CN116426007A - Preparation method and application of synergistic antibacterial antiviral deodorizing master batch - Google Patents
Preparation method and application of synergistic antibacterial antiviral deodorizing master batch Download PDFInfo
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- CN116426007A CN116426007A CN202310353465.4A CN202310353465A CN116426007A CN 116426007 A CN116426007 A CN 116426007A CN 202310353465 A CN202310353465 A CN 202310353465A CN 116426007 A CN116426007 A CN 116426007A
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- Prior art keywords
- antibacterial
- antiviral
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- acid
- master batch
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 152
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 142
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 55
- 230000001877 deodorizing effect Effects 0.000 title claims abstract description 38
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 57
- 229920000728 polyester Polymers 0.000 claims abstract description 30
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000004744 fabric Substances 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 29
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 claims description 26
- 229960002715 nicotine Drugs 0.000 claims description 26
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 claims description 26
- 239000003242 anti bacterial agent Substances 0.000 claims description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 24
- 230000000694 effects Effects 0.000 claims description 24
- -1 polyethylene terephthalate Polymers 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 19
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 14
- 229910001431 copper ion Inorganic materials 0.000 claims description 14
- 235000019441 ethanol Nutrition 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
- 241000588724 Escherichia coli Species 0.000 claims description 13
- 241000191967 Staphylococcus aureus Species 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 13
- 238000006731 degradation reaction Methods 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 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
- 238000002156 mixing Methods 0.000 claims description 9
- 241000700605 Viruses Species 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-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
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000002074 melt spinning Methods 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- 238000010992 reflux 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
- 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 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-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
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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
- 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
- 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
- 229920001707 polybutylene terephthalate Polymers 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
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 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 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
- 229960000583 acetic acid Drugs 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
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 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
- 206010022000 influenza Diseases 0.000 claims 2
- 239000000779 smoke Substances 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 230000000051 modifying effect Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000002045 lasting effect Effects 0.000 abstract 1
- 208000037797 influenza A Diseases 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003443 antiviral agent Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003642 reactive oxygen metabolite Substances 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 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
- 241000894006 Bacteria Species 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 244000052616 bacterial pathogen Species 0.000 description 3
- 229950000244 sulfanilic acid Drugs 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance 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
- 206010011409 Cross infection Diseases 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000006185 dispersion Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a preparation method and application of synergistic antibacterial antiviral deodorizing function master batch, which comprises the steps of firstly preparing nanoscale nitrogen-doped carbon quantum dots by using o-phenylenediamine and acid through a one-step hydrothermal method, then coordinating on the surfaces of the nitrogen-doped carbon quantum dots through an in-situ reduction method to generate nano elemental copper, modifying by carboxylic acid, and introducing polyester through in-situ polymerization to obtain the antibacterial antiviral function master batch. The antibacterial and antiviral functional master batch can be melt-spun with matrix resin according to a certain proportion to obtain antibacterial and antiviral fibers. The antibacterial and antiviral functional master batch prepared by the invention can not cause harm to the environment in the use process, and the antibacterial and antiviral fiber prepared by the antibacterial and antiviral functional master batch has the characteristics of high efficiency, lasting antibacterial and antiviral effects and capability of eliminating smoke odor of fabrics.
Description
Technical Field
The invention relates to the field of preparation of polymer functional master batches, relates to a preparation method and application of a synergistic antibacterial antiviral deodorizing functional master batch, and in particular relates to a preparation method and application of a functional master batch for realizing antibacterial and antiviral effects and eliminating smoke odor effects of fabrics by synergism of nano copper and nitrogen doped carbon quantum dots.
Background
The harm caused by the breeding and cross infection of pathogenic bacteria and viruses to human health is difficult to measure. The textile is a main carrier of pathogenic bacteria and viruses, and the antibacterial and antiviral functions of the textile are also gaining more and more importance to society. In addition, nicotine smoke odor generated by the burning of cigarettes in life is easily adsorbed on the surface of the fiber fabric, and the wearing experience of the fabric is affected. The demand of the textile with the antibacterial, antiviral and deodorizing composite functions is increased year by year, and the prior art can not meet the urgent demands of the fiber with the antibacterial, antiviral and deodorizing composite functions and the textile. Therefore, the development of the antibacterial, antiviral and deodorizing composite functional fiber has important significance.
The polyester material mainly comprises polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate (PBT), has good fiber forming performance, mechanical performance, corrosion resistance, light transmittance, electrical insulation and the like, and is widely used in the fiber field such as textiles, films, industrial yarns and the like. If the antibacterial antiviral and deodorizing capabilities of the polyester fiber are endowed, the application market of the polyester fiber can be widened, and the requirements of people on the antibacterial antiviral and deodorizing composite functional fiber can be met.
The polyester fiber has no antibacterial, antiviral and deodorizing capability, and antibacterial, antiviral and modifying is realized mainly by adding antibacterial and antiviral agents. Silver-containing or copper-containing antibacterial antiviral agents are often combined with fibers to prepare antibacterial and antiviral fibers in recent years, but silver-based antibacterial antiviral agents are expensive and easy to degrade by heating, and the use of nano silver antibacterial antiviral agents on textiles is limited abroad. The copper-based antibacterial antiviral agent is economical, practical, wide in bactericidal spectrum, strong in compatibility, not easy to cause the pathogenic bacteria to generate drug resistance, good in durability and is an antibacterial antiviral agent which is more studied at present. The nano copper belongs to a non-leaching antibacterial antiviral agent, can directly react with water and oxygen in air, and is converted into Reactive Oxygen Species (ROS) to kill bacterial and viruses, and the antibacterial and antiviral effects can be achieved without specific conditions. However, the nano Cu has defects on the surface, is easy to oxidize and agglomerate in the use process, and affects the antibacterial and antiviral effects.
The nitrogen doped carbon quantum dots (N-CQDs) are taken as novel fluorescent carbon nano particles, and have excellent optical characteristics and good biocompatibility. N-CQDs are photocatalytic antibacterial and antiviral agents that are required to function under ultraviolet light conditions. Under the excitation of sunlight, the compound type deodorizing agent not only can generate ROS, resist bacteria and viruses, but also can play a deodorizing role by combining with nicotine in smoke odor. But N-CQDs are also easy to agglomerate, which affects the antibacterial, antiviral and deodorizing effects.
Disclosure of Invention
The invention aims to provide a preparation method and application of an antibacterial, antiviral and deodorizing composite functional master batch, which realizes antibacterial, antiviral and deodorizing effects by the synergistic effect of nano copper and nitrogen doped carbon quantum dots, and improves the durability of antibacterial, antiviral and deodorizing effects.
According to a first aspect of the invention, the invention provides a preparation method of an antibacterial, antiviral and deodorizing functional master batch with a composite function, which adopts the following technical scheme:
o-phenylenediamine and acid are prepared into 3-5nm nitrogen-doped carbon quantum dots (N-CQDs) by a one-step hydrothermal method, then nano elemental copper Cu-N-CQDs are generated on the surfaces of the nitrogen-doped carbon quantum dots by an in-situ reduction method, and the Cu-N-CQDs are modified by carboxylic acid to obtain CM-Cu-N-CQDs which have better compatibility with polyester, can be uniformly and stably dispersed in polyester melt in-situ polymerization of polyester monomers, and can enhance the antibacterial, antiviral and deodorizing durability of the polyester melt.
The size of the nitrogen doped carbon quantum dots (N-CQDs) obtained by the invention is 3-5nm, and the nitrogen doped carbon quantum dots have extremely high antibacterial, antiviral and deodorizing activity of catalytic reaction. Under the photocatalysis condition, the N-CQDs can activate water and oxygen in the air to generate ROS, can directly or indirectly destroy cell structures, play a role in resisting bacteria and viruses, and can generate pi-pi conjugation effect with electron pushing groups C=N or C=O on the surface of the N-CQDs and electron pushing groups C=N on the surface of nicotine to generate fluorescence resonance energy transfer. The fluorescence quenching of the donor N-CQDs and the fluorescence enhancement of the acceptor nicotine can be realized, and after the fluorescence quenching, the N-CQDs can use more energy for degrading nicotine, so that the effect of eliminating smoke odor can be realized. The nano-copper simple substance obtained by the invention has the size of 2-10nm and extremely high antibacterial and antiviral activity of catalytic reaction. Generating nano simple substance copper (Cu-N-CQDs) with the size of 2-10nm on the surface of the N-CQDs by an in-situ reduction method, and then modifying Cu-N-CQDs carboxylic acid to obtain CM-Cu-N-CQDs. The carboxyl can be better complexed with nano-copper to maintain the nano-copper of Cu-N-CQDs in a reduced state all the time, and the sustained release of Reactive Oxygen Species (ROS) plays a role in resisting bacteria and viruses, and the compatibility of the modified carboxyl with polyester polymerization can be improved by modifying the modified carboxyl, so that the antibacterial, antiviral and deodorizing durability of the modified carboxyl is enhanced.
The Cu-N-CQDs obtained through carboxylic acid modification have good compatibility with polyester, can be uniformly and stably dispersed in polyester melt in-situ polymerization of polyester monomers, solves the problem of uneven dispersion of antibacterial, antiviral and deodorant agents in polyester, and solves the defect that N-CQDs can play antibacterial, antiviral and deodorant roles only by sunlight excitation without lighting conditions. The antibacterial and antiviral fiber has synergistic antibacterial, antiviral and deodorizing effects, and further widens the application field of antibacterial, antiviral and deodorizing fiber.
Further, the preparation method of the synergistic antibacterial antiviral deodorizing master batch provided by the invention comprises the following steps of:
(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 washed and centrifugally separated by deionized water and absolute ethanol, and finally, nitrogen-doped carbon quantum dots (N-CQDs) are obtained by drying;
(2) Ultrasonically dispersing 3-10 parts of N-CQDs in 50 parts of deionized water to prepare an N-CQDs aqueous solution, and dissolving 3-4 parts of copper salt 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, adding 50 parts of reducer aqueous solution dropwise into the flask while stirring, and stirring for 3-20 h at 60-90 ℃ to obtain a dark solution; washing and 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 loaded on the surface;
(3) Adding 3-5 parts of aliphatic dibasic acid, 5-10 parts of deionized water and 100-200 parts of Cu-N-CQDs antibacterial agent into 100 parts of ethylene glycol at 80-90 ℃ and stirring for 0.5-5 h to obtain carboxylic acid modified Cu-N-CQDs polyester slurry;
(4) 10-20 parts of carboxylic acid modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid and 35-45 parts of ethylene glycol are added into a polymerization reaction kettle, esterification is carried out, then prepolymerization and final polymerization are carried out, and finally, antibacterial and antiviral master batch is obtained through tape casting and particle cutting.
In the step (1), the condition of ultrasonic dispersion of the o-phenylenediamine and the acid means that the time is 20-60 min, 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 ultrasonic dispersion condition of the N-CQDs 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, suberic 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.
According to a second aspect of the invention, the invention provides an application of the nano-copper antibacterial and antiviral master batch, which adopts the following technical scheme:
and drying the prepared antibacterial and antiviral master batch and matrix resin for a period of time at 90-120 ℃, then blending the antibacterial and antiviral master batch and the matrix resin according to a certain proportion, and adding the mixture into a melt spinning machine for spinning after the mixture is uniformly mixed to obtain the antibacterial and antiviral fiber.
The matrix resin is one of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate.
The antibacterial and antiviral master batch and the matrix resin are in a proportion of 10-20% of the matrix resin.
According to the application of the synergistic antibacterial antiviral deodorizing master batch, the breaking strength of the spun fiber is 2.2-3.5 cN/dtex, the breaking elongation is 15-30%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach more than 99%, the antiviral effect on influenza A H1N1 virus can reach 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 reach more than 99% after 75 minutes of sunlight irradiation, the antibacterial rate on escherichia coli and staphylococcus aureus still reaches more than 97% after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus reaches more than 97% after 75 minutes of sunlight irradiation, and the antibacterial antiviral master batch has good water-washing resistance, high-efficiency antibacterial antiviral and fabric smoke deodorizing performance.
By adopting the technical scheme of the invention, the invention can obtain the following beneficial effects:
1. the nano Cu is adopted as a main antibacterial antiviral agent, so that no ions overflow and no harm to the environment are caused;
2. the N-CQDs loaded nano Cu antibacterial agent adopted by the invention has good dispersibility and compatibility in polyester, and has small influence on the spinning performance and the fiber mechanical property of the polyester;
3. the nano copper in the antibacterial and antiviral master batch is always in a reduced state, and plays an antibacterial and antiviral role by continuously releasing active oxygen free radicals, so that the antibacterial and antiviral master batch has high-efficiency and durable antibacterial and antiviral effects;
4. the N-CQDs in the antibacterial and antiviral master batch plays a role in degrading nicotine by continuously releasing active oxygen free radicals, and has an efficient and durable effect of eliminating smoke odor of fabrics.
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.
Embodiment 1, a preparation method and application of a synergistic antibacterial antiviral deodorizing master batch, specifically comprising 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 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) 5 parts of N-CQDs were added to 50 parts of deionized water, and the mixture was sonicated in an ultrasonic machine at a frequency of 60kHz for 20 minutes to prepare an aqueous solution of N-CQDs. 3 parts of copper sulfate was dissolved in 50 parts of deionized water to prepare an aqueous copper ion solution. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80℃to obtain a dark solution by adding 50 parts of 0.1mol/L aqueous citric acid solution dropwise to the flask with stirring, and stirring at 60℃for 3 hours. Washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol respectively, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper loaded on the surface;
(3) Adding 3 parts of suberic acid, 100 parts of Cu-N-CQDs antibacterial agent and 5 parts of deionized water into 100 parts of ethylene glycol at 80 ℃ and stirring for 0.5h to obtain carboxylic acid modified Cu-N-CQDs polyester slurry;
(4) 10 parts of carboxylic acid modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid and 35 parts of ethylene glycol are put into a polymerization reaction kettle for esterification, the pressure and the temperature of the reaction kettle are controlled to be 0.30MPa and 235 ℃ respectively, and the esterification reaction is carried out for 2 hours; 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 Cu-N-CQDs antibacterial and antiviral master batches;
(5) And (3) drying the prepared Cu-N-CQDs antibacterial and antiviral master batch and polyethylene terephthalate at 100 ℃ for 24 hours, adding the Cu-N-CQDs antibacterial and antiviral master batch into the polyethylene terephthalate according to the proportion of 10%, uniformly mixing, and adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
The Cu-N-CQDs antibacterial and antiviral master batch and polyethylene terephthalate are spun to obtain the antibacterial and antiviral fiber, the breaking strength is 3.2cN/dtex, the breaking elongation is 15%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.5%, the antiviral effect on influenza A H1N1 virus reaches 99.3%, 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% after 75 minutes of sunlight irradiation, the antibacterial rate on escherichia coli and staphylococcus aureus still reaches more than 98% after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus reaches 97.7%, the degradation effect on nicotine reaches more than 97.6% after 75 minutes of irradiation, and the antibacterial and antiviral fiber has better water washing performance, high-efficient antibacterial and antiviral performance and fabric smoke-eliminating performance.
Example 2, a preparation method and application of a synergistic antibacterial antiviral deodorizing master batch, 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, 4 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 5h 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) 6 parts of N-CQDs were added to 50 parts of deionized water, and the mixture was sonicated in an ultrasonic machine at a frequency of 30kHz for 60 minutes to prepare an aqueous solution of N-CQDs. 3 parts of copper nitrate was dissolved in 50 parts of deionized water to prepare an aqueous copper ion solution. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80℃to obtain a dark solution by adding 50 parts of 0.5mol/L aqueous citric acid solution dropwise to the flask with stirring, and stirring at 90℃for 5 hours. Washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol respectively, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper loaded on the surface;
(3) 3.5 parts of suberic acid, 150 parts of Cu-N-CQDs antibacterial agent and 10 parts of deionized water are added into 100 parts of ethylene glycol at 90 ℃ and stirred for 5 hours to obtain carboxylic acid modified Cu-N-CQDs polyester slurry;
(4) 15 parts of carboxylic acid modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid and 45 parts of ethylene glycol are put into a polymerization reaction kettle for esterification, the pressure and the temperature of the reaction kettle are controlled to be 0.430MPa and 255 ℃ respectively, and the esterification reaction is carried out 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 Cu-N-CQDs antibacterial and antiviral master batches;
(5) And drying the prepared Cu-N-CQDs antibacterial and antiviral master batch and polyethylene terephthalate at 100 ℃ for 18 hours, adding the Cu-N-CQDs antibacterial and antiviral master batch into the polyethylene terephthalate according to the proportion of 15%, uniformly mixing, and adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
The Cu-N-CQDs antibacterial and antiviral master batch and polyethylene terephthalate are spun to obtain the antibacterial and antiviral fiber, the breaking strength is 3.4cN/dtex, the breaking elongation is 20%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.9%, the antiviral effect on influenza A H1N1 virus reaches 99.9%, 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 99.8% after 75 minutes of sunlight irradiation, the antibacterial rate on escherichia coli and staphylococcus aureus still reaches more than 98% after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus reaches 99.3%, the degradation effect on nicotine reaches more than 98.1% after 75 minutes of irradiation, and the antibacterial and antiviral fiber has better water washing performance, high-efficient antibacterial and antiviral performance and fabric smoke odor-eliminating performance.
Example 3, a preparation method and application of a synergistic antibacterial antiviral deodorizing master batch, 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) 7 parts of N-CQDs were added to 50 parts of deionized water, and the mixture was sonicated in an ultrasonic machine at a frequency of 40kHz for 40 minutes to prepare an aqueous solution of N-CQDs. 3 parts of copper chloride was dissolved in 50 parts of deionized water to prepare an aqueous copper ion solution. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80℃to obtain a dark solution by adding 50 parts of 0.3mol/L aqueous citric acid solution dropwise to the flask with stirring, and stirring at 90℃for 10 hours. Washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol respectively, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper loaded on the surface;
(3) Adding 4.5 parts of dodecanedioic acid, 120 parts of Cu-N-CQDs antibacterial agent and 10 parts of deionized water into 100 parts of ethylene glycol at 80 ℃, and stirring for 2 hours to obtain carboxylic acid modified Cu-N-CQDs polyester slurry;
(4) 15 parts of carboxylic acid modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid and 35 parts of ethylene glycol are put into a polymerization reaction kettle for esterification, the pressure and the temperature of the reaction kettle are controlled to be 0.37MPa and 235 ℃ respectively, and the esterification is carried out 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 Cu-N-CQDs antibacterial and antiviral master batches;
(5) And (3) drying the prepared Cu-N-CQDs antibacterial and antiviral master batch and polyethylene terephthalate at 100 ℃ for 24 hours, adding the Cu-N-CQDs antibacterial and antiviral master batch into the polyethylene terephthalate according to the proportion of 15%, uniformly mixing, and adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
The Cu-N-CQDs antibacterial and antiviral master batch and polyethylene terephthalate are spun to obtain the antibacterial and antiviral fiber, the breaking strength is 3.5cN/dtex, the breaking elongation is 15%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.5%, the antiviral effect on influenza A H1N1 virus reaches 99.3%, 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% after 75 minutes of sunlight irradiation, the antibacterial rate on escherichia coli and staphylococcus aureus still reaches more than 97% after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus reaches 97.7%, the degradation effect on nicotine reaches more than 97.3% after 75 minutes of irradiation, and the antibacterial and antiviral fiber has better water washing performance, high-efficient antibacterial and antiviral performance and fabric smoke odor-eliminating performance.
Example 4, a preparation method and application of a synergistic antibacterial antiviral deodorizing master batch, specifically comprises the following 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) 8 parts of N-CQDs were added to 50 parts of deionized water, and the mixture was sonicated in an ultrasonic machine at a frequency of 30kHz for 50 minutes to prepare an aqueous solution of N-CQDs. 4 parts of copper sulfate was dissolved in 50 parts of deionized water to prepare an aqueous copper ion solution. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80℃to obtain a dark solution by adding 50 parts of 0.4mol/L aqueous citric acid solution dropwise to the flask with stirring, and stirring at 80℃for 6 hours. Washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol respectively, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper loaded on the surface;
(3) Adding 1.5 parts of sebacic acid, 180 parts of Cu-N-CQDs antibacterial agent and 10 parts of deionized water into 100 parts of ethylene glycol at 85 ℃, and stirring for 5 hours to obtain carboxylic acid modified Cu-N-CQDs polyester slurry;
(4) 15 parts of carboxylic acid modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid and 40 parts of ethylene glycol are put into a polymerization reaction kettle for esterification, the pressure and the temperature of the reaction kettle are controlled to be 0.42MPa and 235 ℃ respectively, and the esterification is carried out for 2 hours; 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 270 ℃ at the moment, and the pre-polymerization is performed for 1.5 hours; the vacuum was increased to 75Pa, the temperature was controlled at 279℃and the final polymerization was carried out for 2h. Finally, carrying out belt casting and grain cutting to obtain Cu-N-CQDs antibacterial and antiviral master batches;
(5) And (3) drying the prepared Cu-N-CQDs antibacterial and antiviral master batch and polyethylene terephthalate at 100 ℃ for 24 hours, adding the Cu-N-CQDs antibacterial and antiviral master batch into the polyethylene terephthalate according to the proportion of 20%, uniformly mixing, and adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
The Cu-N-CQDs antibacterial and antiviral master batch and polyethylene terephthalate are spun to obtain the antibacterial and antiviral fiber, the breaking strength is 2.2cN/dtex, the breaking elongation is 24%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.9%, the antiviral effect on influenza A H1N1 virus reaches 99.9%, 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 99.3% after 75 minutes of sunlight irradiation, the antibacterial rate on escherichia coli and staphylococcus aureus still reaches more than 99% after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus reaches 99.6%, the degradation effect on nicotine reaches more than 97.6% after 75 minutes of irradiation, and the antibacterial and antiviral fiber has better water washing performance, high-efficient antibacterial and antiviral performance and fabric smoke-eliminating performance.
Example 5, a preparation method and application of a synergistic antibacterial antiviral deodorizing master batch, 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 30min at 50kHz to prepare an o-phenylenediamine solution, 10 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) 9 parts of N-CQDs were added to 50 parts of deionized water, and the mixture was sonicated in an ultrasonic machine at a frequency of 50kHz for 30 minutes to prepare an aqueous solution of N-CQDs. 4 parts of copper sulfate was dissolved in 50 parts of deionized water to prepare an aqueous copper ion solution. The N-CQDs aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80℃to obtain a dark solution by adding 50 parts of 0.3mol/L aqueous solution of ascorbic acid dropwise to the flask with stirring, and stirring at 70℃for 5 hours. Washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol respectively, and finally drying to obtain the N-CQDs antibacterial agent (Cu-N-CQDs antibacterial agent) with nano elemental copper loaded on the surface;
(3) Adding 3.5 parts of adipic acid, 160 parts of Cu-N-CQDs antibacterial agent and 6 parts of deionized water into 100 parts of 90 ℃ glycol, and stirring for 3 hours to obtain carboxylic acid modified Cu-N-CQDs polyester slurry;
(4) Adding 20 parts of carboxylic acid modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid and 45 parts of ethylene glycol into a polymerization reaction kettle, and carrying out esterification reaction for 3 hours under the conditions that the pressure and the temperature of the reaction kettle are respectively 0.36MPa and 245 ℃; 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 265 ℃ at the moment, and the pre-polymerization is performed for 0.5h; the vacuum degree is increased to 80Pa, 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 Cu-N-CQDs antibacterial and antiviral master batches;
(5) And (3) drying the prepared Cu-N-CQDs antibacterial and antiviral master batch and polyethylene terephthalate at 100 ℃ for 24 hours, adding 13% of the Cu-N-CQDs antibacterial and antiviral master batch into the polyethylene terephthalate, uniformly mixing, and adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
The Cu-N-CQDs antibacterial and antiviral master batch and polyethylene terephthalate are spun to obtain the antibacterial and antiviral fiber, the breaking strength is 3.1cN/dtex, the breaking elongation is 20%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.7%, the antiviral effect on influenza A H1N1 virus reaches 99.3%, 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% after 75 minutes of sunlight irradiation, the antibacterial rate on escherichia coli and staphylococcus aureus still reaches more than 98% after 50 times of fiber washing, the antiviral effect on influenza A H1N1 virus reaches 98.2%, the degradation effect on nicotine reaches more than 97.8% after 75 minutes of irradiation, and the antibacterial and antiviral fiber has better water washing performance, high-efficient antibacterial and antiviral performance and fabric smoke odor-eliminating performance.
Claims (8)
1. A preparation method of a synergistic antibacterial antiviral deodorizing master batch is characterized by comprising the following steps: the method 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 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 washed and centrifugally separated by deionized water and absolute ethanol, and finally, nitrogen-doped carbon quantum dots (N-CQDs) are obtained by drying;
(2) Ultrasonically dispersing 3-10 parts of N-CQDs in 50 parts of deionized water to prepare an N-CQDs aqueous solution, and dissolving 3-4 parts of copper salt 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, adding 50 parts of reducer aqueous solution dropwise into the flask while stirring, and stirring for 3-20 h at 60-90 ℃ to obtain a dark solution; washing and 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 3-5 parts of aliphatic dibasic acid, 5-10 parts of deionized water and 100-200 parts of Cu-N-CQDs antibacterial agent into 100 parts of ethylene glycol at 80-90 ℃ and stirring for 0.5-5 h to obtain carboxylic acid modified Cu-N-CQDs polyester slurry;
(4) 10-20 parts of carboxylic acid modified Cu-N-CQDs polyester slurry, 80 parts of terephthalic acid and 35-45 parts of ethylene glycol are added into a polymerization reaction kettle, esterification is carried out, then prepolymerization and final polymerization are carried out, and finally, antibacterial and antiviral master batch is obtained through tape casting and particle cutting.
2. The method for preparing the synergistic antibacterial antiviral deodorizing master batch 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 refers to one of benzenesulfonic acid, folic acid, boric acid, acetic acid, terephthalic acid and tartaric acid.
3. The method for preparing the synergistic antibacterial antiviral deodorizing functional master batch according to claim 1, wherein in the step (2), the condition of ultrasonic dispersion of nitrogen-doped carbon quantum dots means that the time is 20-60 min and the ultrasonic frequency is 30-60 kHz; 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 preparation method and application of the synergistic antibacterial antiviral deodorizing functional master batch according to claim 1, wherein in the step (3), the aliphatic dibasic acid is one of adipic acid, suberic acid, sebacic acid and dodecanedioic acid.
5. The method for preparing the synergistic antibacterial antiviral deodorizing functional master batch according to claim 1, wherein 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; 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. An application of a synergistic antibacterial antiviral deodorizing master batch is characterized in that: drying the antibacterial and antiviral master batch and matrix resin prepared by the preparation method of any one of claims 1 to 4 at 90-120 ℃ for a period of time, uniformly mixing the antibacterial and antiviral master batch and matrix resin according to a proportion, and then adding the mixture into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
7. The use of a synergistic antibacterial antiviral deodorizing functional masterbatch according to claim 6, characterized in that the matrix resin is one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate; the proportion of the antibacterial and antiviral master batch to the matrix resin is 10-20% of the antibacterial and antiviral master batch.
8. The application of the synergistic antibacterial antiviral deodorizing functional master batch according to claim 6, wherein the breaking strength of the antibacterial antiviral fiber is 2.2-3.5 cN/dtex, the breaking elongation is 15-30%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach more than 99%, the antiviral effect on influenza A1N 1 virus can reach 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 reach more than 99% after 75 minutes of sunlight irradiation, the antibacterial rate of the fiber after 50 times of washing can still reach more than 97%, the antiviral effect on influenza A1N 1 virus can reach more than 97%, the degradation effect on nicotine after 75 minutes of sunlight irradiation can reach more than 97%, and the antibacterial antiviral fiber has better water-washing performance, high-efficient antibacterial antiviral performance and smoke-eliminating fabric performance.
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