CN116446066A - Preparation method of synergistic antibacterial antiviral deodorizing fiber - Google Patents
Preparation method of synergistic antibacterial antiviral deodorizing fiber Download PDFInfo
- Publication number
- CN116446066A CN116446066A CN202310353464.XA CN202310353464A CN116446066A CN 116446066 A CN116446066 A CN 116446066A CN 202310353464 A CN202310353464 A CN 202310353464A CN 116446066 A CN116446066 A CN 116446066A
- Authority
- CN
- China
- Prior art keywords
- antibacterial
- antiviral
- parts
- acid
- cqds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 131
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 123
- 239000000835 fiber Substances 0.000 title claims abstract description 88
- 230000001877 deodorizing effect Effects 0.000 title claims abstract description 36
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920000728 polyester Polymers 0.000 claims abstract description 47
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 26
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000002074 melt spinning Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 78
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 38
- 239000003242 anti bacterial agent Substances 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 33
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 claims description 31
- 229960002715 nicotine Drugs 0.000 claims description 31
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 230000000694 effects Effects 0.000 claims description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 14
- 241000588724 Escherichia coli Species 0.000 claims description 14
- 241000191967 Staphylococcus aureus Species 0.000 claims description 14
- 229910001431 copper ion Inorganic materials 0.000 claims description 14
- 208000037797 influenza A Diseases 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 238000001195 ultra high performance liquid chromatography Methods 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 13
- 238000006731 degradation reaction Methods 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- 241000222122 Candida albicans Species 0.000 claims description 7
- 229940095731 candida albicans Drugs 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011724 folic acid Substances 0.000 claims description 5
- 229960000304 folic acid Drugs 0.000 claims description 5
- 235000019152 folic acid Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 230000001580 bacterial effect Effects 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229960002645 boric acid Drugs 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 claims 2
- 241000191940 Staphylococcus Species 0.000 claims 1
- HNGOPXBXCIWNMX-UHFFFAOYSA-N acetic acid terephthalic acid Chemical compound C(C1=CC=C(C(=O)O)C=C1)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O HNGOPXBXCIWNMX-UHFFFAOYSA-N 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 17
- 239000000779 smoke Substances 0.000 abstract description 9
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000002045 lasting effect Effects 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 241000894006 Bacteria Species 0.000 description 8
- 239000003642 reactive oxygen metabolite Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 241000700605 Viruses Species 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229950000244 sulfanilic acid Drugs 0.000 description 3
- 102000053602 DNA Human genes 0.000 description 2
- 108020004414 DNA Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- -1 Polyethylene terephthalate Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002866 fluorescence resonance energy transfer Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance 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
- D01F6/92—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a preparation method of synergistic antibacterial antiviral deodorizing fiber, which comprises the steps of firstly preparing o-phenylenediamine and acid by a one-step hydrothermal method to obtain nanoscale nitrogen-doped carbon quantum dots, then coordinating the surfaces of the nitrogen-doped carbon quantum dots by an in-situ reduction method to generate nano elemental copper, modifying by carboxylic acid, introducing polyester by in-situ polymerization to obtain efficient antibacterial antiviral deodorizing polyester, and finally obtaining the antibacterial antiviral deodorizing polyester fiber by melt spinning. The polyester fiber prepared by the invention does not harm the environment in the use process, and has the characteristics of high-efficiency and lasting antibacterial and antiviral properties and capability of eliminating the smoke odor of fabrics.
Description
Technical Field
The invention relates to the field of synthesis of antibacterial and antiviral fibers, in particular to a preparation method of synergistic antibacterial and antiviral deodorizing polyester fibers, and especially relates to a preparation method of antibacterial and antiviral deodorizing polyester fibers with higher mechanical properties and better deodorizing function by synergistic effect of nitrogen-doped carbon quantum dots and nano copper.
Background
The retention time of pathogenic bacteria and viruses on the surface of human fabrics can be as long as 3-7 days, which seriously threatens the health of people. The fiber is one of main carriers for bacteria and viruses to parasitize and reproduce, and if the fiber can endow the fiber with antibacterial and antiviral functions, the comprehensive performance of the fiber product can be further improved, and the fiber product can be more applied to scenes needing antibacterial and antiviral. In addition, many people smoking in daily life, cigarette burning in-process can produce nicotine smell, and this kind of smell is very easy to adsorb on the fabric surface, influences the wearing experience of fabric. In recent years, antibacterial and antiviral and deodorizing composite function textiles are gradually favored by people, but the prior art cannot realize the multifunctional requirements of antibacterial and antiviral and deodorizing composite function fibers and fabrics. Therefore, the research of the antibacterial, antiviral and deodorizing composite functional fiber has important significance.
Polyethylene terephthalate (PET) has good fiber forming property, mechanical property, corrosion resistance, light transmittance and electrical insulation property, and is widely used in the fiber field, such as textile, film, industrial yarn and the like. The antibacterial modification of PET is realized mainly by adding antibacterial agents, and the antibacterial agents are mainly divided into organic antibacterial agents and inorganic antibacterial agents. The organic antibacterial agent has the advantages of wide source, low cost, simple process, high toxicity and poor durability, can cause the microorganism to generate drug resistance, and mainly kills bacteria by entering the inside of bacterial cells and destroying protein structures to deactivate the bacteria. The inorganic antibacterial agent is mainly divided into a metal ion antibacterial agent and a photocatalytic antibacterial agent. The metal ion antibacterial agent can dissolve out heavy metal ions, enter into bacterial cells and are compounded with DNA (deoxyribonucleic acid) of the bacteria, so that genetic materials of the bacteria cannot be copied, cell metabolism is destroyed to sterilize, and the heavy metal ions can be toxic to human bodies after long-time dissolution and accumulation. The photocatalytic antibacterial agent can generate Reactive Oxygen Species (ROS) such as hydroxyl radicals, singlet oxygen and peroxy radicals under the illumination condition, and the ROS has strong oxidation activity and can be combined with organic matters in microorganisms to play an antibacterial and antiviral role.
The nano copper is a non-leaching antibacterial agent, has the characteristics of large specific surface area, no toxicity and stability compared with the common copper antibacterial agent, and can directly react with water and oxygen in the air to convert the water and oxygen into active oxygen free radicals so as to play a role in killing bacteria and viruses. The nano copper has good antibacterial property, but is easy to agglomerate during blending processing, has poor dispersing effect, and has the problems of poor spinnability and antibacterial durability when being applied to polyester fibers.
The nitrogen doped carbon quantum dots (N-CQDs) are novel fluorescent carbon nano particles, belong to photocatalysis type antibacterial antiviral agents, can play a role only under the ultraviolet condition, and have excellent optical characteristics, good biocompatibility and wide raw material sources. Under photocatalysis, N-CQDs not only can generate ROS (reactive oxygen species) antibacterial and antiviral effects, but also can interact with nicotine in smoke odor to achieve the effect of degrading nicotine and deodorizing, but the nanoscale size of the N-CQDs is easy to agglomerate when the polymer is added, so that the spinning performance of the polymer and the antibacterial, antiviral and deodorizing effects are affected.
Disclosure of Invention
The invention aims to provide a preparation method of synergistic antibacterial antiviral deodorizing fiber, which aims to solve the problems of poor spinnability and antibacterial antiviral deodorizing effect when nano copper and nitrogen doped carbon quantum dots are applied to polyester fiber. For this purpose, the invention adopts the following technical scheme:
N-CQDs with the size of 3-5nm are prepared by using o-phenylenediamine and acid through a one-step hydrothermal method, nano elemental copper with the size of 2-10nm is coordinated on the surface of the N-CQDs through an in-situ reduction method to obtain Cu-N-CQDs, the Cu-N-CQDs are modified by carboxylic acid to obtain CM-Cu-N-CQDs so as to improve the compatibility of the CM-Cu-N-CQDs with polymers, then the Cu-N-CQDs are polymerized in-situ in the PET synthesis process to obtain the antibacterial and antiviral polyester, and finally the antibacterial and antiviral fiber with the cross-shaped structure is obtained through melt spinning.
The size of the nitrogen doped carbon quantum dots (N-CQDs) obtained by the invention is 3-5nm, active oxygen free radicals can be generated under sunlight to play a role in efficient antibiosis and antivirus, and electron-pushing groups C=N or C=O on the surfaces of the carbon quantum dots can generate pi-pi conjugation effect with electron-pushing groups C=N on the surfaces of nicotine to generate fluorescence resonance energy transfer, so that the carbon quantum dots can use more energy for degrading nicotine, and the effect of eliminating smoke odor is realized. The nano elemental copper obtained by the method has the size of 2-10nm, the nano elemental copper with the size has higher catalytic reaction antibacterial and antiviral activity, the nano copper can continuously activate oxygen in water and air to generate Reactive Oxygen Species (ROS), and the ROS (hydroxyl free radicals, superoxide free radicals and hydrogen peroxide) have strong oxidizing property, can directly or indirectly damage the structure and function of cells, and cause death of bacteria and viruses. The sizes of the N-CQDs and the nano Cu are nano-scale, and the N-CQDs and the nano Cu are easy to agglomerate in the use process, so that the spinning performance of the polymer and the antibacterial, antiviral and deodorizing effects are affected.
According to the invention, the Cu-N-CQDs are obtained by combining nano copper and nitrogen-doped carbon quantum dots (N-CQDs), and the CM-Cu-N-CQDs are obtained by modifying the Cu-N-CQDs through carboxylic acid so as to improve the dispersibility and compatibility of the Cu-N-CQDs in polyester polymerization, so that the efficient antibacterial, antiviral and deodorizing fiber is developed, the problem that the spinnability and the antibacterial, antiviral and deodorizing durability are poor when the nano copper and nitrogen-doped carbon quantum dots are applied to the polyester fiber is solved, and the higher requirements of different fields on the antibacterial and antiviral properties of the fiber are met. The Cu-N-CQDs obtained through carboxylic acid modification not only have better compatibility with PET, but also can be uniformly and stably dispersed in a melt in-situ polymerization of PET, so that the problem of agglomeration of nano-scale N-CQDs and copper is avoided, but also the carboxyl can be better complexed with nano-copper to maintain the nano-copper of the Cu-N-CQDs in a reduction state all the time, and active oxygen free radicals are continuously released to play a role in resisting bacteria and viruses. In addition, the nano copper can make up the defect that N-CQDs are difficult to play an antibacterial, antiviral and deodorizing role when not irradiated by ultraviolet light, and plays a role in cooperating with efficient antibacterial, antiviral and deodorizing. Therefore, the fiber obtained by the invention has high-efficiency and durable antibacterial, antiviral and deodorizing effects, has higher mechanical properties, and can be used in the field with higher requirements on the antibacterial, antiviral and deodorizing properties of the fiber.
The invention relates to a preparation method of synergistic antibacterial antiviral deodorizing fiber, which comprises the following specific steps:
(1) According to parts by mass, 2-5 parts of o-phenylenediamine is ultrasonically dispersed in 100 parts of 95% ethanol to prepare o-phenylenediamine solution, 2-10 parts of acid is ultrasonically dispersed in 100 parts of 95% ethanol to prepare acid solution, the o-phenylenediamine solution and the acid solution are mixed and then added into a stainless steel autoclave, the mixture reacts for 0.5-18 hours at 160-260 ℃ to obtain dark brown solution, the obtained product is centrifugally washed for 3-5 times by deionized water and absolute ethyl alcohol, and finally, nitrogen-doped carbon quantum dots (N-CQDs) are obtained by drying;
(2) 2-4 parts of N-CQDs are ultrasonically dispersed in 50 parts of deionized water under certain conditions to prepare an N-CQDs aqueous solution, and 0.8-1.4 parts of copper salt is dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution; mixing the N-CQDs aqueous solution and the copper ion aqueous solution in a flask, condensing and refluxing after mixing, then stirring, adding 50 parts of reducer aqueous solution dropwise into the flask at the same time, and stirring for 3-24 hours at 60-90 ℃ to obtain a dark solution; centrifugally separating the obtained product by deionized water and absolute ethyl alcohol, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper generated on the surface;
(3) Adding 100 parts of absolute ethyl alcohol into 1-3 parts of aliphatic dibasic acid, 15-20 parts of Cu-N-CQDs antibacterial agent and 0.5-2 parts of ethylene glycol, condensing, refluxing and stirring for 0.5-5 hours to obtain carboxylic acid modified Cu-N-CQDs slurry, then putting the modified Cu-N-CQDs slurry into a centrifuge tube for centrifugation, removing sediment obtained by supernatant, washing with ethyl alcohol and water for 3-5 times, and drying to obtain carboxylic acid modified Cu-N-CQDs;
(4) Adding 1-3 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 35-45 parts of ethylene glycol into a polymerization reaction kettle, esterifying, pre-polymerizing, final polymerizing, and finally carrying out tape casting and granulating to obtain an antibacterial and antiviral polyester chip;
(5) Drying the antibacterial and antiviral polyester chips for a period of time at 90-120 ℃, and adding the dried antibacterial and antiviral polyester chips into a melt spinning machine for spinning to obtain the antibacterial and antiviral polyester fiber with the cross-section structure.
In the step (1), the condition of ultrasonic dispersion of o-phenylenediamine and acid means that the time is 20-60 min and the ultrasonic frequency is 30-60 kHz;
in the step (1), the acid refers to one of benzenesulfonic acid, folic acid, boric acid, acetic acid, terephthalic acid and tartaric acid;
in the step (2), the certain condition of ultrasonic dispersion of N-CQDs under certain conditions means that the time is 20-60 min and the ultrasonic frequency is 30-60 kHz;
in the step (2), the copper salt refers to one of copper chloride, copper sulfate and copper nitrate;
in the step (2), the aqueous solution of the reducing agent is one of 0.1-0.5 mol/L of aqueous solution of citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride;
in the step (3), the aliphatic dibasic acid refers to one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid;
in the step (4), the esterification reaction condition is that the temperature is 235-255 ℃, the pressure is 0.3-0.4 MPa, and the time is 2-3 h;
in the step (4), the reaction condition of the prepolymerization is that the temperature is 260-270 ℃, the pressure is-0.09-0.10 MPa, and the time is 0.5-1.5 h;
in the step (4), the final polymerization reaction condition is that the temperature is 270-280 ℃, the pressure is 20-100 Pa, and the time is 2-3 h;
in the step (5), the spinneret plate is in a cross-shaped spinneret hole shape during spinning, and the spun fiber is in a cross-shaped abnormal structure;
according to the preparation method of the synergistic antibacterial antiviral deodorizing fiber, in the step (5), the breaking strength of the antibacterial antiviral polyester fiber is 2.0-3.5 cN/dtex, the breaking elongation is 15-30%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can be more than 99%, the antiviral effect on influenza A H1N1 virus can be more than 99%, the photocatalytic degradation effect of the antibacterial antiviral fiber on nicotine under simulated sunlight is detected by ultra-high performance liquid chromatography (UPLC), the degradation effect of the antibacterial antiviral fiber on nicotine can be more than 99% after 75 minutes of sunlight irradiation, the antibacterial rate of the antibacterial fiber on escherichia coli and staphylococcus aureus can still be more than 97%, the antiviral effect on influenza A H1N1 virus can be more than 97%, the degradation effect on nicotine can be more than 97% after 75 minutes of sunlight irradiation, and the antibacterial antiviral fiber has better water washing performance, high-efficient antibacterial antiviral performance and fabric smoke deodorizing performance.
The invention has the beneficial effects that:
(1) Safety: the Cu-N-CQDs prepared by the method are non-leaching antibacterial and antiviral auxiliary agents, have no ion overflow phenomenon, cannot cause harm to human bodies and the environment, and are safer and more environment-friendly;
(2) Durable antibacterial: the nano copper prepared by the method is always in a reduced state, and has lasting antibacterial and antiviral effects by continuously releasing active oxygen free radicals;
(3) High-efficiency antibacterial: the nano copper can still play an antibacterial and antiviral effect when no ultraviolet irradiation is performed, and can realize higher antibacterial and antiviral effects and eliminate the nicotine effect of the fabric by combining with N-CQDs;
(4) High strength: the carboxylic acid modified Cu-N-CQDs prepared by the invention have good dispersibility, and the prepared antibacterial and antiviral polyester composite fiber has good spinnability and high mechanical properties.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1, a preparation method of synergistic antibacterial antiviral deodorizing fiber comprises the following specific steps:
(1) According to parts by mass, 2.5 parts of o-phenylenediamine is ultrasonically dispersed in 100 parts of 95% ethanol for 20min at a frequency of 60kHz to prepare an o-phenylenediamine solution, 2 parts of terephthalic acid is ultrasonically dispersed in 100 parts of 95% ethanol for 20min at a frequency of 60kHz to prepare a terephthalic acid solution, the o-phenylenediamine solution and the terephthalic acid solution are mixed and then added into a stainless steel autoclave to react for 3h at 160 ℃ to obtain a dark brown solution, the obtained product is centrifugally washed with deionized water and absolute ethanol for 3 times, and finally, nitrogen-doped carbon quantum dots (N-CQDs) are obtained by drying;
(2) 2 parts of nano N-CQDs are ultrasonically dispersed in 50 parts of deionized water at the frequency of 60kHz for 20min to prepare an aqueous solution of N-CQDs, and 0.8 part of anhydrous copper sulfate is dissolved in 50 parts of deionized water to prepare an aqueous solution of copper ions. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask and then subjected to condensation reflux at 80℃and then stirred while 50 parts of 0.1mol/L aqueous solution of citric acid were added dropwise to the flask and stirred at 60℃for 3 hours to obtain a dark solution. Centrifugally separating the obtained product by deionized water and absolute ethyl alcohol, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper generated on the surface;
(3) Adding 1.5 parts of adipic acid, 15 parts of Cu-N-CQDs antibacterial agent and 0.5 part of ethylene glycol into 100 parts of absolute ethyl alcohol, condensing and refluxing at 80 ℃ and stirring for 2 hours to obtain carboxylic acid modified Cu-N-CQDs slurry, then putting the carboxylic acid modified Cu-N-CQDs slurry into a centrifuge tube for centrifugation, removing a precipitate obtained by supernatant, washing with ethanol and water for 3 times, and drying to obtain carboxylic acid modified Cu-N-CQDs;
(4) 1.5 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 35 parts of ethylene glycol are added into a polymerization reaction kettle, and the reaction kettle is pressurized and heated after being closed. Controlling the pressure and the temperature of the reaction kettle to be 0.34MPa and 235 ℃ respectively, and carrying out esterification reaction for 2h; then a vacuum pump is started to perform pre-polycondensation, and the pressure and the temperature of the reaction kettle are respectively-0.09 MPa and 260 ℃ at the moment, and the pre-polymerization is performed for 0.5h; the vacuum was increased to 20Pa, the temperature was controlled at 270℃and the final polymerization was carried out for 2h. Finally, carrying out belt casting and grain cutting to obtain the antibacterial and antiviral polyester chip with the function of eliminating the nicotine of the fabric;
(5) Drying the antibacterial and antiviral polyester chips in a drying oven at 100 ℃ for 16 hours, adding the dried antibacterial and antiviral polyester chips into melt spinning for spinning, wherein a spinneret plate is a spinneret hole with a cross structure, and thus the antibacterial and antiviral polyester fiber with the cross section structure is obtained.
The antibacterial and antiviral polyester fiber has the breaking strength of 3.5cN/dtex, the breaking elongation of 30 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.0 percent, the antiviral effect on influenza A H1N1 virus of 99.0 percent, the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight detected by ultra-high performance liquid chromatography (UPLC), the degradation effect of the antibacterial and antiviral fiber on nicotine of 99.2 percent after 75 minutes of sunlight irradiation, the antibacterial rate of the fiber on escherichia coli and staphylococcus aureus of 97 percent after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus of 97.1 percent after 75 minutes of sunlight irradiation, the degradation effect on nicotine of 97.1 percent, and the antibacterial and antiviral fiber has better water washing resistance, high-efficiency antibacterial and antiviral performance and fabric smoke odor elimination performance.
Example 2, a preparation method of synergistic antibacterial antiviral deodorizing fiber, specifically comprises the following steps:
(1) According to parts by mass, 2.5 parts of o-phenylenediamine is ultrasonically dispersed in 100 parts of 95% ethanol for 60min at the frequency of 30kHz to prepare an o-phenylenediamine solution, 3 parts of tartaric acid is ultrasonically dispersed in 100 parts of 95% ethanol for 60min at the frequency of 30kHz to prepare a tartaric acid solution, the o-phenylenediamine solution and the tartaric acid solution are mixed and then added into a stainless steel autoclave, the reaction is carried out for 3h at 200 ℃ to obtain a dark brown solution, the obtained product is centrifugally washed for 4 times by deionized water and absolute ethanol, and finally, nitrogen-doped carbon quantum dots (N-CQDs) are obtained by drying;
(2) 2.5 parts of nano N-CQDs are ultrasonically dispersed in 50 parts of deionized water at the frequency of 30kHz for 60min to prepare an aqueous solution of N-CQDs, and 1 part of cupric chloride is dissolved in 50 parts of deionized water to prepare an aqueous solution of copper ions. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask and then subjected to condensation reflux at 80℃and then stirred while 50 parts of 0.5mol/L aqueous solution of ascorbic acid was added dropwise to the flask and stirred at 90℃for 24 hours to obtain a dark solution. Centrifugally separating the obtained product by deionized water and absolute ethyl alcohol, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper generated on the surface;
(3) Adding 100 parts of absolute ethyl alcohol into 2.5 parts of suberic acid, 20 parts of Cu-N-CQDs antibacterial agent and 1 part of ethylene glycol, condensing and refluxing at 80 ℃ and stirring for 5 hours to obtain carboxylic acid modified Cu-N-CQDs slurry, then putting the carboxylic acid modified Cu-N-CQDs slurry into a centrifuge tube for centrifugation, removing a precipitate obtained by supernatant, washing with ethanol and water for 5 times, and drying to obtain carboxylic acid modified Cu-N-CQDs;
(4) 1.5 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 40 parts of ethylene glycol are added into a polymerization reaction kettle, and the reaction kettle is pressurized and heated after being closed. Controlling the pressure and the temperature of the reaction kettle to be 0.40MPa and 255 ℃ respectively, and carrying out esterification reaction for 3 hours; then a vacuum pump is started to perform pre-polycondensation, and the pressure and the temperature of the reaction kettle are respectively-0.10 MPa and 270 ℃ at the moment, and the pre-polymerization is performed for 1.5 hours; the vacuum degree is increased to 100Pa, the temperature is controlled at 280 ℃, and the final polymerization is carried out for 3h. Finally, carrying out belt casting and grain cutting to obtain the antibacterial and antiviral polyester chip with the function of eliminating the nicotine of the fabric;
(5) Drying the antibacterial and antiviral polyester chips in a drying oven at 100 ℃ for 24 hours, adding the dried antibacterial and antiviral polyester chips into melt spinning for spinning, wherein a spinneret plate is a spinneret hole with a cross structure, and thus the antibacterial and antiviral polyester fiber with the cross section structure is obtained.
The antibacterial and antiviral polyester fiber has the breaking strength of 2.8cN/dtex, the breaking elongation of 20 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.3 percent, the antiviral effect on influenza A H1N1 virus can reach 99.2 percent, the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight is detected by ultra-high performance liquid chromatography (UPLC), the degradation effect of the antibacterial and antiviral fiber on nicotine can reach more than 99.6 percent after 75 minutes of sunlight irradiation, the antibacterial rate of the fiber on escherichia coli and staphylococcus aureus can still reach more than 97.3 percent after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus can reach 97.2 percent, the degradation effect on nicotine after 75 minutes of sunlight irradiation can reach more than 97.5 percent, and the antibacterial and antiviral fiber has better water-washing resistance, high-efficiency antibacterial and antiviral performance and capability of eliminating smoke odor of fabrics.
Example 3, a preparation method of synergistic antibacterial antiviral deodorizing fiber, specifically comprises the following steps:
(1) According to parts by mass, 3.5 parts of o-phenylenediamine is ultrasonically dispersed in 100 parts of 95% ethanol for 40min at 40kHz to prepare an o-phenylenediamine solution, 4 parts of 4-aminobenzenesulfonic acid is ultrasonically dispersed in 100 parts of 95% ethanol for 40min at 40kHz to prepare a 4-aminobenzenesulfonic acid solution, the o-phenylenediamine solution and the 4-aminobenzenesulfonic acid solution are mixed and then added into a stainless steel autoclave, the mixture is reacted for 8h at 220 ℃ to obtain a dark brown solution, the obtained product is centrifugally washed with deionized water and absolute ethyl alcohol for 3 times, and finally, the nitrogen-doped carbon quantum dots (N-CQDs) are obtained by drying;
(2) 3 parts of nano N-CQDs are ultrasonically dispersed in 50 parts of deionized water at the frequency of 40kHz for 40min to prepare an aqueous solution of N-CQDs, and 1.2 parts of cupric chloride is dissolved in 50 parts of deionized water to prepare an aqueous solution of copper ions. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask and then subjected to condensation reflux at 80℃and then stirred while 50 parts of 0.3mol/L aqueous solution of ascorbic acid was added dropwise to the flask and stirred at 70℃for 20 hours to obtain a dark solution. Centrifugally separating the obtained product by deionized water and absolute ethyl alcohol, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper generated on the surface;
(3) Adding 100 parts of absolute ethyl alcohol into 2.5 parts of dodecanedioic acid, 15 parts of Cu-N-CQDs antibacterial agent and 1.5 parts of ethylene glycol, condensing and refluxing at 80 ℃ and stirring for 2 hours to obtain carboxylic acid modified Cu-N-CQDs slurry, then putting the carboxylic acid modified Cu-N-CQDs slurry into a centrifuge tube for centrifugation, removing a precipitate obtained by supernatant, washing with ethyl alcohol and water for 5 times, and drying to obtain carboxylic acid modified Cu-N-CQDs;
(4) 2 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 40 parts of ethylene glycol are added into a polymerization reaction kettle, and the reaction kettle is pressurized and heated after being sealed. Controlling the pressure and the temperature of the reaction kettle to be 0.35MPa and 245 ℃ respectively, and carrying out esterification reaction for 3 hours; then starting a vacuum pump to perform pre-polycondensation, wherein the pressure and the temperature of the reaction kettle are respectively-0.10 MPa and 265 ℃, and the pre-polymerization is performed for 1h; the vacuum was raised to 60Pa, the temperature was controlled at 278℃and the final polymerization was carried out for 2.5h. Finally, carrying out belt casting and grain cutting to obtain the antibacterial and antiviral polyester chip with the function of eliminating the nicotine of the fabric;
(5) Drying the antibacterial and antiviral polyester chips in a drying oven at 100 ℃ for 36 hours, adding the dried antibacterial and antiviral polyester chips into melt spinning for spinning, wherein a spinneret plate is a spinneret hole with a cross structure, and thus the antibacterial and antiviral polyester fiber with the cross section structure is obtained.
The antibacterial and antiviral polyester fiber has the breaking strength of 3.1cN/dtex, the breaking elongation of 24 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.5 percent, the antiviral effect on influenza A H1N1 virus can reach 99.5 percent, the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight is detected by ultra-high performance liquid chromatography (UPLC), the degradation effect of the antibacterial and antiviral fiber on nicotine can reach more than 99.2 percent after 75 minutes of sunlight irradiation, the antibacterial rate of the fiber on escherichia coli and staphylococcus aureus still reaches more than 97 percent after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus reaches 97.1 percent, the degradation effect on nicotine reaches more than 97.2 percent after 75 minutes of sunlight irradiation, and the antibacterial and antiviral fiber has better water washing resistance, high-efficiency antibacterial and antiviral performance and fabric smoke odor elimination performance.
Example 4, a method for preparing synergistic antibacterial antiviral deodorizing fiber, comprises the following specific steps:
(1) According to parts by mass, 4.5 parts of o-phenylenediamine is ultrasonically dispersed in 100 parts of 95% ethanol for 50min at the frequency of 30kHz to prepare an o-phenylenediamine solution, 6 parts of folic acid is ultrasonically dispersed in 100 parts of 95% ethanol for 50min at the frequency of 30kHz to prepare a folic acid solution, the o-phenylenediamine solution and the folic acid solution are mixed and then added into a stainless steel autoclave, the reaction is carried out for 10h at 240 ℃ to obtain a dark brown solution, the obtained product is centrifugally washed for 5 times by deionized water and absolute ethyl alcohol, and finally, nitrogen-doped carbon quantum dots (N-CQDs) are obtained by drying;
(2) 4 parts of nano N-CQDs are ultrasonically dispersed in 50 parts of deionized water at the frequency of 30kHz for 50min to prepare an aqueous solution of N-CQDs, and 1.4 parts of cupric chloride is dissolved in 50 parts of deionized water to prepare an aqueous solution of copper ions. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask and then subjected to condensation reflux at 80℃and then stirred while 50 parts of 0.4mol/L aqueous solution of ascorbic acid was added dropwise to the flask and stirred at 80℃for 20 hours to obtain a dark solution. Centrifugally separating the obtained product by deionized water and absolute ethyl alcohol, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper generated on the surface;
(3) Adding 100 parts of absolute ethyl alcohol into 2.5 parts of sebacic acid, 17 parts of Cu-N-CQDs antibacterial agent and 2 parts of ethylene glycol, condensing and refluxing at 80 ℃ and stirring for 3 hours to obtain carboxylic acid modified Cu-N-CQDs slurry, then placing the carboxylic acid modified Cu-N-CQDs slurry into a centrifuge tube for centrifugation, removing sediment obtained by supernatant, washing with ethanol and water for 5 times, and drying to obtain carboxylic acid modified Cu-N-CQDs;
(4) 1.5 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 45 parts of ethylene glycol are added into a polymerization reaction kettle, and the reaction kettle is pressurized and heated after being closed. Controlling the pressure and the temperature of the reaction kettle to be 0.40MPa and 245 ℃ respectively, and carrying out esterification reaction for 2h; then a vacuum pump is started to perform pre-polycondensation, and the pressure and the temperature of the reaction kettle are respectively-0.08 MPa and 270 ℃ at the moment, and the pre-polymerization is performed for 1.5 hours; the vacuum was raised to 60Pa, the temperature was controlled at 278℃and the final polymerization was carried out for 3h. Finally, carrying out belt casting and grain cutting to obtain the antibacterial and antiviral polyester chip with the function of eliminating the nicotine of the fabric;
(5) Drying the antibacterial and antiviral polyester chips in a drying oven at 100 ℃ for 24 hours, adding the dried antibacterial and antiviral polyester chips into melt spinning for spinning, wherein a spinneret plate is a spinneret hole with a cross structure, and thus the antibacterial and antiviral polyester fiber with the cross section structure is obtained.
The antibacterial and antiviral polyester fiber has the breaking strength of 3.4cN/dtex, the breaking elongation of 20 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.3 percent, the antiviral effect on influenza A H1N1 virus can reach 99.1 percent, the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight is detected by ultra-high performance liquid chromatography (UPLC), the degradation effect of the antibacterial and antiviral fiber on nicotine can reach more than 99.4 percent after 75 minutes of sunlight irradiation, the antibacterial rate of the fiber on escherichia coli and staphylococcus aureus can still reach more than 97.5 percent after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus can reach 97.4 percent, the degradation effect on nicotine after 75 minutes of sunlight irradiation can reach more than 97.3 percent, and the antibacterial and antiviral fiber has better water-washing resistance, high-efficiency antibacterial and antiviral performance and capability of eliminating smoke odor of fabrics.
Example 5, a method for preparing synergistic antibacterial antiviral deodorizing fiber, comprises the following specific steps:
(1) According to parts by mass, 4.5 parts of o-phenylenediamine is ultrasonically dispersed in 100 parts of 95% ethanol for 30min at 50kHz to prepare an o-phenylenediamine solution, 8 parts of acetic acid is ultrasonically dispersed in 100 parts of 95% ethanol for 30min at 50kHz to prepare an acetic acid solution, the o-phenylenediamine solution and the acetic acid solution are mixed and then added into a stainless steel autoclave, the reaction is carried out for 14h at 260 ℃ to obtain a dark brown solution, the obtained product is centrifugally washed for 5 times by deionized water and absolute ethyl alcohol, and finally, nitrogen-doped carbon quantum dots (N-CQDs) are obtained by drying;
(2) 3.5 parts of nano N-CQDs are ultrasonically dispersed in 50 parts of deionized water at 50kHz frequency for 30min to prepare an aqueous solution of N-CQDs, and 1.4 parts of cupric chloride is dissolved in 50 parts of deionized water to prepare an aqueous solution of copper ions. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask and then subjected to condensation reflux at 80℃and then stirred while 50 parts of 0.3mol/L aqueous solution of ascorbic acid was added dropwise to the flask and stirred at 80℃for 22 hours to obtain a dark solution. Centrifugally separating the obtained product by deionized water and absolute ethyl alcohol, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper generated on the surface;
(3) Adding 100 parts of absolute ethyl alcohol into 2 parts of sebacic acid, 15 parts of Cu-N-CQDs antibacterial agent and 1.5 parts of ethylene glycol, condensing and refluxing at 80 ℃ and stirring for 3 hours to obtain carboxylic acid modified Cu-N-CQDs slurry, then placing the carboxylic acid modified Cu-N-CQDs slurry into a centrifuge tube for centrifugation, removing sediment obtained by supernatant, washing with ethanol and water for 5 times, and drying to obtain carboxylic acid modified Cu-N-CQDs;
(4) 2.5 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 45 parts of ethylene glycol are added into a polymerization reaction kettle, and the reaction kettle is pressurized and heated after being closed. Controlling the pressure and the temperature of the reaction kettle to be 0.36MPa and 245 ℃ respectively, and carrying out esterification reaction for 3 hours; then a vacuum pump is started to perform pre-polycondensation, and the pressure and the temperature of the reaction kettle are respectively-0.10 MPa and 265 ℃ at the moment, and the pre-polymerization is performed for 0.5h; the vacuum degree is increased to 100Pa, the temperature is controlled at 280 ℃, and the final polymerization is carried out for 3h. Finally, carrying out belt casting and grain cutting to obtain the antibacterial and antiviral polyester chip with the function of eliminating the nicotine of the fabric;
(5) Drying the antibacterial and antiviral polyester chips in a drying oven at 100 ℃ for 36 hours, adding the dried antibacterial and antiviral polyester chips into melt spinning for spinning, wherein a spinneret plate is a spinneret hole with a cross structure, and thus the antibacterial and antiviral polyester fiber with the cross section structure is obtained.
The antibacterial and antiviral polyester fiber has the breaking strength of 3.0cN/dtex, the breaking elongation of 21 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.4 percent, the antiviral effect on influenza A H1N1 virus of 99.5 percent, the photocatalytic degradation effect of the antibacterial and antiviral fiber on nicotine under simulated sunlight detected by ultra-high performance liquid chromatography (UPLC), the degradation effect of the antibacterial and antiviral fiber on nicotine of 99.5 percent after 75 minutes of sunlight irradiation, the antibacterial rate of the fiber on escherichia coli and staphylococcus aureus of 97.8 percent after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus of 97.4 percent after 75 minutes of sunlight irradiation, the degradation effect on nicotine of 97.6 percent, and the antibacterial and antiviral fiber has better water washing resistance, high-efficiency antibacterial and antiviral performance and capability of eliminating smoke odor of fabrics.
Claims (6)
1. A method for preparing synergistic antibacterial antiviral deodorizing fiber, which is characterized by comprising the following steps:
(1) According to parts by mass, 2-5 parts of o-phenylenediamine is ultrasonically dispersed in 100 parts of 95% ethanol to prepare o-phenylenediamine solution, 2-10 parts of acid is ultrasonically dispersed in 100 parts of 95% ethanol to prepare acid solution, the o-phenylenediamine solution and the acid solution are mixed and then added into a stainless steel autoclave, the mixture reacts for 0.5-18 hours at 160-260 ℃ to obtain dark brown solution, the obtained product is centrifugally washed for 3-5 times by deionized water and absolute ethyl alcohol, and finally, nitrogen-doped carbon quantum dots (N-CQDs) are obtained by drying;
(2) 2-4 parts of N-CQDs are ultrasonically dispersed in 50 parts of deionized water under certain conditions to prepare an N-CQDs aqueous solution, and 0.8-1.4 parts of copper salt is dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution; mixing the N-CQDs aqueous solution and the copper ion aqueous solution in a flask, condensing and refluxing after mixing, then stirring, adding 50 parts of reducer aqueous solution dropwise into the flask at the same time, and stirring for 3-24 hours at 60-90 ℃ to obtain a dark solution; centrifugally separating the obtained product by deionized water and absolute ethyl alcohol, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper generated on the surface;
(3) Adding 100 parts of absolute ethyl alcohol into 1-3 parts of aliphatic dibasic acid, 15-20 parts of Cu-N-CQDs antibacterial agent and 0.5-2 parts of ethylene glycol, condensing, refluxing and stirring for 0.5-5 hours to obtain carboxylic acid modified Cu-N-CQDs slurry, then putting the modified Cu-N-CQDs slurry into a centrifuge tube for centrifugation, removing sediment obtained by supernatant, washing with ethyl alcohol and water for 3-5 times, and drying to obtain carboxylic acid modified Cu-N-CQDs;
(4) Adding 1-3 parts of carboxylic acid modified Cu-N-CQDs, 80 parts of terephthalic acid and 35-45 parts of ethylene glycol into a polymerization reaction kettle, esterifying, pre-polymerizing, final polymerizing, and finally carrying out tape casting and granulating to obtain an antibacterial and antiviral polyester chip;
(5) Drying the antibacterial and antiviral polyester chips for a period of time at 90-120 ℃, and adding the dried antibacterial and antiviral polyester chips into a melt spinning machine for spinning to obtain the antibacterial and antiviral polyester fiber with the cross-section structure.
2. The method for preparing the synergistic antibacterial antiviral deodorizing fiber according to claim 1, wherein in the step (1), the condition of ultrasonic dispersion of o-phenylenediamine and acid means that the time is 20-60 min, and the ultrasonic frequency is 30-60 kHz; the acid is benzenesulfonic acid, folic acid, boric acid, acetic acid terephthalic acid, tartaric acid.
3. The method for preparing synergistic antibacterial antiviral deodorizing fiber according to claim 1, wherein in the step (2), the certain condition of ultrasonic dispersion of N-CQDs under certain conditions means a time of 20 to 60min and an ultrasonic frequency of 30 to 60kHz; the copper salt refers to one of copper chloride, copper sulfate and copper nitrate; the aqueous solution of the reducing agent is one of 0.1-0.5 mol/L of citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride.
4. The method for preparing a synergistic antibacterial antiviral deodorizing fiber according to claim 1, wherein in step (3), the aliphatic dibasic acid is one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
5. The method for preparing synergistic antibacterial antiviral deodorizing fiber according to claim 1, wherein in step (4), the esterification reaction condition is that the temperature is 235-255 ℃, the pressure is 0.3-0.4 MPa, and the time is 2-3 hours; the reaction condition of the prepolymerization is that the temperature is 260-270 ℃, the pressure is-0.09-0.10 MPa, and the time is 0.5-1.5 h; the final polymerization reaction condition is 270-280 deg.c, 20-100 Pa absolute pressure and 2-3 hr.
6. The preparation method of the synergistic antibacterial antiviral deodorizing fiber according to claim 1, wherein in the step (5), the spinneret plate is in a cross-shaped spinneret hole, the prepared antibacterial antiviral polyester fiber has a breaking strength of 2.0-3.5 cN/dtex, an elongation at break of 15-30%, an antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of more than 99%, an antiviral effect on influenza A H1N1 virus of more than 99%, a photocatalytic degradation effect on nicotine of the antibacterial antiviral fiber under simulated sunlight detected by ultra-high performance liquid chromatography (UPLC), after sunlight irradiation for 75 minutes, the antibacterial antiviral fiber has a degradation effect on nicotine of more than 99%, after the fiber is washed for 50 times, the antibacterial rate on escherichia coli and staphylococcus still has a bacterial inhibition rate of more than 97%, an antiviral effect on influenza A H1N1 virus has a bacterial inhibition effect on staphylococcus aureus of more than 97%, and after irradiation for 75 minutes, the antibacterial fiber has a good water-washing resistance, high-efficiency and smoke-eliminating performance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310353464.XA CN116446066A (en) | 2023-04-04 | 2023-04-04 | Preparation method of synergistic antibacterial antiviral deodorizing fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310353464.XA CN116446066A (en) | 2023-04-04 | 2023-04-04 | Preparation method of synergistic antibacterial antiviral deodorizing fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116446066A true CN116446066A (en) | 2023-07-18 |
Family
ID=87126474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310353464.XA Pending CN116446066A (en) | 2023-04-04 | 2023-04-04 | Preparation method of synergistic antibacterial antiviral deodorizing fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116446066A (en) |
-
2023
- 2023-04-04 CN CN202310353464.XA patent/CN116446066A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Adnan et al. | Mitigation of pollutants by chitosan/metallic oxide photocatalyst: a review | |
| Chen et al. | Strategic combination of nitrogen-doped carbon quantum dots and g-C3N4: efficient photocatalytic peroxydisulfate for the degradation of tetracycline hydrochloride and mechanism insight | |
| Yang et al. | Recent progress in preparation and application of nano‐chitin materials | |
| CN114875521B (en) | Preparation method of efficient antibacterial and antiviral fiber | |
| Yue et al. | Highly recyclable and super-tough hydrogel mediated by dual-functional TiO2 nanoparticles toward efficient photodegradation of organic water pollutants | |
| Salama et al. | Carboxymethyl cellulose prepared from mesquite tree: New source for promising nanocomposite materials | |
| Mahmoodi et al. | Metal-organic framework (ZIF-8)/inorganic nanofiber (Fe2O3) nanocomposite: Green synthesis and photocatalytic degradation using LED irradiation | |
| Ratshiedana et al. | Titanium dioxide and graphitic carbon nitride–based nanocomposites and nanofibres for the degradation of organic pollutants in water: a review | |
| CN115044073A (en) | Preparation method and application of nano-copper master batch with antibacterial and antiviral functions | |
| CN112225893B (en) | Porphyrin and hydantoin-based porous organic polymer and preparation method and application thereof | |
| CN111054417A (en) | High-efficiency iron monatomic Fenton catalyst, and synthesis method and application thereof | |
| CN112341707A (en) | Antibacterial PP plastic and preparation method thereof | |
| CN112795098A (en) | Antibacterial plastic and preparation method thereof | |
| CN114989577B (en) | Preparation method and application of antibacterial and antiviral master batch | |
| CN115058787B (en) | Preparation method of antibacterial and antiviral cool feeling fiber | |
| Emmanuel et al. | A pragmatic review on bio-polymerized metallic nano-architecture for photocatalytic degradation of recalcitrant dye pollutants | |
| Yadav et al. | Potential applications of chitosan nanocomposites: recent trends and challenges | |
| CN114875513B (en) | Preparation method of nano-copper antibacterial antiviral black fiber | |
| CN116446066A (en) | Preparation method of synergistic antibacterial antiviral deodorizing fiber | |
| Liu et al. | Self-cleaning and photodegradle PVDF separation membranes modified with self-assembled TiO2-g-CS/CNTs particle | |
| CN111995799B (en) | Preparation method of nano-silver/cellulose composite antibacterial material | |
| CN110871099A (en) | Ag-containing material3PO4And carboxylated g-C3N4Preparation method of photocatalytic degradation nano-fiber | |
| CN110229384B (en) | Silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel and preparation method thereof | |
| CN116426007A (en) | Preparation method and application of synergistic antibacterial antiviral deodorizing master batch | |
| CN109610165B (en) | Preparation method of antibacterial photocatalytic fibrilia |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |