20:100, the master batch and the polyphenylene sulfide 6 resin are immersed into 5% v butanol aqueous solution for surface treatment, and after the treatment is finished, the master batch and the polyphenylene sulfide 6 resin are dried, thus obtaining the antibacterial and antiviral fiber alpha MPU6.
To verify the appearance quality of the antibacterial and antiviral fiber prepared in the examples of the present application, the antibacterial and antiviral fiber αmpu1 prepared in example 1 was subjected to appearance characterization, and the results are shown in fig. 1 to 2. Wherein, fig. 1 is an overall appearance diagram of an antibacterial and antiviral fiber αmpu 1; fig. 2A is a longitudinal cross-sectional SEM view of fig. 1, and fig. 2B is a cross-sectional SEM view of fig. 1.
According to FIGS. 1 to 2, the organic-TiO 2 composite functional component of the antibacterial and antiviral fiber prepared by the method is uniformly dispersed in the fiber, no obvious granular boundaries are generated, and uniform substances are formed on the surface of the fiber, so that the organic-TiO can be prepared 2 The composite functional component is effectively wrapped inside, has good appearance and melt spinning trafficability, and has excellent industrial production prospect.
Meanwhile, in order to verify the antibacterial and antiviral properties of the antibacterial and antiviral fibers αmpu1- αmpu6 prepared in the above examples, the present application provides the following detailed description of comparative examples 1-3.
Comparative example 1
The comparative example provides a preparation method of an antibacterial and antiviral fiber beta MPU1, which specifically comprises the following steps:
s701: mixing 100g of polyhexamethylene monoguanidine hydrochloride and 100g of benzalkonium chloride, and fully and uniformly stirring to obtain a composite antibacterial component;
s702: blending and granulating the composite antibacterial component and polyamide 56 resin according to the mass ratio of 1:9 to obtain a functional master batch;
s703: under the protection of nitrogen, the functionalized master batch and polyamide 56 resin are subjected to melt spinning according to the mass ratio of 1:9, so that the antibacterial and antiviral fiber beta MPU1 is obtained.
Comparative example 2
The comparative example provides a preparation method of antibacterial and antiviral fiber beta MPU2, which specifically comprises the following steps:
s801: after 100g of polyhexamethylene monoguanidine hydrochloride is dissolved in 100mL of ethanol with the concentration of 75% v, the mixture is fully stirred to obtain an antibacterial solution;
s802: antibacterial liquid and TiO 2 The mass ratio is 2:1, and carrying out two-stage vacuum drying with vacuum pressure of 0.1Mpa, wherein the temperature of the first-stage drying is 75 ℃ and the time is 2h. The second stage of drying is carried out at 100 ℃ for 1h to obtain a composite antibacterial component;
s803: blending and granulating the composite antibacterial component and polyamide 56 resin according to the mass ratio of 1:9 to obtain a functional master batch;
s804: under the protection of nitrogen, the functionalized master batch and polyamide 56 resin are subjected to melt spinning according to the mass ratio of 1:9, so that the antibacterial and antiviral fiber beta MPU2 is obtained.
Comparative example 3
The comparative example provides a preparation method of antibacterial and antiviral fiber beta MPU3, which specifically comprises the following steps:
s901: after 100g of polyhexamethylene monoguanidine hydrochloride and 100g of benzalkonium chloride were dissolved in 100mL of 75% v ethanol, the mixture was thoroughly stirred to obtain an organic composite component liquid phase;
s902: and carrying out two-stage vacuum drying on the organic composite component liquid phase under the vacuum pressure of 0.1Mpa, wherein the temperature of the first-stage drying is 75 ℃ and the time is 2h. The second stage of drying is carried out at 100 ℃ for 1h to obtain a composite antibacterial component;
s903: blending and granulating the composite antibacterial component and polyamide 56 resin according to the mass ratio of 1:9 to obtain a functional master batch;
s904: under the protection of nitrogen, the functionalized master batch and polyamide 56 resin are subjected to melt spinning according to the mass ratio of 1:9, so that the antibacterial and antiviral fiber beta MPU2 is obtained.
Evaluation of antibacterial Properties according to GB/T20944.3-2008, section 3: the antibacterial and antiviral fibers αmpu1 to αmpu6 prepared in examples 1 to 6 and the antibacterial and antiviral fibers βmpu1 to βmpu3 prepared in comparative examples 1 to 3 were subjected to antibacterial and antiviral performance tests by oscillation method and ISO 18184 "textile antiviral test", and the test results are described in table 1.
Table 1: antibacterial and antiviral Performance test of alpha MPU 1-alpha MPU6 and beta MPU 1-beta MPU3
As can be seen from Table 1, the examples of the present application are prepared by reacting a polymeric guanidine salt, a cationMicrobial agent and TiO 2 Compound preparation of organic-TiO 2 After the composite functional component is compounded into the resin fiber, the antibacterial performance and the antiviral performance of the fiber can be obviously enhanced, which indicates that the macromolecular guanidine salt antibacterial agent, the cationic antibacterial agent and the TiO 2 The antibacterial agent has obvious synergistic effect. Meanwhile, compared with comparative example 1 and comparative example 3, the composite powder of the polymer guanidine salt and the cationic antibacterial agent has obvious difference in antibacterial performance and antiviral performance compared with the composite liquid phase formed by the polymer guanidine salt and the cationic antibacterial agent in an organic solvent, and particularly, the difference in antiviral performance is obvious, so that the improvement of the uniformity of mixing the cationic antibacterial agent and the polymer guanidine salt is very critical for improving the antibacterial and antiviral performance of a product.
To verify the antibacterial and antiviral properties of the antibacterial and antiviral fibers αmpu1- αmpu6 prepared in the above examples in an anionic environment, the present application provides the following detailed description of comparative example 4.
Comparative example 4
The embodiment provides a preparation method of an antibacterial and antiviral fiber beta MPU4, which specifically comprises the following steps:
s101: after 100g of polyhexamethylene monoguanidine hydrochloride and 100g of benzalkonium chloride are dissolved in 100mL of ethanol with a concentration of 75% v, the mixture is fully stirred to obtain an organic composite component liquid phase;
s102: liquid phase of organic composite component and TiO 2 The mass ratio is 2:1, and carrying out two-stage vacuum drying with vacuum pressure of 0.1Mpa, wherein the temperature of the first-stage drying is 75 ℃ and the time is 2h; the second stage of drying is carried out at 100 ℃ for 1h to obtain the organic-TiO 2 A composite functional component;
s103: organic-TiO 2 The mass ratio of the composite functional component to the polyamide 56 resin to the aminopropyl triethoxysilane is 11.5:100:6, blending and granulating in proportion to obtain functional master batches;
s104: under the protection of nitrogen, the functionalized master batch and polyamide 56 resin are subjected to melt spinning according to the mass ratio of 10:100, and the antibacterial and antiviral fiber gamma MPU1 is obtained.
Anion dyeing is carried out on the antibacterial and antiviral fibers alpha MPU1 and the antibacterial and antiviral fibers gamma MPU1, and specifically, after dyeing for 30min at 95 ℃ by using black acid dye, the antibacterial performance evaluation part 3 is respectively carried out according to GB/T20944.3-2008 & lt- & gt: the dyed samples were subjected to antibacterial and antiviral property tests by the shaking method and ISO 18184 "textile antiviral test", and the results are shown in table 2.
Table 2: antibacterial and antiviral properties of alpha MPU1 and gamma MPU1 in anionic environments
As can be seen from Table 2, after the antibacterial and antiviral fiber formed by melt spinning is immersed into the aqueous solution containing alcohol for surface treatment, the durability and effectiveness of the antibacterial and antiviral fiber in an anionic environment can be obviously improved, and the treatment of the aqueous solution containing alcohol can hydrolyze silane groups grafted on the surface of the antibacterial and antiviral fiber to form a stable membranous structure, and can inhibit the polycondensation precipitation of the silane groups, so that the film forming efficiency and the stability of the membranous structure are greatly improved, and the modified fiber maintains durable and efficient antibacterial and antiviral functions.
Various embodiments in this specification are described in an incremental manner, and identical or similar parts of the various embodiments are referred to each other, with each embodiment focusing on differences from the other embodiments.
The above embodiments are only for illustrating the technical solution of the present application, and not for limiting the present application; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced with equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions.
Claims (10)
1. A method of making an antimicrobial antiviral fiber, the method comprising:
mixing the high molecular guanidine salt and the cationic antibacterial agent in an organic solvent to form an organic composite component liquid phase;
the organic composite component liquid phase and TiO 2 After mixing, vacuum drying to form organic-TiO 2 A composite functional component;
combining a first resin, an aminosilane coupling agent, and the organic-TiO 2 Blending and granulating the composite functional components to form functional master batches;
melt spinning the second resin and the functionalized master batch to obtain antibacterial and antiviral fibers;
wherein the first resin is the same as or different from the second resin.
2. The method of manufacturing according to claim 1, wherein the method further comprises:
immersing the antibacterial and antiviral fiber formed by melt spinning into an aqueous solution containing alcohol for surface treatment, and drying the surface treated product.
3. The preparation method according to claim 2, wherein the polymer guanidine salt is one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene guanidine hydrochloride and polyhexamethylene guanidine phosphate.
4. The preparation method according to claim 2, wherein the cationic antibacterial agent is one or more of quaternary ammonium salt antibacterial agent, chlorhexidine salt antibacterial agent, and halamine salt antibacterial agent.
5. The method according to claim 2, wherein the aminosilane coupling agent is one of aminopropyl triethoxysilane, aminopropyl trimethoxysilane, aminopropyl methyldimethoxysilane, aminopropyl triethoxysilane, aminopropyl methyldiethoxysilane, benzyl triethoxysilane, benzyl trimethoxysilane, and aminoethyl aminopropyl trimethoxysilane.
6. The method according to claim 2, wherein the first resin and the second resin are the same or different and are one or more of polyamide, polyethylene, polypropylene, polyester, polylactic acid, polyurethane, polyimide, and polyphenylene sulfide resins.
7. The method of claim 2, wherein the organic-TiO 2 The mass ratio of the composite functional component to the first resin is 5-60:100.
8. the preparation method according to claim 2, wherein the mass ratio of the functionalized masterbatch to the second resin is 5-25:100.
9. an antibacterial and antiviral fine denier monofilament, multifilament or profiled fiber produced according to the method of any one of claims 1-8.
10. Use of an antibacterial and antiviral fiber according to any of claims 1-8 for the manufacture of an antibacterial and antiviral fiber product.
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