CN113005774B - Preparation method and antibacterial application of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber - Google Patents
Preparation method and antibacterial application of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber Download PDFInfo
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- 229920002972 Acrylic fiber Polymers 0.000 title claims abstract description 66
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- -1 thiosemicarbazone compound Chemical class 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- CLFRCXCBWIQVRN-UHFFFAOYSA-N 2,5-dihydroxybenzaldehyde Chemical compound OC1=CC=C(O)C(C=O)=C1 CLFRCXCBWIQVRN-UHFFFAOYSA-N 0.000 claims description 8
- WZUODJNEIXSNEU-UHFFFAOYSA-N 2-Hydroxy-4-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(O)=C1 WZUODJNEIXSNEU-UHFFFAOYSA-N 0.000 claims description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
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- 238000010992 reflux Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 5
- CWKXDPPQCVWXAG-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-6-carbaldehyde Chemical compound O1CCOC2=CC(C=O)=CC=C21 CWKXDPPQCVWXAG-UHFFFAOYSA-N 0.000 claims description 4
- QNZWAJZEJAOVPN-UHFFFAOYSA-N 4-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC(Cl)=CC=C1C=O QNZWAJZEJAOVPN-UHFFFAOYSA-N 0.000 claims description 4
- FUGKCSRLAQKUHG-UHFFFAOYSA-N 5-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Cl)C=C1C=O FUGKCSRLAQKUHG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 239000004753 textile Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 5
- 244000063299 Bacillus subtilis Species 0.000 abstract description 3
- 235000014469 Bacillus subtilis Nutrition 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
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- 238000000034 method Methods 0.000 description 13
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- 229920002239 polyacrylonitrile Polymers 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
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- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- SRVJKTDHMYAMHA-WUXMJOGZSA-N thioacetazone Chemical compound CC(=O)NC1=CC=C(\C=N\NC(N)=S)C=C1 SRVJKTDHMYAMHA-WUXMJOGZSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 101001108356 Homo sapiens Nardilysin Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 206010024229 Leprosy Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 102100021850 Nardilysin Human genes 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
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- 238000005452 bending Methods 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 229940042396 direct acting antivirals thiosemicarbazones Drugs 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 150000003584 thiosemicarbazones Chemical class 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a preparation method and antibacterial application of thiosemicarbazone-Cu (II) complex molecular covalent grafting acrylic fiber, which comprises the following steps: (1) hydrolyzing acrylic fibers; (2) preparing a thiosemicarbazone-Cu (II) complex; (3) thiosemicarbazone-Cu (II) complex grafted hydrolyzed acrylic fiber. The invention endows the acrylic fiber with excellent antibacterial performance, has good inhibition effect on gram-positive bacteria staphylococcus aureus and bacillus subtilis, makes up for the defect that the acrylic fiber does not have antibacterial property, has simple and convenient preparation process and mild conditions, and has good application prospect in the fields of close-fitting household textile materials and medical textile materials.
Description
Technical Field
The invention belongs to the technical field of fiber material modification, and particularly relates to a preparation method and an antibacterial application of thiosemicarbazone-Cu (II) complex molecular covalent grafting acrylic fiber.
Background
Polyacrylonitrile fiber is one of three synthetic fibers in the world, is spun by polyacrylonitrile or a copolymer with the acrylonitrile content accounting for more than 85 percent, and the fabric woven by the polyacrylonitrile fiber has good elasticity, soft hand feeling and good heat retention property, and is called synthetic wool. However, because polyacrylonitrile fibers have no antibacterial property, the application space of polyacrylonitrile fibers in the fields of close-fitting household textile materials and medical textile materials is limited.
Thiosemicarbazones refer to compounds obtained by condensing thiourea with an appropriate aldehyde under certain conditions. Researches show that the thiosemicarbazone compound not only has antiviral activity, but also has various biological activities of resisting bacteria, tumors, leprosy and the like. Vanmei et al (a novel thiosemicarbazone and a metal complex thereof synthesis, characterization and biological activity research [ J ] chemical reagent, 2010,32(12): 1076-. Therefore, the reasonable addition of the thiosemicarbazone-Cu (II) complex can endow the polyacrylonitrile fiber with excellent antibacterial performance.
Silver and copper are currently widely used antibacterial agents, but in 2014, the us natural resource protection council (NRDC) announced to limit the use of nano-silver on textiles. The following problems are caused: ag+The silver is easy to be oxidized into brown silver oxide or reduced into black simple substance silver, which not only reduces the antibacterial activity of the silver, but also limits the application of the silver in white or light-colored fabrics; the price is high, and the production cost is high; the problems that the antibacterial agent containing some heavy metal ions may permeate into the body and cause heavy metal accumulation when worn next to the skin, and the health is damaged in a long time and the like are solved. In contrast, copper is the second life element in the human body, second to iron and zinc, in the 3 rd position among trace elements. It is a catalyst for oxidation process in cell, has inhibition effect on bacteria and virus, and has been widely used in water purification, algae removal, fungus removal and other fields.
The invention adopts a chemical method to modify polyacrylonitrile fiber, and amino in the thiosemicarbazone-Cu (II) complex and carboxyl in the hydrolyzed acrylic fiber are subjected to dehydration condensation reaction to generate amido bond, so as to obtain the novel thiosemicarbazone-Cu (II) complex covalent grafting acrylic fiber. The method for covalently grafting the thiosemicarbazone-Cu (II) complex to the acrylic fiber not only can successfully graft the thiosemicarbazone-Cu (II) complex to the hydrolyzed acrylic fiber, retain the good elasticity and hand feeling of the modified hydrolyzed acrylic fiber, but also endow the modified hydrolyzed acrylic fiber with excellent antibacterial activity and illumination self-cleaning property. The preparation method disclosed by the invention is simple in preparation process, green and environment-friendly in process and high in economic added value of products.
Disclosure of Invention
The invention aims to provide a preparation method and antibacterial application of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber, which are green, environment-friendly and simple in process.
The invention is realized by the following steps:
the preparation method and the antibacterial application of the thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber have the core thought that:
firstly, the acrylic fiber is hydrolyzed by sodium hydroxide solution to convert cyano (-CN) on the side chain structure of the molecule toThe thiosemicarbazone compound is synthesized by carboxyl (-COOH) and salicylaldehyde (taking salicylaldehyde as an example) and thiomethylhydrazine, and the molecules of the thiosemicarbazone compound contain multiple coordination atoms such as nitrogen and sulfur with strong coordination capacity, so that the thiosemicarbazone compound can be used as a ligand to provide an electron pair and a copper ion through an S atom and a hydrazine N atom to generate a copper complex; due to amino groups (-NH) on the thiosemicarbazone molecule2) Can generate an amido bond by dehydration reaction with carboxyl (-COOH) on the surface of the acrylic fiber, so that the thiosemicarbazone-copper complex after biological activity screening and the hydrolyzed acrylic fiber are subjected to covalent grafting. The thiosemicarbazone-Cu (II) complex covalent grafting acrylic fiber combines the high-efficiency antibacterial activity of the thiosemicarbazone-copper complex with the fluffy and high-elasticity characteristics of the acrylic fiber to develop a novel antibacterial fiber material.
(1) Acrylic fiber hydrolysis: putting the acrylic fiber into a sodium hydroxide solution with the mass percentage concentration of 8-15% and the temperature of 70-90 ℃ for hydrolysis for 5-15 min, taking out the fiber after the reaction is finished, washing and drying to constant weight;
(2) the reaction process and the molecular structural formula of the invention are as follows:
wherein, in the formula R, the Y is at least one of hydrogen, alkyl containing 1-3 carbon atoms, halogen, hydroxyl, methoxyl, amino, sulfonic group, nitryl, carboxyl, sulfydryl, methylamino, ethylamino, dimethylamino or diethylamino independently; for further illustrative understanding, the structural formula R, as illustrated herein, is representative of the structure R1，R2，R3，R4，R5，R6And the like aldehydes such as salicylaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 4-chloro-2-hydroxybenzaldehyde, 2, 5-dihydroxybenzaldehyde, 3, 4-ethylenedioxybenzaldehyde are given as examples.
(3) Preparing a thiosemicarbazone-Cu (II) complex: and (2) putting the thiomethylhydrazine into a two-neck flask containing a mixed solution of ethanol and water, and stirring and refluxing at the temperature of 50-80 ℃ until the thiomethylhydrazine is dissolved. Weighing salicylaldehyde (taking salicylaldehyde as an example) in equal proportion, diluting the salicylaldehyde with ethanol, cooling to 30-60 ℃, slowly dropwise adding the diluted salicylaldehyde solution, dropwise adding a proper amount of acetic acid for catalysis, stirring and refluxing for 4-8 hours, cooling to room temperature, performing suction filtration, washing a filter cake with hot water and ethanol for 2-3 times respectively, volatilizing the ethanol at room temperature, and drying in an oven at 60-90 ℃ to obtain light yellow powder (a thiosemicarbazone compound). Weighing a thiosemicarbazone compound in a DMSO solution, taking anhydrous copper sulfate in distilled water, stirring to dissolve the thiosemicarbazone compound, slowly pouring a ligand solution into a copper sulfate solution, stirring to react for 4-8 hours at room temperature, adding a proper amount of water, standing until the precipitate is completely separated out, performing suction filtration and drying to obtain dark green powder (thiosemicarbazone-Cu (II) complex);
(4) grafting and hydrolyzing acrylic fibers by a thiosemicarbazone-Cu (II) complex: weighing the components in a mass ratio of 1: 2, dissolving the thiosemicarbazone-Cu (II) complex in a DMF (dimethyl formamide) solution at the temperature of 40-70 ℃, uniformly dispersing the hydrolyzed acrylic fibers in the solution, and adding Dicyclohexylcarbodiimide (DCC) with the molar ratio of 1:10 to the thiosemicarbazone-Cu (II) complex to promote the formation of an amido bond. Reacting in a constant-temperature water bath at 40-70 ℃ for 12-24 h. And after the reaction is finished, washing the product for 2-3 times by using deionized water and ethanol, and drying the product at the temperature of 40-60 ℃ to obtain a grafted product.
The further scheme is as follows:
the mass percentage concentration of the sodium hydroxide solution in the step (1) is 8-15%.
The further scheme is as follows:
and (3) putting the thiomethylhydrazine in the mixed solution of ethanol and water at the temperature of 50-80 ℃.
The further scheme is as follows:
the molecular structural formula of the reaction process in the step (2) is shown in the specification, wherein Y in the formula R is at least one of hydrogen, alkyl containing 1-3 carbon atoms, halogen, hydroxyl, methoxy, amino, sulfonic group, nitro, carboxyl, sulfydryl, methylamino, ethylamino, dimethylamino or diethylamino independently; is composed ofA further illustrative understanding of the formula R set forth in the description of the invention is provided by the representative structure R1，R2，R3，R4，R5，R6And the like aldehydes such as salicylaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 4-chloro-2-hydroxybenzaldehyde, 2, 5-dihydroxybenzaldehyde, 3, 4-ethylenedioxybenzaldehyde are given as examples.
The further scheme is as follows:
in the step (3), the stirring reflux time of the salicylaldehyde and the thiomethylhydrazine and the stirring reaction of the ligand solution and the copper sulfate solution are all 4-8 hours.
The further scheme is as follows:
the mass ratio of the hydrolyzed acrylic fibers to the thiosemicarbazone-Cu (II) complex in the step (4) is 1: 2.
The further scheme is as follows:
the reaction temperature for hydrolyzing the acrylic fiber and the thiosemicarbazone-Cu (II) complex in the step (4) is as follows: the reaction time is as follows at 40-70 deg.C: 12-24 h.
The invention has the following beneficial effects:
(1) the method takes acrylic fibers as a base material, firstly hydrolyzes the acrylic fibers, converts cyano (-CN) on a molecular side chain structure into carboxyl (-COOH), then synthesizes thiosemicarbazone compound through salicylaldehyde and thiohydrazine, and uses the thiosemicarbazone compound as a ligand to provide an electron pair and a metal copper ion through S, O and a hydrazine N atom to generate a thiosemicarbazone-copper complex; and finally, carrying out covalent grafting on the thiosemicarbazone-copper complex and the hydrolyzed acrylic fiber. The method ensures that the prepared acrylic fiber has excellent antibacterial performance and illumination self-cleaning performance, and makes up for the defect that the acrylic fiber does not have antibacterial performance.
(2) The invention has simple and convenient process, can be widely applied to the fields of close-fitting household textile materials, medical textile materials and the like, and has wide market application prospect.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) comparison of acrylon as it is with hydrolyzed acrylon and modified acrylon.
FIG. 2 is a graph showing the antibacterial effect of acrylic fibers and modified acrylic fibers.
FIG. 3 is a graph comparing the infrared spectra (FTIR) of acrylic as such and modified acrylic.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
Examples 1
(1) Acrylic fiber hydrolysis: putting the acrylic fiber into a sodium hydroxide solution with the mass percentage concentration of 10% and the temperature of 75 ℃ for hydrolysis for 8min, taking out the fiber after the reaction is finished, washing and drying to constant weight;
(2) preparing a thiosemicarbazone-Cu (II) complex: the method comprises the steps of placing thiomethylhydrazine in a two-neck flask containing a mixed solution of ethanol and water, stirring at the temperature of 60 ℃ until the thiomethylhydrazine is dissolved, weighing salicylaldehyde (taking the salicylaldehyde as an example) in equal proportion, diluting with ethanol, dissolving the thiomethylhydrazine, cooling to 40 ℃, slowly dropwise adding the diluted salicylaldehyde solution, dropwise adding an appropriate amount of acetic acid for catalysis, stirring and refluxing for 5 hours, cooling to room temperature, carrying out suction filtration, washing a filter cake with hot water and ethanol for 2-3 times respectively, volatilizing the ethanol at the room temperature, and drying in an oven at 70 ℃ to obtain light yellow powder (a thiosemicarbazone compound). Weighing thiosemicarbazone compound in a DMSO solution, taking anhydrous copper sulfate in distilled water, stirring to dissolve the thiosemicarbazone compound, slowly pouring a ligand solution into a copper sulfate solution, stirring and reacting for 5 hours at room temperature, adding a proper amount of water, standing until the precipitate is completely separated out, performing suction filtration and drying to obtain dark green powder (thiosemicarbazone-Cu (II) complex);
(3) grafting and hydrolyzing acrylic fibers by a thiosemicarbazone-Cu (II) complex: weighing the components in a mass ratio of 1: 2, dissolving the thiosemicarbazone-Cu (II) complex in a DMF solution at 50 ℃, uniformly dispersing the hydrolyzed acrylic fiber in the solution, adding Dicyclohexylcarbodiimide (DCC) with the molar ratio of 1:10 to the thiosemicarbazone-Cu (II) complex to promote the generation of amido bonds, and reacting for 16 hours in a constant-temperature water bath at 45 ℃. And after the reaction is finished, washing the product for 2-3 times by using deionized water and ethanol, and drying the product at room temperature to obtain a grafted product.
EXAMPLES example 2
(1) Acrylic fiber hydrolysis: putting the acrylic fiber into a sodium hydroxide solution with the mass percentage concentration of 12% and the temperature of 85 ℃ for hydrolysis for 12min, taking out the fiber after the reaction is finished, washing and drying to constant weight;
(2) preparing a thiosemicarbazone-Cu (II) complex: the method comprises the steps of placing thiomethylhydrazine in a two-neck flask containing a mixed solution of ethanol and water, stirring at the temperature of 70 ℃ until the thiomethylhydrazine is dissolved, weighing salicylaldehyde (taking the salicylaldehyde as an example) in equal proportion, diluting with ethanol, dissolving the thiomethylhydrazine, cooling to 50 ℃, slowly dropwise adding the diluted salicylaldehyde solution, dropwise adding a drop of acetic acid for catalysis, stirring and refluxing for 7 hours, cooling to room temperature, carrying out suction filtration, washing a filter cake with hot water and ethanol for 2-3 times respectively, volatilizing the ethanol at the room temperature, and drying in an oven at the temperature of 80 ℃ to obtain light yellow powder (thiosemicarbazone compound). Weighing thiosemicarbazone compound in a DMSO solution, taking anhydrous copper sulfate in distilled water, stirring to dissolve the thiosemicarbazone compound, slowly pouring a ligand solution into a copper sulfate solution, stirring and reacting for 7 hours at room temperature, adding a proper amount of water, standing until the precipitate is completely separated out, performing suction filtration and drying to obtain dark green powder (thiosemicarbazone-Cu (II) complex);
(3) grafting and hydrolyzing acrylic fibers by a thiosemicarbazone-Cu (II) complex: weighing the components in a mass ratio of 1: 2, dissolving the thiosemicarbazone-Cu (II) complex in a DMF solution at the temperature of 60 ℃, uniformly dispersing the hydrolyzed acrylic fiber in the solution, adding Dicyclohexylcarbodiimide (DCC) with the molar ratio of 1:10 to the thiosemicarbazone-Cu (II) complex to promote the generation of amido bonds, and reacting for 20 hours in a constant-temperature water bath at the temperature of 55 ℃. And after the reaction is finished, washing the product for 2-3 times by using deionized water and ethanol, and drying the product at room temperature to obtain a grafted product.
Infrared spectroscopy test (FTIR) and conclusion: a is an infrared spectrum before the acrylic fiber is grafted; b infrared spectrum of acrylic fiber after grafting. As can be seen from the graphs a and b, there are some common absorption peaks before and after modification of acrylic fiber, such as 2243cm-1，1730cm-1The accessory has characteristic absorption peaks of cyano and methyl methacrylate groups, and the absorption peak is 2922cm-1、1450cm-1Absorption of alkane radicals occurs nearbyThe peak is collected, the graph b is compared with the graph a and is at 1645cm-1、1535cm-1、2362cm-1Three new absorption peaks appeared nearby, corresponding to the C ═ O stretching vibration and N — H bending vibration absorption peaks of the amide group, and the C ═ N absorption peak, respectively. In addition, the thickness is 3359cm-1The absorption peak of carboxyl appears nearby, and is at 2243cm-1The absorption peak of the cyano group is weakened because the cyano group on the surface of the acrylic fiber is partially hydrolyzed into carboxyl group, the content is obviously reduced, and the grafted compound has hydroxyl group on the substituent per se, so 3359cm-1The vicinities also correspond to the hydroxyl groups on the graft compound. The generation of the new absorption peaks and the change of the peak heights of the absorption peaks show that the hydrolyzed acrylon and thiosemicarbazone-Cu (II) complex molecules successfully undergo dehydration condensation reaction to form a stable compound structure.
Electron Microscopy (SEM) testing and conclusions: as can be seen from the figure, the surface ravines of the hydrolyzed polyacrylonitrile fiber are obviously deepened, but after the thiosemicarbazone-Cu (II) complex is grafted, cracks and ravines on the surface of the fiber are filled with the thiosemicarbazone-Cu (II) complex, fine ravines and corrosion on the surface of the fiber are not obvious any more, and smooth corrosion is recovered, and meanwhile, a layer of obvious film is formed on the surface of the grafted and modified polyacrylonitrile fiber, so that the thiosemicarbazone-Cu (II) complex not only fills the cracks and the ravines on the surface of the hydrolyzed polyacrylonitrile fiber, but also covers an obvious film layer.
Antibacterial testing and conclusion: the invention takes common acrylic fiber as a control, selects gram-positive bacteria staphylococcus aureus and bacillus subtilis as experimental strains, and adopts the following steps in GB/T20944.3-2008, evaluation part 3 of antibacterial performance of textiles: slightly improved on the basis of the oscillation method, and the antibacterial performance of the modified acrylic fiber is researched by adopting an antibacterial ring method. The specific operation is as follows: weighing a certain mass of modified acrylic fiber, and sterilizing for 30min under the irradiation of an ultraviolet lamp; sequentially adding 4mL of LB culture solution and 10mL of PBS solution into a centrifuge tube to completely immerse the fibers; sequentially adding 1mL of activated staphylococcus aureus and bacillus subtilis (OD600 is approximately equal to 0.5-0.6) into each centrifugal tube; placing the sealed centrifuge tube into a shaking table to oscillate for 24h, setting the rotating speed at 150rmp and the temperatureThe degree is controlled at 24 +/-1 ℃; sucking 100 μ L of each treated bacterial liquid, and diluting to 10% by 10-fold dilution method-1、 10-2、10-3、10-4、10-5Finally at a dilution of 10-4、10-5Taking 100 mu L of the sample, coating the sample on a sterile plate, inverting the sterile plate, putting the sterile plate into a constant-temperature incubator at the temperature of 37 ℃ for culturing for 24-48 h, observing the growth condition of bacterial colonies on the plate, and counting by adopting a plate counting method. In examples 1 and 2, staphylococcus aureus was used as the experimental species, and the experimental data are as follows:
TABLE 1 statistics of antibacterial ratio of acrylic fiber samples to Staphylococcus aureus
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (8)
1. A preparation method of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber is characterized by comprising the following steps:
(1) acrylic fiber hydrolysis: putting the acrylic fiber into a sodium hydroxide solution with the mass percentage concentration of 8-15% and the temperature of 70-90 ℃ for hydrolysis for 5-15 min, taking out the fiber after the reaction is finished, washing, and drying to constant weight;
(2) the reaction flow and the molecular structural formula are shown as follows:
wherein R is selected from the structure R1，R2，R3，R4，R5，R6I.e. salicylaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 4-chloro-2-hydroxybenzaldehyde, 2, 5-dihydroxybenzaldehyde, 3, 4-ethylenedioxybenzaldehyde;
(3) preparing a thiosemicarbazone-Cu (II) complex: putting the thiomethylhydrazine into a two-neck flask containing a mixed solution of ethanol and water, stirring at the temperature of 50-80 ℃ until the thiomethylhydrazine is dissolved, weighing salicylaldehyde in equal proportion, diluting with ethanol, cooling to 30-60 ℃, slowly dripping diluted salicylaldehyde solution, dripping a proper amount of acetic acid for catalysis, stirring and refluxing for 4-8 h, cooling to room temperature, performing suction filtration, washing a filter cake with hot water and ethanol for 2-3 times respectively, drying in an oven at 60-90 ℃ after ethanol volatilizes at room temperature to obtain light yellow powder (thiosemicarbazone compound), weighing the thiosemicarbazone compound in a DMSO solution, dissolving anhydrous copper sulfate in distilled water by stirring, slowly pouring the ligand solution into the copper sulfate solution, stirring and reacting for 4-8 h at room temperature, adding a proper amount of water, standing until precipitation is completely separated out, performing suction filtration and drying to obtain dark green powder (thiosemicarbazone-Cu (II) complex);
(4) grafting and hydrolyzing acrylic fibers by a thiosemicarbazone-Cu (II) complex: weighing the components in a mass ratio of 1: dissolving the thiosemicarbazone-Cu (II) complex in a DMF (dimethyl formamide) solution at the dissolving temperature of 40-70 ℃, uniformly dispersing the hydrolyzed acrylic fiber in the solution, adding Dicyclohexylcarbodiimide (DCC) with the molar ratio of 1:10 to the thiosemicarbazone-Cu (II) complex to promote the generation of an amido bond, reacting for 12-24 hours in a constant-temperature water bath at the temperature of 40-70 ℃, washing for 2-3 times by deionized water and ethanol after the reaction is finished, and drying at the temperature of 40-60 ℃ to obtain a grafting product.
2. The preparation method of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber according to claim 1, which is characterized in that:
the mass percentage concentration of the sodium hydroxide solution in the step (1) is 8-15%.
3. The preparation method of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber according to claim 1, which is characterized in that: and (3) putting the thiomethylhydrazine in the mixed solution of the ethanol and the water at the temperature of 50-80 ℃.
4. The preparation method of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber according to claim 1, which is characterized in that:
the reaction flow in the step (2) has a molecular structural formula, and the formula R is selected from a structure R1，R2，R3，R4，R5，R6I.e. salicylaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 4-chloro-2-hydroxybenzaldehyde, 2, 5-dihydroxybenzaldehyde, 3, 4-ethylenedioxybenzaldehyde.
5. The preparation method of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber according to claim 1, which is characterized in that:
in the step (3), the stirring reflux time of the salicylaldehyde and the thiomethylhydrazine and the stirring reaction of the ligand solution and the copper sulfate solution are all 4-8 hours.
6. The preparation method of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber according to claim 1, which is characterized in that:
the mass ratio of the hydrolyzed acrylic fibers to the thiosemicarbazone-Cu (II) complex in the step (4) is 1: 2.
7. the preparation method of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber according to claim 1, which is characterized in that:
the reaction temperature for hydrolyzing the acrylic fiber and the thiosemicarbazone-Cu (II) complex in the step (4) is as follows: at the temperature of 40-70 ℃, the reaction time is as follows: 12-24 h.
8. An antibacterial application of thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber is characterized in that the acrylic fiber prepared by the preparation method of the thiosemicarbazone-Cu (II) complex molecule covalent grafting acrylic fiber in any claim from 1 to 7 is applied to the antibacterial aspect.
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