CN114989577B - Preparation method and application of antibacterial and antiviral master batch - Google Patents
Preparation method and application of antibacterial and antiviral master batch Download PDFInfo
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- CN114989577B CN114989577B CN202210632777.4A CN202210632777A CN114989577B CN 114989577 B CN114989577 B CN 114989577B CN 202210632777 A CN202210632777 A CN 202210632777A CN 114989577 B CN114989577 B CN 114989577B
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 167
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 139
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 118
- 239000000835 fiber Substances 0.000 claims abstract description 48
- 239000002135 nanosheet Substances 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 27
- -1 polyethylene terephthalate Polymers 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000002002 slurry 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
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 17
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 15
- 229910001431 copper ion Inorganic materials 0.000 claims description 15
- 241000588724 Escherichia coli Species 0.000 claims description 14
- 241000191967 Staphylococcus aureus Species 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 12
- 238000002074 melt spinning Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 241000222122 Candida albicans Species 0.000 claims description 7
- 229940095731 candida albicans Drugs 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 7
- 239000006228 supernatant 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
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 208000037797 influenza A Diseases 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 229920001707 polybutylene terephthalate Polymers 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
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 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
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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
- 239000002904 solvent Substances 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
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims 1
- 239000002064 nanoplatelet Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000003242 anti bacterial agent Substances 0.000 description 15
- 239000003443 antiviral agent Substances 0.000 description 14
- 206010069767 H1N1 influenza Diseases 0.000 description 10
- 241000712431 Influenza A virus Species 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 10
- 201000010740 swine influenza Diseases 0.000 description 10
- 230000032050 esterification Effects 0.000 description 8
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- 238000005266 casting Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 241000700605 Viruses Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 244000052616 bacterial pathogen Species 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 206010059866 Drug resistance Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000009385 viral infection Effects 0.000 description 1
Classifications
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- 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
- C08J3/223—Packed additives
-
- 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
- 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)
- Textile Engineering (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a preparation method and application of an antibacterial and antiviral functional master batch, in particular to a preparation method and application of a functional master batch for realizing antibacterial and antiviral effects through nano copper and molybdenum disulfide. MoS is firstly carried out 2 Performing ultrasonic treatment on the powder to obtain MoS 2 Nanosheets prepared by in situ reduction in MoS 2 Generating nano simple substance copper on the surface of the nano sheet, and then generating MoS of the nano simple substance copper on the surface 2 The nano-sheet carboxylic acid is modified and then is polymerized in situ to be introduced into polyester for synthesis to obtain the master batch with antibacterial and antiviral functions. 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 master batch 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.
Description
Technical Field
The invention belongs to the field of preparation of polymer functional master batches, relates to a preparation method and application of an antibacterial and antiviral functional master batch, and in particular relates to a preparation method and application of a functional master batch for realizing antibacterial and antiviral effects through nano copper and molybdenum disulfide.
Background
Currently, the problem of bacterial viral infections has become a public health challenge, which is one of the ten leading causes of death worldwide. Various textiles contacted in our daily life are composed of porous object shapes and some other high molecular polymers. These chemical structures are beneficial for bacterial viruses to attach and multiply on, and at the same time, sebum, sweat and human body secretions can be smeared when people wear clothes and use other fiber textiles, so that nutrients are provided for bacteria and germs, and a large amount of bacteria breeding opportunities are provided. During the reproduction and transmission of pathogenic bacteria, the fiber textile generally becomes a good habitat for pathogenic bacteria, thereby becoming an important infectious source of diseases and seriously threatening human health. Therefore, the production of high-efficiency antibacterial and antiviral fibers is urgent.
The antibacterial fiber comprises organic antibacterial fiber, inorganic antibacterial fiber, etc. The organic antibacterial fiber can realize antibacterial effect by adding a trace amount of organic antibacterial agent, and has the advantages of low price and quick sterilization, but the organic antibacterial agent has the problems of poor heat resistance, easy generation of microbial drug resistance and the like. The inorganic antibacterial fiber is generally prepared by introducing metal and a compound thereof as an antibacterial agent into the fiber, so that the fiber has antibacterial property, has good antibacterial effect and washing resistance, has relatively fewer defects, and is the most widely used type of antibacterial fiber in the market at present.
The inorganic antibacterial fiber is mainly prepared from master batches prepared from inorganic antibacterial antiviral agents and different matrix materials through melt spinning to achieve the antibacterial effect. The existing antibacterial and antiviral master batch has the problems of poor chemical stability, uneven dispersion of antibacterial agent and the like, and the added inorganic antibacterial and antiviral agent mainly comprises Ag ion antibacterial and antiviral agent, znO antibacterial and antiviral agent and TiO 2 Antibacterial antiviral agents and the like, after the antibacterial antiviral agents are prepared into antibacterial master batches, the dispersibility of the antibacterial master batches in a slice matrix is poor, the spinnability of the later-stage fibers is influenced by the formed agglomerates, so that the addition amount of the antibacterial and antiviral master batches is increased, the antibacterial and antiviral effects are also influenced, in addition, ag ions are high in price and easy to overflow in the use process, serious harm is caused to human bodies, ag belongs to active metals, and oxidation-reduction reaction is easy to occur after the fibers are spun, so that the fibers are discolored; znO, tiO 2 Belongs to a photocatalysis type antibacterial antiviral agent, which can excite antibacterial and antiviral properties under illumination condition, and has limited use condition.
The nano Cu can be used as an antibacterial antiviral agent to well solve the problems, has good antibacterial and antiviral properties, does not overflow ions during antibacterial and antiviral processes, and is healthy and environment-friendly. Meanwhile, compared with nano Ag, the nano Cu-Cu composite antibacterial antiviral agent has relatively low price, can be used as an antibacterial antiviral agent, has defects on the surface of nano Cu, and has the problems of easy oxidization and easy aggregation in the use process, so that the antibacterial and antiviral effects are affected.
Molybdenum disulfide is used as a typical two-dimensional nano material, has the advantages of higher specific surface area, wide spectral effect, narrower band gap and the like, meanwhile, mo is an indispensable trace element in a plurality of enzyme molecules, S is a common composition component of protein, has good biocompatibility, and MoS 2 Harmless to human body, thus MoS 2 Can be used as a carrier of nano Cu and can be used for synergistic antibacterial with the nano Cu.
The invention provides a preparation method and application of an antibacterial and antiviral functional master batch, aiming at solving a series of problems that the current antibacterial and antiviral agent causes serious harm to human health due to metal ion overflow when exerting antibacterial and antiviral effects, the antibacterial and antiviral agent is easy to agglomerate in the master batch, the antibacterial and antiviral master batch is poor in chemical stability and the like.
Disclosure of Invention
The invention aims to provide a preparation method and application of an antibacterial and antiviral functional master batch, in particular to a preparation method and application of a functional master batch for realizing antibacterial and antiviral effects through nano copper and molybdenum disulfide. By loading nano Cu powder on MoS with uniform dispersion 2 On the nanosheets, the dispersibility of nano Cu can be improved, the antibacterial and antiviral effects can be improved, and MoS can be realized at the same time 2 The nano-sheet also has a certain antibacterial and antiviral effect, and can cooperate with antibacterial and antiviral effects to further improve the antibacterial and antiviral effects. Unlike the dissolution type antibacterial and antiviral mechanism of copper ions, elemental copper is used for catalyzing reaction antibacterial and antiviral, and the elemental copper plays an antibacterial and antiviral role by releasing active oxygen free Radicals (ROS) and does not pollute the environment during antibacterial and antiviral. The nano simple substance copper obtained by the method has the size of 2-10nm, the nano simple substance copper with the size has higher catalytic reaction antibacterial and antiviral activity, the nano copper can activate oxygen in water and air to generate ROS (hydroxyl free radicals, superoxide free radicals and hydrogen peroxide), the ROS has strong oxidizing property, the structure and the function of cells can be directly or indirectly damaged, and cell membrane rupture is caused, so that bacteria die. Cu@MoS further modified by carboxylic acid 2 Not only has better compatibility with polyester, but also has Cu@MoS modified by carboxylic acid in the in-situ polymerization of polyester monomers 2 Can be used forUniformly and stably dispersed in polyester, and nano-scale Cu@MoS is avoided 2 Agglomeration problems of (2). The 2-10 nm-sized nano copper has more exposed surface defects, and the carboxyl can be better complexed with the nano copper to maintain Cu@MoS 2 The nano copper is always in a reduced state, the active oxygen free radical is continuously released to play an antibacterial and antiviral role, and the complexed carboxyl can promote the nano copper to generate the active oxygen free radical, so that the antibacterial and antiviral role is further improved. Therefore, the master batch obtained by the invention has high-efficiency and durable antibacterial and antiviral effects, and can be spun into fibers by different matrixes, thereby meeting the higher requirements of different fields on the antibacterial and antiviral properties of the fibers. The prepared Cu@MoS is prepared by utilizing aliphatic dibasic acid 2 The carboxylic acid is modified, and the carboxyl can be combined with the exposed defect on the surface of the nano Cu, so that the stability of the nano Cu structure is facilitated, the antibacterial and antiviral aging is prolonged, the generation of peroxy free radicals is facilitated, and the antibacterial and antiviral effects are enhanced.
The invention relates to a Cu@MoS containing alloy 2 The preparation method and the application of the antibacterial and antiviral master batch solve the problem that Ag ions overflow to harm physical health, meanwhile, cu can play an antibacterial and antiviral role under the condition of no illumination, the application range is wide, and nano Cu is loaded on nano MoS 2 The dispersibility of the nano Cu can be improved, and in addition, the nano Cu and the nano MoS 2 Synergistic antibacterial and antiviral effects can be enhanced. Nanometer MoS 2 The addition of the antibacterial and antiviral master batch enables the antibacterial and antiviral master batch to have biocompatibility, and can be widely used in the field of biomedicine. The prepared Cu@MoS is prepared by using a melt spinning technology 2 The antibacterial and antiviral master batch and matrix resin are melt spun, so that the fiber yield can be improved.
According to a first aspect of the invention, the invention provides a preparation method of an antibacterial and antiviral functional master batch, which comprises the following steps:
(1) Nanometer MoS 2 Is dispersed in the solvent: 3 to 6 parts of MoS 2 Adding the powder into 50 parts of deionized water, ultrasonically oscillating for 6-10 hours, washing the reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 A nanosheet;
(2) According to the mass parts, 2-5 parts of nano-sheets are ultrasonically dispersed in 50 parts of deionized water to prepare MoS 2 And (3) dissolving 0.2-1.0 part of copper salt in 50 parts of deionized water to prepare the copper ion aqueous solution. MoS is carried out 2 Mixing the aqueous solution and the copper ion aqueous solution in a flask, condensing and refluxing after mixing, dropwise adding 50 parts of the reducing agent aqueous solution into the flask while stirring, and stirring for 3-24 hours at 60-90 ℃ to obtain a dark solution. Washing and centrifugally separating the obtained product with deionized water and absolute ethyl alcohol, and finally drying to obtain MoS with nano elemental copper generated on the surface 2 Nanometer sheet (Cu@MoS) 2 ) An antibacterial agent. The size of the generated nano elemental copper is 2-10nm;
(3) Adding 1-3 parts of aliphatic dibasic acid, 15-20 parts of Cu@MoS2 and 0.5-2 parts of ethylene glycol into 100 parts of absolute ethyl alcohol, condensing, refluxing and stirring for 0.5-5 hours to obtain MoS of which the carboxylic acid modified surface is used for generating nano elemental copper 2 Nanosheet paste (CM-Cu@MoS) 2 Slurry) and then subjecting the modified Cu@MoS 2 Placing the slurry into a centrifuge tube for centrifugation, removing sediment obtained by supernatant, washing with ethanol and water for 3-5 times, and drying to obtain MoS with carboxylic acid modified surface to generate nano elemental copper 2 Nanosheets (CM-Cu@MoS) 2 )；
(4) 10 to 20 parts of CM-Cu@MoS 2 Adding 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 the antibacterial and antiviral master batch.
In the preparation method of the master batch with the antibacterial and antiviral functions, in the step (2), molybdenum disulfide (MoS 2 ) The ultrasonic dispersion condition of the nano-sheet 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 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 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 is applied, wherein the ratio of the antibacterial and antiviral master batch to the matrix resin is 10-20% of the antibacterial and antiviral master batch;
according to the application of the antibacterial and antiviral master batch, the breaking strength of the spun fiber is 2.8-3.8 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 H1N1 influenza A virus can reach more than 99%, the antibacterial rate on escherichia coli and staphylococcus aureus can still reach more than 97% after the fiber is washed for 50 times, the antiviral effect on H1N1 influenza A virus can reach more than 97%, and the antibacterial and antiviral master batch has good water-washing resistance and efficient antibacterial and antiviral performance.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. the nano Cu is adopted as the main antibacterial antiviral agent, no ion overflows, the nano Cu is healthy and environment-friendly, and meanwhile, the price of the nano Cu is relatively low, so that the cost of the antibacterial and antiviral master batch can be reduced.
2. The invention adopts MoS 2 The nanosheets are used as carriers of antibacterial antiviral agent nano Cu, so that small-size nano Cu can be dispersed more uniformly, and MoS is achieved at the same time 2 Has antibacterial and antiviral effects, and can cooperate with nanometer Cu to resist bacteria and viruses and enhance antibacterial and antiviral effects.
3. Cu@MoS in PET antibacterial and antiviral master batch 2 The nano copper is always in a reduced state, plays an antibacterial and antiviral role by continuously releasing active oxygen free radicals, and has high-efficiency and durable antibacterial and antiviral effects.
4. The PET antibacterial and antiviral master batch plays an antibacterial and antiviral role, does not overflow ions, can play an antibacterial and antiviral role under a dark reaction condition, has a wide application range, has good biocompatibility, can be woven into fibers by different matrixes, and meets the higher requirements of different fields on the antibacterial and antiviral properties of the fibers, and particularly meets the requirements of the biomedical field.
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 high-efficiency antibacterial and antiviral master batch, specifically comprising the following steps:
(1) 3 parts of MoS 2 Adding the powder into 50 parts of deionized water, ultrasonically oscillating for 6 hours, washing the reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 A nano-sheet.
(2) 2 parts of MoS by mass 2 Adding the nano-sheets into 50 parts of deionized water, and performing ultrasonic treatment in an ultrasonic machine with the frequency of 60kHz for 20min to prepare MoS 2 An aqueous solution. 0.2 part of CuSO 4 Dissolving in 50 parts of deionized water to prepare a copper ion aqueous solution. MoS is carried out 2 The aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80℃and 50 parts of 0.1mol/L aqueous citric acid solution was added dropwise to the flask with stirring, and the mixture was stirred at 60℃for 3 hours to obtain a dark solution. Washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for 3 times respectively, and finally drying to obtain Cu@MoS 2 An antibacterial agent.
(3) 1 part of suberic acid, 15 parts of Cu@MoS 2 Adding 0.5 part of glycol into 100 parts of absolute ethyl alcohol, condensing and refluxing at 80 ℃ and stirring for 12 hours to obtain carboxylic acid modified Cu@MoS 2 Slurry (CM-Cu@MoS) 2 Slurry), and then subjecting the modified CM-Cu@MoS 2 Centrifuging the slurry in a centrifuge tube, removing the precipitate obtained by supernatant, washing with ethanol and water, centrifuging for 3 times, and drying to obtain carboxylic acid modified Cu@MoS 2 (CM-Cu@MoS 2 )。
(4) 10 parts of CM-Cu@MoS 2 Putting 80 parts of terephthalic acid and 35 parts of ethylene glycol into a polymerization reaction kettle, carrying out esterification and polycondensation reaction, controlling the pressure and the temperature of the reaction kettle to be 0.30MPa and 235 ℃ respectively, and carrying out esterification reaction 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 granulating to obtain Cu@MoS 2 Antibacterial and antiviral master batch.
(5) The prepared Cu@MoS 2 Drying antibacterial and antiviral master batch and polyethylene terephthalate at 110deg.C for 24 hr, and drying Cu@MoS 2 Antibacterial and antiviral master batch according to 10% of polyethylene terephthalate is added, and the mixture is added into a melt spinning machine for spinning after being uniformly mixed, so that the antibacterial and antiviral fiber is obtained.
Cu@MoS prepared by the method 2 The antibacterial and antiviral master batch and polyethylene terephthalate are spun to obtain the antibacterial and antiviral fiber, the breaking strength is 3.8cN/dtex, the breaking elongation is 15%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.1%, the antiviral effect on H1N1 influenza A virus reaches 99.2%, the antibacterial rate on escherichia coli and staphylococcus aureus still reaches more than 97% after the fiber is washed for 50 times, the antiviral effect on H1N1 influenza A virus reaches 98.2%, and the antibacterial and antiviral fiber has good washing resistance and efficient antibacterial and antiviral performance.
Example 2, a preparation method and application of a high-efficiency antibacterial and antiviral master batch, specifically comprises the following steps:
(1) 6 parts of MoS 2 Adding the powder into 50 parts of deionized water, ultrasonically oscillating for 10 hours, washing the reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 A nano-sheet.
(2) 5 parts by mass of MoS 2 Adding the nano-sheets into 50 parts of deionized water, and performing ultrasonic treatment in an ultrasonic machine with the frequency of 30kHz for 60min to prepare MoS 2 An aqueous solution. 1 part of CuSO 4 Dissolving in 50 parts of deionized water to prepare a copper ion aqueous solution. MoS is carried out 2 The aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80℃and 50 parts of 0.5mol/L aqueous citric acid solution was added dropwise to the flask with stirring, and the mixture was stirred at 90℃for 24 hours to obtain a dark solution. Washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for 3 times respectively, and finally drying to obtain Cu@MoS 2 An antibacterial agent.
(3) 3 parts of suberic acid, 20 parts of Cu@MoS 2 Adding 2 parts of glycol into 100 parts of absolute ethyl alcohol, condensing and refluxing at 80 ℃ and stirring for 5 hours to obtain carboxylic acid modified Cu@MoS 2 Slurry (CM-Cu@MoS) 2 Slurry), and then subjecting the modified CM-Cu@MoS 2 Centrifuging the slurry in a centrifuge tube, and removing the supernatant to obtain precipitateWashing with ethanol and water, centrifuging for 3 times, and drying to obtain carboxylic acid modified Cu@MoS 2 (CM-Cu@MoS 2 )。
(4) 20 parts of CM-Cu@MoS 2 Putting 80 parts of terephthalic acid and 45 parts of ethylene glycol into a polymerization reaction kettle, carrying out esterification and polycondensation reaction, controlling the pressure and the temperature of the reaction kettle to be 0.430MPa 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; raising the vacuum degree to 100Pa, controlling the temperature to 280 ℃, carrying out final polymerization for 3h, and finally carrying out belt casting and granulating to obtain Cu@MoS 2 Antibacterial and antiviral master batch.
(5) The prepared Cu@MoS 2 Drying antibacterial and antiviral master batch and polyethylene terephthalate at 110deg.C for 24 hr, and drying Cu@MoS 2 The antibacterial and antiviral master batch is added with the polytrimethylene terephthalate according to the proportion of 20 percent, and is added into a melt spinning machine for spinning after being uniformly mixed to obtain the antibacterial and antiviral fiber.
Cu@MoS prepared by the method 2 The antibacterial and antiviral master batch and polyethylene terephthalate are spun to obtain the antibacterial and antiviral fiber, the breaking strength is 2.8cN/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 H1N1 influenza A virus reaches 99.9%, the antibacterial rate on escherichia coli and staphylococcus aureus still reaches more than 98% after the fiber is washed for 50 times, the antiviral effect on H1N1 influenza A virus reaches 99.3%, and the antibacterial and antiviral fiber has good washing resistance and efficient antibacterial and antiviral performance.
Embodiment 3, a preparation method and application of a high-efficiency antibacterial and antiviral master batch, specifically comprising the following steps:
(1) 4 parts of MoS 2 Adding the powder into 50 parts of deionized water, ultrasonically oscillating for 8 hours, washing the reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 A nano-sheet.
(2) 3 parts of MoS by mass 2 Adding the nano-sheet into 50 parts of deionized water, and performing ultrasonic treatment in an ultrasonic machine with the frequency of 40kHz for 40min to obtain the nano-sheetMoS 2 An aqueous solution. An aqueous copper ion solution was prepared by dissolving 0.5 part of copper chloride in 50 parts of deionized water. MoS is carried out 2 The aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80℃and 50 parts of 0.3mol/L aqueous citric acid solution was added dropwise to the flask with stirring, and the mixture was stirred at 90℃for 12 hours to obtain a dark solution. Washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for 3 times respectively, and finally drying to obtain Cu@MoS 2 An antibacterial agent.
(3) 2 parts of suberic acid, 15 parts of Cu@MoS 2 Adding 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@MoS 2 Slurry (CM-Cu@MoS) 2 Slurry), and then subjecting the modified CM-Cu@MoS 2 Centrifuging the slurry in a centrifuge tube, removing the precipitate obtained by supernatant, washing with ethanol and water, centrifuging for 3 times, and drying to obtain carboxylic acid modified Cu@MoS 2 (CM-Cu@MoS 2 )。
(4) 15 parts of CM-Cu@MoS 2 Putting 80 parts of terephthalic acid and 40 parts of ethylene glycol into a polymerization reaction kettle, carrying out esterification and polycondensation, controlling the pressure and the temperature of the reaction kettle to be 0.35MPa and 245 ℃ respectively, and carrying out esterification 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 1.5 hours; raising the vacuum degree to 60Pa, controlling the temperature to 278 ℃, carrying out final polymerization for 2.5h, and finally carrying out belt casting and granulating to obtain Cu@MoS 2 Antibacterial and antiviral master batch.
(5) The prepared Cu@MoS 2 Drying antibacterial and antiviral master batch and polyethylene terephthalate at 110deg.C for 24 hr, and drying Cu@MoS 2 The antibacterial and antiviral master batch is added with polybutylene terephthalate according to the proportion of 15 percent, and is added into a melt spinning machine for spinning after being uniformly mixed to obtain the antibacterial and antiviral fiber.
Cu@MoS prepared by the method 2 The antibacterial and antiviral master batch and polyethylene terephthalate are spun to obtain the antibacterial and antiviral fiber with the breaking strength of 3.3cN/dtex and the breaking elongation of 23 percent, and the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.6 percent and the influenza A H1N1 diseaseThe antiviral effect of the virus reaches 99.7%, the antibacterial rate of the fiber to escherichia coli and staphylococcus aureus still reaches more than 97% after the fiber is washed for 50 times, the antiviral effect to influenza A H1N1 virus reaches 98.3%, and the fiber has better water-washing resistance and efficient antibacterial and antiviral properties.
Example 4, a preparation method and application of high-efficiency antibacterial and antiviral master batch, specifically comprises the following steps:
(1) 5 parts of MoS 2 Adding the powder into 50 parts of deionized water, ultrasonically oscillating for 9 hours, washing the reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 A nano-sheet.
(2) Based on the mass parts, 4 parts of MoS 2 Adding the nano-sheets into 50 parts of deionized water, and performing ultrasonic treatment in an ultrasonic machine with the frequency of 30kHz for 50min to obtain MoS 2 An aqueous solution. 0.7 part of CuSO 4 Dissolving in 50 parts of deionized water to prepare a copper ion aqueous solution. MoS is carried out 2 The aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80℃and 50 parts of 0.4mol/L aqueous citric acid solution was added dropwise to the flask with stirring, and the mixture was stirred at 80℃for 12 hours to obtain a dark solution. Washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for 3 times respectively, and finally drying to obtain Cu@MoS 2 An antibacterial agent.
(3) 3 parts of dodecanedioic acid and 15 parts of Cu@MoS 2 Adding 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@MoS 2 Slurry (CM-Cu@MoS) 2 Slurry), and then subjecting the modified CM-Cu@MoS 2 Centrifuging the slurry in a centrifuge tube, removing the precipitate obtained by supernatant, washing with ethanol and water, centrifuging for 3 times, and drying to obtain carboxylic acid modified Cu@MoS 2 (CM-Cu@MoS 2 )。
(4) 10 parts of CM-Cu@MoS 2 Putting 80 parts of terephthalic acid and 45 parts of ethylene glycol into a polymerization reaction kettle, carrying out esterification and polycondensation, controlling the pressure and the temperature of the reaction kettle to be 0.40MPa and 245 ℃ respectively, and carrying out esterification for 2 hours; then a vacuum pump is started to perform pre-polycondensation, the pressure and the temperature of the reaction kettle are respectively-0.09 MPa and 270 ℃,prepolymerizing for 0.5h; the vacuum was increased to 60Pa, the temperature was controlled at 279℃and the final polymerization was carried out for 2h. Finally, carrying out belt casting and granulating to obtain Cu@MoS 2 Antibacterial and antiviral master batch.
(5) The prepared Cu@MoS 2 Drying antibacterial and antiviral master batch and polyethylene terephthalate at 110deg.C for 24 hr, and drying Cu@MoS 2 The antibacterial and antiviral master batch is added with polyethylene terephthalate according to the proportion of 20 percent, and is added into a melt spinning machine for spinning after being uniformly mixed to obtain the antibacterial and antiviral fiber.
Cu@MoS prepared by the method 2 The antibacterial and antiviral master batch and polyethylene terephthalate are spun to obtain the antibacterial and antiviral fiber, the breaking strength is 3.3cN/dtex, the breaking elongation is 24%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.8%, the antiviral effect on H1N1 influenza A virus reaches 99.5%, the antibacterial rate on escherichia coli and staphylococcus aureus still reaches more than 97% after the fiber is washed for 50 times, the antiviral effect on H1N1 influenza A virus reaches 98.6%, and the antibacterial and antiviral fiber has good washing resistance and efficient antibacterial and antiviral performance.
Example 5, a preparation method and application of high-efficiency antibacterial and antiviral master batch, specifically comprises the following steps:
(1) 3 parts of MoS 2 Adding the powder into 50 parts of deionized water, ultrasonically oscillating for 6 hours, washing the reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 A nano-sheet.
(2) Based on the mass parts, 4 parts of MoS 2 Adding the nano-sheets into 50 parts of deionized water, and performing ultrasonic treatment in an ultrasonic machine with the frequency of 50kHz for 30min to obtain MoS 2 An aqueous solution. 0.6 part of CuSO 4 Dissolving in 50 parts of deionized water to prepare a copper ion aqueous solution. MoS is carried out 2 The aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80℃and 50 parts of 0.3mol/L aqueous solution of ascorbic acid were added dropwise to the flask with stirring, and stirred at 80℃for 20 hours to obtain a dark solution. Washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for 3 times respectively, and finally drying to obtain Cu@MoS 2 An antibacterial agent.
(3) 3 parts of suberic acid, 15 parts of Cu@MoS 2 Adding 1 part of glycol into 100 parts of absolute ethyl alcohol, condensing and refluxing at 80 ℃ and stirring for 2 hours to obtain carboxylic acid modified Cu@MoS 2 Slurry (CM-Cu@MoS) 2 Slurry), and then subjecting the modified CM-Cu@MoS 2 Centrifuging the slurry in a centrifuge tube, removing the precipitate obtained by supernatant, washing with ethanol and water, centrifuging for 3 times, and drying to obtain carboxylic acid modified Cu@MoS 2 (CM-Cu@MoS 2 )。
(4) 20 parts of CM-Cu@MoS 2 Putting 80 parts of terephthalic acid and 40 parts of ethylene glycol into a polymerization reaction kettle, carrying out esterification and polycondensation, controlling the pressure and the temperature of the reaction kettle to be 0.36MPa and 245 ℃ respectively, and carrying out esterification 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-0.09 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 granulating to obtain Cu@MoS 2 Antibacterial and antiviral master batch.
(5) The prepared Cu@MoS 2 Drying antibacterial and antiviral master batch and polyethylene terephthalate at 110deg.C for 24 hr, and drying Cu@MoS 2 The antibacterial and antiviral master batch is added with polyethylene terephthalate according to the proportion of 10 percent, and is added into a melt spinning machine for spinning after being uniformly mixed to obtain the antibacterial and antiviral fiber.
Cu@MoS prepared by the method 2 The 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 20%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.7%, the antiviral effect on H1N1 influenza A virus reaches 99.5%, the antibacterial rate on escherichia coli and staphylococcus aureus still reaches more than 97% after the fiber is washed for 50 times, the antiviral effect on H1N1 influenza A virus reaches 98.2%, and the antibacterial and antiviral fiber has good washing resistance and efficient antibacterial and antiviral performance.
Claims (6)
1. A preparation method of an antibacterial and antiviral master batch is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Nanometer MoS 2 Is dispersed in the solvent: 3-6 parts of MoS 2 Adding the powder into 50 parts of deionized water, ultrasonically oscillating for 6-10 hours, washing the reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 A nanosheet;
(2) 2-5 parts of MoS by mass 2 The nano-sheet is dispersed in 50 parts of deionized water by ultrasonic to prepare MoS 2 Dissolving 0.2-1.0 part of copper salt in 50 parts of deionized water to prepare copper ion aqueous solution; moS is carried out 2 Mixing the aqueous solution and the copper ion aqueous solution in a flask, condensing and refluxing after mixing, dropwise adding 50 parts of reducing agent aqueous solution into the flask while stirring, and stirring for 3-24 hours at 60-90 ℃ to obtain a dark solution; washing and centrifugally separating the obtained product with deionized water and absolute ethyl alcohol, and finally drying to obtain MoS with nano elemental copper generated on the surface 2 A nanoplatelet antimicrobial agent;
(3) MoS with 1-3 parts of aliphatic dibasic acid and 15-20 parts of surface-generated nano elemental copper 2 Adding 100 parts of absolute ethyl alcohol into 0.5-2 parts of ethylene glycol and performing condensation reflux and stirring for 0.5-5 hours to obtain MoS of carboxylic acid modified surface-generated nano elemental copper 2 Nanosheet slurry, and then generating MoS of nano elemental copper on the modified surface 2 Centrifuging the nanosheet slurry in a centrifuge tube, removing a precipitate obtained by supernatant, washing with ethanol and water for 3-5 times, and drying to obtain the MoS with carboxylic acid modified surface and nano elemental copper 2 A nanosheet;
(4) MoS for generating nano elemental copper on 10-20 parts of carboxylic acid modified surface 2 Adding the nanosheets, 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 antibacterial and antiviral master batches;
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 to-0.10 MPa, and the time is 0.5-1.5 h; 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;
the size of the nano elemental copper is 2-10nm.
2. The method for preparing an antibacterial and antiviral master batch according to claim 1, wherein in the step (2), moS is 2 The ultrasonic dispersion condition of the nanosheets 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 aqueous solution of citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride.
3. The method for preparing an antibacterial and antiviral 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.
4. An application of an antibacterial and antiviral 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 3 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.
5. The use of an antibacterial and antiviral functional masterbatch according to claim 4 wherein said 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.
6. The application of the antibacterial and antiviral master batch according to claim 4, wherein the antibacterial and antiviral fiber breaking strength is 2.8-3.8 cN/dtex, the elongation at break is 15-30%, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can be over 99%, the antiviral effect on influenza A H1N1 virus can be over 99%, the antibacterial rate on escherichia coli and staphylococcus aureus can still be over 97% after the fiber is washed for 50 times, and the antiviral effect on influenza A H1N1 virus can be over 97%.
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| WO2017092236A1 (en) * | 2015-12-01 | 2017-06-08 | 东华大学 | Method for using in situ polymerization to prepare antibacterial material based on copper oxide/cuprous oxide |
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| CN105332088A (en) * | 2015-12-01 | 2016-02-17 | 东华大学 | Method for preparing copper-filled antibacterial fibers |
| WO2017092236A1 (en) * | 2015-12-01 | 2017-06-08 | 东华大学 | Method for using in situ polymerization to prepare antibacterial material based on copper oxide/cuprous oxide |
| CN112323173A (en) * | 2020-11-04 | 2021-02-05 | 宁波三邦超细纤维有限公司 | Organic copper antibacterial polyester fiber and preparation method thereof |
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