CN114989577A - 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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- CN114989577A CN114989577A CN202210632777.4A CN202210632777A CN114989577A CN 114989577 A CN114989577 A CN 114989577A CN 202210632777 A CN202210632777 A CN 202210632777A CN 114989577 A CN114989577 A CN 114989577A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 173
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 145
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 49
- 239000000835 fiber Substances 0.000 claims abstract description 47
- 239000002135 nanosheet Substances 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 238000002074 melt spinning Methods 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 37
- 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 28
- 238000005406 washing Methods 0.000 claims description 27
- -1 polyethylene terephthalate Polymers 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 20
- 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 17
- 238000002156 mixing 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
- 206010069767 H1N1 influenza Diseases 0.000 claims description 14
- 241000712431 Influenza A virus 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
- 201000010740 swine influenza Diseases 0.000 claims description 14
- 238000005886 esterification reaction Methods 0.000 claims description 13
- 238000009987 spinning Methods 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
- 239000002244 precipitate Substances 0.000 claims description 9
- 230000006870 function Effects 0.000 claims description 8
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- 229940095731 candida albicans Drugs 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
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- 235000019441 ethanol Nutrition 0.000 claims description 7
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- 239000000047 product Substances 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
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 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
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000000203 mixture Substances 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
- 229960005070 ascorbic acid Drugs 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
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic 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
- 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
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract description 121
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 47
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000006378 damage Effects 0.000 abstract description 4
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- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000003242 anti bacterial agent Substances 0.000 description 16
- 239000003443 antiviral agent Substances 0.000 description 13
- 238000009833 condensation Methods 0.000 description 10
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- 238000006068 polycondensation reaction Methods 0.000 description 10
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- 230000032050 esterification Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 241000700605 Viruses Species 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000003642 reactive oxygen metabolite Substances 0.000 description 4
- 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
- 239000004753 textile Substances 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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- 239000011787 zinc oxide Substances 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
- C08J3/223—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)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (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 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. Firstly, MoS is carried out 2 Powder ultrasonic treatment to obtain MoS 2 Nanosheets in MoS by in situ reduction 2 Nano generation on the surface of nano sheetElemental copper, and then generating MoS of nano elemental copper on the surface 2 After the nano-sheet carboxylic acid is modified, polyester is introduced for synthesis through in-situ polymerization to obtain the antibacterial and antiviral master batch. The antibacterial and antiviral master batch and matrix resin can be subjected to melt spinning according to a certain proportion to obtain the antibacterial and antiviral fiber. The antibacterial and antiviral master batch prepared by the invention does not cause harm to the environment in the using process and has the characteristics of high efficiency and lasting antibacterial and antiviral property.
Description
Technical Field
The invention belongs to the field of preparation of high-molecular functional master batches, relates to a preparation method and application of an antibacterial and antiviral functional master batch, and particularly 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 and viral infection has become a public health challenge, which is one of ten causes of death worldwide. The various textiles we contact in our daily life are composed of porous shapes and some other high molecular polymers. The chemical structures are beneficial to the attachment and propagation of bacteria and viruses, and meanwhile, sebum, sweat and human body secretion can be stained when people wear clothes and use other fiber textiles, so that nutrient substances are provided for bacteria and germs, and the opportunity for the breeding of a large amount of bacteria is provided. During the propagation and transmission of pathogenic bacteria, the fiber textile often becomes a good habitat of the pathogenic bacteria, thereby becoming an important infection source of diseases and seriously threatening human health. Therefore, the production of high-efficiency antibacterial and antiviral fiber is imminent.
The antibacterial fiber includes organic antibacterial fiber, inorganic antibacterial fiber, etc. The organic antibacterial fiber can realize antibiosis by adding a trace amount of organic antibacterial agent, has low price and quick sterilization, but has the problems of poor heat resistance, easy generation of microbial drug resistance and the like. The inorganic antibacterial fiber is generally introduced into the fiber by taking metal and compounds thereof as antibacterial agents, so that the inorganic antibacterial fiber has antibacterial property, good antibacterial effect, washing resistance and relatively few defects, and is the most widely used antibacterial fiber in the market at present.
The inorganic antibacterial fiber is prepared by melt spinning master batch prepared from inorganic antibacterial antiviral agent and different matrix materials to achieve the antibacterial effect. The existing antibacterial and antiviral master batch has the problems of poor chemical stability, nonuniform dispersion of antibacterial agent and the like, and the added inorganic antibacterial and antiviral agents mainly comprise Ag ion antibacterial and antiviral agents, ZnO antibacterial and antiviral agents and TiO ions 2 Antibacterial and antiviral agents, and the like, after the antibacterial and antiviral agents are prepared into antibacterial master batches, the antibacterial master batches are usually poor in dispersibility in a slice matrix, and formed aggregates influence the spinnability of later-stage fibers, so that the antibacterial and antiviral master batchesThe addition of the particles is increased, the antibacterial and antiviral effects are also influenced, in addition, Ag ions are expensive and easily overflow in the using process, so that the Ag ions cause serious harm to human bodies, and Ag belongs to an active metal, so that the Ag ions are easily subjected to redox reaction after being spun into fibers to change the color of the fibers; ZnO, TiO 2 Belongs to a photocatalytic antibacterial antiviral agent, can excite the antibacterial antiviral property of the compound under the condition of illumination, and has limited use conditions.
The nano Cu can well solve the problems as an antibacterial antiviral agent, has good antibacterial and antiviral properties, does not have ion overflow during antibacterial and antiviral processes, and is healthy and environment-friendly. Meanwhile, compared with nano Ag, the nano Cu antibacterial antiviral material has relatively low price and can be used as an antibacterial antiviral agent, but the surface of the nano Cu has defects, and the nano Cu antibacterial antiviral material has the problems of easy oxidation and easy agglomeration in the using process, so that the antibacterial antiviral effect is influenced.
Molybdenum disulfide as a typical two-dimensional nano material has the advantages of high specific surface area, wide spectrum effect, narrow band gap and the like, Mo is an indispensable trace element in a plurality of enzyme molecules, S is a common constituent of protein, and has good biocompatibility, and MoS 2 Is harmless to human body, therefore MoS 2 Can be used as a carrier of the nano Cu and is antibacterial with the nano Cu.
The invention provides a preparation method and application of an antibacterial and antiviral master batch, aiming at solving a series of problems that the current antibacterial and antiviral agent causes serious harm to human health due to overflow of metal ions when playing an antibacterial and antiviral role, the antibacterial and antiviral agent is easy to agglomerate in the master batch, the chemical stability of the antibacterial and antiviral master batch is poor, and the like.
Disclosure of Invention
The invention aims to provide a preparation method and application of an antibacterial and antiviral functional master batch, and particularly relates 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 in uniformly dispersed MoS 2 On the nano sheet, the dispersibility of nano Cu can be improvedHigh antibacterial and antiviral effects, and MoS 2 The nano-sheets also have certain antibacterial and antiviral effects, and can be used for synergistically resisting bacteria and viruses to further improve the antibacterial and antiviral effects. Different from the dissolution type antibacterial and antiviral mechanism of copper ions, the elemental copper is used for catalyzing reaction and has antibacterial and antiviral effects, and the elemental copper can release Reactive Oxygen Species (ROS) to play an antibacterial and antiviral role and cannot pollute the environment during antibacterial and antiviral processes. The size of the nano elemental copper obtained by the invention is 2-10nm, the nano elemental copper 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), and the ROS (hydroxyl free radicals, superoxide free radicals and hydrogen peroxide) has strong oxidizability and can directly or indirectly damage the structure and function of cells, so that cell membranes are broken to cause bacterial death. Cu @ MoS further modified by carboxylic acid 2 Not only has better compatibility with polyester, but also is carboxylic acid modified Cu @ MoS in-situ polymerization of polyester monomer 2 Can be uniformly and stably dispersed in polyester, and avoids nanoscale Cu @ MoS 2 The problem of agglomeration. The nano copper with the size of 2-10nm has more exposed surface defects, and carboxyl can be better complexed with the nano copper to maintain Cu @ MoS 2 The nano copper is always in a reduction state, active oxygen free radicals are continuously released to play a role in resisting bacteria and viruses, and the complexed carboxyl can promote the nano copper to generate the active oxygen free radicals, so that the antibacterial and antiviral effects are further improved. Therefore, the master batch obtained by the invention has high-efficiency and durable antibacterial and antiviral effects, and the antibacterial and antiviral master batch can be spun into fibers by using different matrixes, so that the higher requirements of different fields on the antibacterial and antiviral performance of the fibers are met. Prepared Cu @ MoS by using aliphatic dibasic acid 2 The carboxylic acid is modified, the carboxyl can be combined with the exposed defects on the surface of the nano Cu, the stability of the nano Cu structure is facilitated, the antibacterial and antiviral aging is prolonged, the generation of peroxy radicals is facilitated, and the antibacterial and antiviral effects are enhanced.
The invention relates to a Cu @ MoS-containing material 2 The preparation method and the application of the antibacterial and antiviral master batch solve the problem that the overflow of Ag ions harms the health of a human body, simultaneously Cu can play the antibacterial and antiviral role under the condition of no light,wide application range, and the nano Cu is loaded on the nano MoS 2 In addition, the nano Cu and the nano MoS can improve the dispersity of the nano Cu 2 Has synergistic antibacterial and antiviral effects. Nano MoS 2 The antibacterial and antiviral master batch has biocompatibility due to the addition of the (D) and can be widely used in the field of biomedicine. The prepared Cu @ MoS is prepared by a melt spinning technology 2 The antibacterial and antiviral master batch and the matrix resin are subjected to melt spinning, so that the yield of the fiber can be improved.
According to a first aspect of the present invention, the present invention provides a method for preparing an antibacterial and antiviral functional master batch, comprising the following steps:
(1) nano MoS 2 Dispersion of (2): 3-6 parts of MoS 2 Adding the powder into 50 parts of deionized water, carrying out ultrasonic oscillation for 6-10 h, washing a reaction product with the deionized water for three times, centrifugally collecting, and drying for 24h to obtain MoS 2 Nanosheets;
(2) ultrasonically dispersing 2-5 parts of nanosheet in 50 parts of deionized water by mass to prepare MoS 2 And (3) dissolving 0.2-1.0 part of copper salt in 50 parts of deionized water to prepare a copper ion aqueous solution. Mixing MoS 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 by using deionized water and absolute ethyl alcohol, and finally drying to obtain MoS with the surface generating nano elemental copper 2 Nanosheet (Cu @ MoS) 2 ) An antibacterial agent. The size of the generated nano simple substance copper is 2-10 nm;
(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 h to obtain MoS with carboxylic acid modified surface generating nano elemental copper 2 Nanosheet slurry (CM-Cu @ MoS) 2 Slurry) and then modifying the Cu @ MoS 2 Centrifuging the slurry in a centrifuge tube, removing supernatant to obtain precipitate, washing the precipitate with ethanol and water for 3-5 times, and drying to obtain carboxylic acid modified MoS with nano elemental copper generated on the surface 2 Nanosheet (CM-Cu @ MoS) 2 )；
(4) Adding 10-20 parts of CM-Cu @ MoS 2 80 parts of terephthalic acid and 35-45 parts of ethylene glycol are added into a polymerization reaction kettle, esterification is carried out firstly, then prepolymerization and final polymerization are carried out, and finally, the antibacterial and antiviral master batch is obtained through belt casting and grain cutting.
The preparation method of the antibacterial and antiviral master batch comprises the step (2) of preparing molybdenum disulfide (MoS) 2 ) The ultrasonic dispersion condition of the nano-sheets is that the time is 20-60 min, and the ultrasonic frequency is 30-60 kHz;
in the above method for preparing the antibacterial and antiviral master batch, in the step (2), the copper salt is one of copper chloride, copper sulfate and copper nitrate;
in the preparation method of the antibacterial and antiviral master batch, in the step (2), the reducing agent aqueous solution is one of 0.1-0.5 mol/L citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride aqueous solution;
in the preparation method of the antibacterial and antiviral master batch, in the step (3), the aliphatic dibasic acid is one of adipic acid, suberic acid, sebacic acid and dodecanedioic acid;
according to the preparation method of the antibacterial and antiviral master batch, in the step (4), the esterification reaction conditions are that the temperature is 235-255 ℃, the pressure is 0.3-0.4 MPa, and the time is 2-3 h;
in the preparation method of the antibacterial and antiviral master batch, in the step (4), the reaction conditions of prepolymerization are that the temperature is 260-270 ℃, the pressure is-0.09-0.10 MPa, and the time is 0.5-1.5 h;
according to the preparation method of the antibacterial and antiviral master batch, in the step (4), the final polymerization reaction conditions are that the temperature is 270-280 ℃, the pressure is 20-100 Pa absolute, and the time is 2-3 h;
according to a second aspect of the present invention, the present invention provides an application of the antibacterial and antiviral master batch, which adopts the following technical scheme:
drying the prepared antibacterial and antiviral master batch and matrix resin at 90-120 ℃ for a period of time, blending the two according to a certain proportion, uniformly mixing, and adding the mixture into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
The application of the antibacterial and antiviral master batch is characterized in that the matrix resin is one of polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate;
according to the application of the antibacterial and antiviral functional master batch, the antibacterial and antiviral master batch accounts for 10-20% of the matrix resin in proportion to the matrix resin;
according to the application of the antibacterial and antiviral functional master batch, the spun fiber has the breaking strength of 2.8-3.8 cN/dtex, the elongation at break of 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 functional master batch has good water washing resistance and high-efficiency antibacterial and antiviral performance.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. the invention adopts the nano Cu as the main antibacterial antiviral agent, has no ion overflow, is healthy and environment-friendly, has relatively low price of the Cu, and can reduce the cost of the antibacterial antiviral master batch.
2. The invention adopts MoS 2 The nano-sheet is used as a carrier of the antibacterial antiviral agent nano-Cu, so that the small-size nano-Cu can be dispersed more uniformly, and the MoS 2 Has certain antibacterial and antiviral effects, and can cooperate with nano Cu to enhance antibacterial and antiviral effects.
3. Cu @ MoS in PET antibacterial and antiviral master batch 2 The nano copper is always in a reduction state, plays a role in resisting bacteria and viruses by continuously releasing active oxygen free radicals, and has high-efficiency and lasting antibacterial and antiviral effects.
4. The PET antibacterial and antiviral master batch provided by the invention has the advantages that no ions overflow when the antibacterial and antiviral action is exerted, the antibacterial and antiviral action can be exerted under the dark reaction condition, the application range is wide, simultaneously, the used carrier has good biocompatibility, the antibacterial and antiviral master batch can be woven into fibers by using different matrixes, and the higher requirements of different fields on the antibacterial and antiviral properties of the fibers, particularly the requirements of the biomedical field, are met.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Embodiment 1, a preparation method and application of a master batch with high-efficiency antibacterial and antiviral functions, comprising the following specific steps:
(1) 3 parts of MoS 2 Adding the powder into 50 parts of deionized water, carrying out ultrasonic oscillation for 6 hours, washing a reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 Nanosheets.
(2) According to the mass part, 2 parts of MoS 2 Adding the nanosheets into 50 parts of deionized water, and carrying out 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 Dissolved in 50 parts of deionized water to prepare an aqueous solution of copper ions. Mixing MoS 2 The aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80 ℃, 50 parts of 0.1mol/L citric acid aqueous solution was added dropwise to the flask while stirring, and stirred at 60 ℃ for 3 hours to obtain a dark solution. Washing and centrifuging the obtained product for 3 times by using deionized water and absolute ethyl alcohol 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, carrying out condensation reflux at the temperature of 80 ℃, and stirring for 12 hours to obtain carboxylic acid modified Cu @ MoS 2 Slurry (CM-Cu @ MoS) 2 Slurry material) Then the modified CM-Cu @ MoS 2 Centrifuging the slurry in a centrifuge tube, removing supernatant to obtain precipitate, washing with ethanol and water, centrifuging for 3 times, and drying to obtain carboxylic acid modified Cu @ MoS 2 (CM-Cu@MoS 2 )。
(4) Adding 10 parts of CM-Cu @ MoS 2 80 parts of terephthalic acid and 35 parts of ethylene glycol are put into a polymerization reaction kettle, esterification and polycondensation are carried out, the pressure and the temperature of the reaction kettle are respectively controlled to be 0.30MPa and 235 ℃, and the esterification reaction is carried out for 2 hours; then starting a vacuum pump to carry out pre-polycondensation, wherein the pressure and the temperature of the reaction kettle are-0.09 MPa and 260 ℃ respectively, and the pre-polymerization reaction lasts for 0.5 h; the vacuum degree is increased to 20Pa, the temperature is controlled at 270 ℃, and the final polymerization reaction is carried out for 2 h. Finally, casting belt and granulating to obtain Cu @ MoS 2 An antibacterial and antiviral master batch.
(5) The prepared Cu @ MoS 2 Drying the antibacterial and antiviral master batch and polyethylene terephthalate at 110 ℃ for 24h, and then adding Cu @ MoS 2 Adding the antibacterial and antiviral master batch into polyethylene terephthalate according to the proportion of 10 percent, uniformly mixing, and then adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
Cu @ MoS prepared by the invention 2 The antibacterial and antiviral fiber obtained by spinning the antibacterial and antiviral master batch and polyethylene terephthalate has the breaking strength of 3.8cN/dtex, the elongation at break of 15 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.1 percent, the antiviral effect on H1N1 influenza A virus of 99.2 percent, the antibacterial rate on escherichia coli and staphylococcus aureus of more than 97 percent after the fiber is washed for 50 times, the antiviral effect on H1N1 influenza A virus of 98.2 percent, and the antibacterial and antiviral fiber has better water washing resistance and high-efficiency antibacterial and antiviral performance.
Embodiment 2, a preparation method and application of a master batch with high-efficiency antibacterial and antiviral functions, comprising the following specific steps:
(1) 6 parts of MoS 2 Adding the powder into 50 parts of deionized water, carrying out ultrasonic oscillation 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 Nanosheets.
(2) According to the mass part, 5 parts of MoS 2 Adding the nanosheets into 50 parts of deionized water, and carrying out 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 Dissolved in 50 parts of deionized water to prepare an aqueous solution of copper ions. Mixing MoS 2 The aqueous solution and the aqueous solution of copper ions were mixed in a flask, and then subjected to condensation reflux at 80 ℃, 50 parts of 0.5mol/L aqueous solution of citric acid was added dropwise to the flask while stirring, and stirred at 90 ℃ for 24 hours to obtain a dark solution. Washing the obtained product with deionized water and absolute ethyl alcohol respectively, centrifuging for 3 times, 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, carrying out condensation reflux at 80 ℃, and stirring for 5 hours to obtain carboxylic acid modified Cu @ MoS 2 Slurry (CM-Cu @ MoS) 2 Slurry) and then modifying the CM-Cu @ MoS 2 Centrifuging the slurry in a centrifuge tube, removing supernatant to obtain precipitate, 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 80 parts of terephthalic acid and 45 parts of ethylene glycol are put into a polymerization reaction kettle, esterification and polycondensation are carried out, the pressure and the temperature of the reaction kettle are respectively controlled to be 0.430MPa and 255 ℃, and the esterification reaction is carried out for 3 hours; then starting a vacuum pump to carry out pre-polycondensation, wherein the pressure and the temperature of the reaction kettle are-0.10 MPa and 270 ℃ respectively, and the pre-polymerization reaction lasts for 1.5 h; raising the vacuum degree to 100Pa, controlling the temperature at 280 ℃, performing final polymerization reaction for 3h, and finally performing casting belt and grain cutting to obtain Cu @ MoS 2 An antibacterial and antiviral master batch.
(5) The prepared Cu @ MoS 2 Drying the antibacterial and antiviral master batch and polyethylene terephthalate at 110 ℃ for 24h, and then adding Cu @ MoS 2 The antibacterial and antiviral master batch is added with the polytrimethylene terephthalate according to the proportion of 20 percent, and the antibacterial and antiviral master batch 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 invention 2 The breaking strength of the antibacterial and antiviral fiber obtained by spinning the antibacterial and antiviral master batch and the polyethylene terephthalate is 2.8cN/dtex, the elongation at break is 20 percent,the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans can reach 99.9%, the antiviral effect on H1N1 influenza A virus can reach 99.9%, the antibacterial rate on escherichia coli and staphylococcus aureus can still reach more than 98% after fibers are washed for 50 times, the antiviral effect on H1N1 influenza A virus can reach 99.3%, and the antibacterial and antiviral fiber has good water washing resistance and high-efficiency antibacterial and antiviral performance.
Embodiment 3, a preparation method and application of a master batch with efficient antibacterial and antiviral functions, specifically comprising the following steps:
(1) 4 parts of MoS 2 Adding the powder into 50 parts of deionized water, carrying out ultrasonic oscillation for 8 hours, washing a reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 Nanosheets.
(2) According to the mass part, 3 parts of MoS 2 Adding the nanosheets into 50 parts of deionized water, and carrying out ultrasonic treatment in an ultrasonic machine with the frequency of 40kHz for 40min to prepare MoS 2 An aqueous solution. 0.5 part of copper chloride was dissolved in 50 parts of deionized water to prepare an aqueous copper ion solution. Mixing MoS 2 The aqueous solution and the copper ion aqueous solution were mixed in a flask, and then subjected to condensation reflux at 80 ℃, 50 parts of 0.3mol/L citric acid aqueous solution was dropwise added to the flask while stirring, and stirred at 90 ℃ for 12 hours to obtain a dark solution. Washing and centrifuging the obtained product for 3 times by using deionized water and absolute ethyl alcohol 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 glycol into 100 parts of absolute ethyl alcohol, carrying out condensation reflux at the temperature of 80 ℃, and stirring for 2 hours to obtain carboxylic acid modified Cu @ MoS 2 Slurry (CM-Cu @ MoS) 2 Slurry) and then modifying the CM-Cu @ MoS 2 Centrifuging the slurry in a centrifuge tube, removing supernatant to obtain precipitate, 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 80 parts of terephthalic acid and 40 parts of ethylene glycol are put into a polymerization reaction kettle, esterification and polycondensation are carried out, the pressure and the temperature of the reaction kettle are respectively controlled to be 0.35MPa and 245 ℃, and the esterification reaction lasts for 3 hours; however, the device is not limited to the specific type of the deviceThen starting a vacuum pump to carry out pre-polycondensation, wherein the pressure and the temperature of the reaction kettle are-0.10 MPa and 265 ℃, and the pre-polymerization reaction lasts for 1.5 h; raising the vacuum degree to 60Pa, controlling the temperature at 278 ℃, performing final polymerization reaction for 2.5h, and finally performing belt casting and grain cutting to obtain Cu @ MoS 2 An antibacterial and antiviral master batch.
(5) The prepared Cu @ MoS 2 Drying the antibacterial and antiviral master batch and polyethylene terephthalate at 110 ℃ for 24h, and then adding Cu @ MoS 2 The antibacterial and antiviral master batch is added with polybutylene terephthalate according to the proportion of 15 percent, and the mixture is evenly mixed and then added into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
Cu @ MoS prepared by the invention 2 The antibacterial and antiviral fiber obtained by spinning the antibacterial and antiviral master batch and polyethylene terephthalate has the breaking strength of 3.3cN/dtex, the elongation at break of 23 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.6 percent, the antiviral effect on H1N1 influenza A virus of 99.7 percent, the antibacterial rate on escherichia coli and staphylococcus aureus of more than 97 percent after the fiber is washed for 50 times, the antiviral effect on H1N1 influenza A virus of 98.3 percent, and the antibacterial and antiviral fiber has better water washing resistance and high-efficiency antibacterial and antiviral performance.
Embodiment 4, a preparation method and application of a master batch with high-efficiency antibacterial and antiviral functions, comprising the following specific steps:
(1) 5 parts of MoS 2 Adding the powder into 50 parts of deionized water, carrying out ultrasonic oscillation for 9 hours, washing a reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 Nanosheets.
(2) According to the mass part, 4 parts of MoS 2 Adding the nanosheets into 50 parts of deionized water, and carrying out ultrasonic treatment for 50min in an ultrasonic machine with the frequency of 30kHz to prepare MoS 2 An aqueous solution. 0.7 part of CuSO 4 Dissolved in 50 parts of deionized water to prepare an aqueous solution of copper ions. Mixing MoS 2 The aqueous solution and the aqueous solution of copper ions were mixed in a flask, and then subjected to condensation reflux at 80 ℃, 50 parts of 0.4mol/L aqueous solution of citric acid was added dropwise to the flask while stirring, and stirred at 80 ℃ for 12 hours to obtain a dark solution. Obtained byWashing and centrifuging the product for 3 times by using deionized water and absolute ethyl alcohol 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 glycol into 100 parts of absolute ethyl alcohol, performing condensation reflux at 80 ℃, and stirring for 2 hours to obtain carboxylic acid modified Cu @ MoS 2 Slurry (CM-Cu @ MoS) 2 Slurry) and then modifying the CM-Cu @ MoS 2 Centrifuging the slurry in a centrifuge tube, removing supernatant to obtain precipitate, washing with ethanol and water, centrifuging for 3 times, and drying to obtain carboxylic acid modified Cu @ MoS 2 (CM-Cu@MoS 2 )。
(4) Adding 10 parts of CM-Cu @ MoS 2 80 parts of terephthalic acid and 45 parts of ethylene glycol are put into a polymerization reaction kettle, esterification and polycondensation are carried out, the pressure and the temperature of the reaction kettle are respectively controlled to be 0.40MPa and 245 ℃, and the esterification reaction lasts for 2 hours; then starting a vacuum pump to carry out pre-polycondensation, wherein the pressure and the temperature of the reaction kettle are-0.09 MPa and 270 ℃ respectively, and the pre-polymerization reaction lasts for 0.5 h; the vacuum degree is increased to 60Pa, the temperature is controlled at 279 ℃, and the final polymerization reaction is carried out for 2 h. Finally, casting belt and granulating to obtain Cu @ MoS 2 An antibacterial and antiviral master batch.
(5) The prepared Cu @ MoS 2 Drying the antibacterial and antiviral master batch and polyethylene terephthalate at 110 ℃ for 24h, and then adding Cu @ MoS 2 Adding the antibacterial and antiviral master batch into polyethylene terephthalate according to the proportion of 20 percent, uniformly mixing, and then adding into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
Cu @ MoS prepared by the invention 2 The antibacterial and antiviral fiber obtained by spinning the antibacterial and antiviral master batch and polyethylene terephthalate has the breaking strength of 3.3cN/dtex, the elongation at break of 24 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.8 percent, the antiviral effect on H1N1 influenza A virus of 99.5 percent, the antibacterial rate on escherichia coli and staphylococcus aureus of more than 97 percent after the fiber is washed for 50 times, the antiviral effect on H1N1 influenza A virus of 98.6 percent, and the antibacterial and antiviral fiber has better water washing resistance and high-efficiency antibacterial and antiviral performance.
Embodiment 5, a preparation method and application of a master batch with high-efficiency antibacterial and antiviral functions, comprising the following specific steps:
(1) 3 parts of MoS 2 Adding the powder into 50 parts of deionized water, carrying out ultrasonic oscillation for 6 hours, washing a reaction product with the deionized water for three times, centrifugally collecting, and drying for 24 hours to obtain MoS 2 Nanosheets.
(2) According to the mass part, 4 parts of MoS 2 Adding the nanosheets into 50 parts of deionized water, and carrying out ultrasonic treatment in an ultrasonic machine with the frequency of 50kHz for 30min to prepare MoS 2 An aqueous solution. 0.6 part of CuSO 4 Dissolved in 50 parts of deionized water to prepare an aqueous solution of copper ions. Mixing MoS 2 The aqueous solution and the copper ion aqueous solution are mixed in a flask, then condensation reflux is carried out at the temperature of 80 ℃, 50 parts of 0.3mol/L ascorbic acid aqueous solution is dropwise added into the flask while stirring, and stirring is carried out at the temperature of 80 ℃ for 20 hours to obtain a dark solution. Washing and centrifuging the obtained product for 3 times by using deionized water and absolute ethyl alcohol 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, carrying out condensation reflux at 80 ℃, and stirring for 2 hours to obtain carboxylic acid modified Cu @ MoS 2 Slurry (CM-Cu @ MoS) 2 Slurry) and then modifying the CM-Cu @ MoS 2 Centrifuging the slurry in a centrifuge tube, removing supernatant to obtain precipitate, 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 80 parts of terephthalic acid and 40 parts of ethylene glycol are put into a polymerization reaction kettle, esterification and polycondensation are carried out, the pressure and the temperature of the reaction kettle are respectively controlled to be 0.36MPa and 245 ℃, and esterification reaction is carried out for 3 hours; then starting a vacuum pump to carry out pre-polycondensation, wherein the pressure and the temperature of the reaction kettle are-0.09 MPa and 265 ℃, and the pre-polymerization reaction is carried out for 0.5 h; raising the vacuum degree to 80Pa, controlling the temperature at 280 ℃ and carrying out final polymerization reaction for 3 h. Finally, casting belt and granulating to obtain Cu @ MoS 2 An antibacterial and antiviral master batch.
(5) The prepared Cu @ MoS 2 Drying the antibacterial and antiviral master batch and polyethylene terephthalate at 110 ℃ for 24h, and then adding Cu @ MoS 2 Antibacterial and antiviralThe master batch is added with polyethylene terephthalate according to the proportion of 10 percent, and the mixture 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 invention 2 The antibacterial and antiviral fiber obtained by spinning the antibacterial and antiviral master batch and polyethylene terephthalate has the breaking strength of 3.5cN/dtex, the elongation at break of 20 percent, the antibacterial effect on staphylococcus aureus, escherichia coli and candida albicans of 99.7 percent, the antiviral effect on H1N1 influenza A virus of 99.5 percent, the antibacterial rate on escherichia coli and staphylococcus aureus of more than 97 percent after the fiber is washed for 50 times, the antiviral effect on H1N1 influenza A virus of 98.2 percent, and the antibacterial and antiviral fiber has better water washing resistance and high-efficiency antibacterial and antiviral performance.
Claims (7)
1. A preparation method of antibacterial and antiviral master batch is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) nano MoS 2 Dispersing: 3-6 parts of MoS 2 Adding the powder into 50 parts of deionized water, carrying out ultrasonic oscillation for 6-10 h, washing a reaction product with the deionized water for three times, centrifugally collecting, and drying for 24h to obtain MoS 2 Nanosheets;
(2) 2-5 parts of MoS by mass 2 The nano-sheet is ultrasonically dispersed in 50 parts of deionized water to prepare MoS 2 An aqueous solution, wherein 0.2-1.0 part of copper salt is dissolved in 50 parts of deionized water to prepare a copper ion aqueous solution; mixing MoS 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 by using deionized water and absolute ethyl alcohol, and finally drying to obtain MoS with the surface generating nano elemental copper 2 A nanosheet antimicrobial;
(3) 1-3 parts of aliphatic dibasic acid and 15-20 parts of MoS with surface generating nano elemental copper 2 Adding 100 parts of absolute ethyl alcohol into the nanosheet and 0.5-2 parts of ethylene glycol, condensing, refluxing and stirring for 0.5-5 h to obtain the carboxylic acid modified surface-generated nano-monomerMoS of 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 supernatant to obtain precipitate, washing the precipitate with ethanol and water for 3-5 times, and drying to obtain carboxylic acid modified MoS with nano elemental copper generated on surface 2 Nanosheets;
(4) MoS for generating nano elemental copper on surface of 10-20 parts of carboxylic acid modified 2 Adding the nanosheets, 80 parts of terephthalic acid and 35-45 parts of ethylene glycol into a polymerization reaction kettle, esterifying, then carrying out prepolymerization and final polymerization, and finally carrying out casting belt and grain cutting to obtain the antibacterial and antiviral master batch.
2. The method for preparing the master batch with antibacterial and antiviral functions according to claim 1, wherein in the step (2), MoS 2 The ultrasonic dispersion conditions of the nanosheets refer to that the time is 20-60 min, and the ultrasonic frequency is 30-60 kHz; the copper salt is one of copper chloride, copper sulfate and copper nitrate; the reducing agent aqueous solution is one of 0.1-0.5 mol/L citric acid, hydrazine hydrate, sodium borohydride, ascorbic acid, sodium hypophosphite and tetrabutylammonium borohydride aqueous solution.
3. The method for preparing the master batch with antibacterial and antiviral functions as claimed in claim 1, wherein in the step (3), the aliphatic dibasic acid is one of adipic acid, suberic acid, sebacic acid and dodecanedioic acid.
4. The preparation method of the antibacterial and antiviral master batch according to claim 1, wherein in the step (4), the esterification reaction conditions are 235-255 ℃, the pressure is 0.3-0.4 MPa, and the time is 2-3 hours; the reaction conditions of the prepolymerization are 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 conditions are that the temperature is 270-280 ℃, the pressure is 20-100 Pa absolute pressure, and the time is 2-3 h.
5. The application of the antibacterial and antiviral master batch is characterized in that: drying the antibacterial and antiviral master batch prepared by the preparation method of any one of claims 1 to 4 and matrix resin at 90-120 ℃ for a period of time, uniformly mixing the antibacterial and antiviral master batch and the matrix resin according to a proportion, and adding the mixture into a melt spinning machine for spinning to obtain the antibacterial and antiviral fiber.
6. The use of the masterbatch of claim 5, wherein the matrix resin is one of polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate; the ratio of the antibacterial and antiviral master batch to the matrix resin is 10-20% of the antibacterial and antiviral master batch in the matrix resin.
7. The application of the antibacterial and antiviral functional master batch according to claim 5, wherein the breaking strength of the antibacterial and antiviral 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, and the antiviral effect on H1N1 influenza A virus can reach more than 97%.
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| CN114009447A (en) * | 2021-11-08 | 2022-02-08 | 陕西科技大学 | Copper nanoparticle-loaded polydopamine-modified sheet MoS2Nano antibacterial agent and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115787282A (en) * | 2022-12-19 | 2023-03-14 | 南通大学 | Two-dimensional alkene modified antiviral photo-thermal nanofiber and preparation method thereof |
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