CN116145280A - TiO (titanium dioxide) 2 PHMG composite modified PET antibacterial fabric and preparation method thereof - Google Patents
TiO (titanium dioxide) 2 PHMG composite modified PET antibacterial fabric and preparation method thereof Download PDFInfo
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- CN116145280A CN116145280A CN202211738852.1A CN202211738852A CN116145280A CN 116145280 A CN116145280 A CN 116145280A CN 202211738852 A CN202211738852 A CN 202211738852A CN 116145280 A CN116145280 A CN 116145280A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 52
- 239000004744 fabric Substances 0.000 title claims abstract description 50
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 41
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 28
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 17
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002074 melt spinning Methods 0.000 claims abstract description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 120
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 120
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 63
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- -1 polyethylene terephthalate Polymers 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 16
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 11
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 11
- 238000009987 spinning Methods 0.000 claims description 11
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims 1
- 241000894006 Bacteria Species 0.000 abstract description 5
- 244000005700 microbiome Species 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 230000004060 metabolic process Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 208000017520 skin disease Diseases 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- CJPIDIRJSIUWRJ-UHFFFAOYSA-N benzene-1,2,4-tricarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(C(Cl)=O)=C1 CJPIDIRJSIUWRJ-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to the technical field of antibacterial fabrics, and discloses a TiO (titanium dioxide) 2 PHMG compound modified PET antibacterial fabric, nano titanium dioxide reacts with trimesoyl chloride to obtain acyl chloride titanium dioxide, the acyl chloride titanium dioxide reacts with PET to obtain PET grafted titanium dioxide, the PET grafted titanium dioxide further reacts with epoxidized PHMG to obtain PET grafted TiO 2 PHMG composite master batch, and finally obtaining TiO by melt spinning the composite master batch 2 The PHMG compound modified PET antibacterial fabric improves the dispersibility of titanium dioxide through chemical bond connection, the titanium dioxide can be sterilized under the illumination condition, the PHMG can be adsorbed on the surface of bacteria microorganisms, and is combined with negatively charged phosphoric acid to destroy the metabolism and reproduction process of cells, so that the antibacterial effect is finally achieved, the antibacterial performance of the PET base fabric is effectively improved through the combined action of nano titanium dioxide and PHMG, and the application of PET is further expandedThe application range is as follows.
Description
Technical Field
The invention relates to the technical field of antibacterial fabrics, in particular to a TiO (titanium dioxide) 2 PHMG composite modified PET antibacterial fabric and preparation method thereof.
Background
In daily life, human beings inevitably contact a large number of microorganisms such as bacteria and fungi in the external environment, the microorganisms can be stimulated by skin for a long time to induce various skin diseases, even various skin diseases can be transmitted, so that the protection of bacteria is necessary in daily life, the fabric is used as a direct barrier for blocking human beings and the external environment and has an antibacterial function, however, the PET is used as a fabric carrier in the market at present, the PET does not have antibacterial performance, so that the PET needs to be modified, the PEF antibacterial performance can be endowed in a short time by a common antibacterial agent soaking type modification method, but the antibacterial agent is difficult to fall off due to cleaning and friction, the antibacterial function is difficult to keep for a long time, the antibacterial agent is required to be combined with the PET in a firmer way, an inorganic nano material or an organic polymer material with the antibacterial performance can be chemically bonded in a PET matrix in a grafting way, and the phenomenon of falling off of the antibacterial agent can be effectively avoided.
The nano titanium dioxide is an inorganic nano material with wide application, has the advantages of low toxicity, good safety and high biocompatibility, is greatly valued in the field of nano materials, is gradually applied to various fields such as paint, coating, photocatalysis and the like, and can be used as a functional reinforcing agent for modifying an organic high polymer material, but the nano titanium dioxide has high specific surface energy and is difficult to disperse in a polymer mechanism, the nano titanium dioxide is easily aggregated in the organic high polymer material due to a common physical mixing mode, the ideal modifying effect cannot be achieved, and the nano titanium dioxide has limited practicability in the aspect of antibiosis, so that the nano titanium dioxide needs to be modified, the functionality of the nano titanium dioxide is enhanced, and the application range of the nano titanium dioxide is further improved.
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a TiO 2 The PHMG composite modified PET antibacterial fabric and the preparation method thereof solve the problem that the PET fabric does not have antibacterial performance.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: tiO (titanium dioxide) 2 -PHMG composite modified PET antibacterial fabric, said TiO 2 The preparation method of the PHMG composite modified PET antibacterial fabric comprises the following steps:
(1) Preparation of acid chloride titanium dioxide: adding a dichloromethane solvent and nano titanium dioxide into a reactor, performing ultrasonic dispersion uniformly, continuously adding trimesoyl chloride and triethylamine, stirring uniformly, transferring into an oil bath kettle, reacting for 20-30h at 30-50 ℃, performing reduced pressure distillation to remove the solvent after the reaction is finished, washing with dichloromethane, placing into a vacuum drying oven, and drying for 1-3h at 20-40 ℃ to obtain acyl chloride titanium dioxide;
(2) Preparation of polyethylene terephthalate (PET) grafted titanium dioxide: adding dichloroethane solvent and titanium dioxide acyl chloride into a reactor, uniformly dispersing by ultrasonic, continuously adding PET, uniformly stirring by magnetic force, transferring into an oil bath, raising the temperature for reaction, and carrying out reduced pressure distillation, washing and drying after the reaction is finished to obtain PET grafted titanium dioxide;
(3) Preparation of epoxidized polyhexamethylene diamido guanidine hydrochloride: adding 120-240mL of tetrahydrofuran solvent, 25-45g of polyhexamethylene diamido guanidine hydrochloride (PHMG), 20-40g of epichlorohydrin and 0.3-0.6g of boron trifluoride diethyl ether complex into a reactor, stirring until the mixture is completely dissolved, reacting for 4-8 hours at 50-70 ℃, adding 10-30g of sodium ethoxide into the system after the reaction is complete, continuously reacting for 6-12 hours at 20-30 ℃, filtering, washing and drying the product to obtain the epoxidized PHMG;
(4) PET grafted TiO 2 Preparation of PHMG composite master batch: adding PET grafted titanium dioxide and epoxidized PHMG into a reactor, fully and uniformly mixing, transferring into a torque rheometer, and raising the temperature to react to obtain PET grafted TiO 2 -PHMG composite master batch;
(5)TiO 2 preparation of PHMG composite modified PET antibacterial fabric: adding PET grafted TiO into melt spinning equipment 2 PHMG composite master batch, spinning after setting spinning parameters, obtaining TiO 2 -PHMG composite modified PET antibacterial fabric.
Preferably, the dosage ratio of the dichloromethane solvent, the nano titanium dioxide, the trimesoyl chloride and the triethylamine in the step (1) is 120-240mL, 4-8g, 12-24g and 2-6mL.
Preferably, the dosage ratio of the dichloroethane solvent, the titanium dioxide acyl chloride and the PET in the step (2) is 60-100mL, 0.02-0.1g and 10g.
Preferably, the temperature of the reaction in the step (2) is 70-90 ℃, and the reaction is carried out for 48-76h under the protection of nitrogen.
Preferably, the dosage ratio of the PET grafted titanium dioxide to the epoxidized PHMG in the step (4) is 10g:0.04-0.08g.
Preferably, the temperature of the reaction in the step (4) is 260-280 ℃ and the time is 4-8min.
Preferably, in the step (4), the temperatures of the screw sections are 280-285 ℃, 300-310 ℃, 290-295 ℃ and 290-295 ℃ respectively, the temperature of the metering pump is 290-300 ℃, the temperature of the die is 300-310 ℃, and the traction speed is 900-1200m/min.
(III) beneficial technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the TiO 2 The PHMG compound modified PET antibacterial fabric comprises a large amount of hydroxyl groups on the surface of nano titanium dioxide, wherein the nano titanium dioxide is subjected to esterification reaction with acyl chloride groups in trimesoyl chloride under the action of an accelerant triethylamine to obtain acyl chloride titanium dioxide, the hydroxyl groups in PET can be subjected to esterification reaction with the acyl chloride groups in the acyl chloride titanium dioxide to obtain PET grafted titanium dioxide, the amino groups in PHMG are subjected to substitution reaction with chlorine atoms in epichlorohydrin under the action of a boron trifluoride diethyl ether complex catalyst, the part of the epoxy chloropropane, which is subjected to ring-opening reaction by the amino groups in PHMG, is subjected to ring-opening reaction to obtain epoxidized PHMG, and the carboxyl groups in the PET grafted titanium dioxide and the epoxy groups in the epoxidized PHMG are subjected to ring-opening reaction in a melt grafting mode to obtain PET grafted TiO 2 The PHMG composite master batch is characterized in that the surface of the nano titanium dioxide is covalently grafted with acyl chloride groups in a chemical bond connection mode, and PET and PHMG are further introduced through the acyl chloride groups, so that the functionality of the nano titanium dioxide is further enhanced, and the application range of the nano titanium dioxide is widened.
The TiO 2 PHMG composite modified PET antibacterial fabric, PET is grafted with TiO by melt spinning 2 PHMG composite master batch melt spinning to finally obtain TiO 2 The PHMG composite modified PET antibacterial fabric effectively enhances the interfacial compatibility between the nano materials and the organic polymer materials by connecting the nano materials and the organic polymer materials through chemical bonds, avoids the agglomeration and the shedding of the nano titanium dioxide, and ensures that the nano titanium dioxide uniformly dispersed in the PET fabric matrix is subjected to optical irradiationWhen the PET-based fabric is irradiated, photo-generated electrons and holes are generated and further react with oxygen and water adsorbed on the surface of the fabric substrate to generate super-oxygen free radicals and hydroxyl free radicals with extremely strong oxidizing property, and finally microorganisms such as bacteria and fungi are oxidized into carbon dioxide and water, and PHMG is used as a cationic compound, can be adsorbed on the surface of negatively charged bacteria microorganisms and gradually permeates into bacterial cells to be combined with negatively charged phosphoric acid, so that the selective permeability of cell membranes is changed, the metabolism and the reproduction process of the cells are damaged, the sterilization effect is finally achieved, and the antibacterial performance of the PET-based fabric is effectively improved by combining the combined action of nano titanium dioxide and PHMG, and the application range of PET is further expanded.
Detailed Description
In order to achieve the above object, the present invention provides the following specific embodiments and examples: tiO (titanium dioxide) 2 -PHMG composite modified PET antibacterial fabric, the preparation method comprises the following steps:
(1) Preparation of acid chloride titanium dioxide: adding a dichloromethane solvent and nano titanium dioxide into a reactor, carrying out ultrasonic dispersion uniformly, continuously adding trimesoyl chloride and triethylamine, wherein the dosage ratio of the dichloromethane solvent to the nano titanium dioxide to the trimesoyl chloride to the triethylamine is 120-240mL:4-8g:12-24g:2-6mL, stirring uniformly, transferring into an oil bath kettle, reacting for 20-30h at 30-50 ℃, carrying out reduced pressure distillation to remove the solvent after the reaction is finished, washing with dichloromethane, placing into a vacuum drying box, and drying for 1-3h at 20-40 ℃ to obtain the acyl chloride titanium dioxide;
(2) Preparation of polyethylene terephthalate (PET) grafted titanium dioxide: adding dichloroethane solvent and titanium dioxide acyl chloride into a reactor, dispersing uniformly by ultrasonic, continuously adding PET, wherein the dosage ratio of the dichloroethane solvent to the titanium dioxide acyl chloride to the PET is 60-100mL:0.02-0.1g:10g, stirring uniformly by magnetic force, transferring into an oil bath, reacting for 48-76h at 70-90 ℃ under the protection of nitrogen, and carrying out reduced pressure distillation, washing and drying after the reaction is finished to obtain PET grafted titanium dioxide;
(3) Preparation of epoxidized polyhexamethylene diamido guanidine hydrochloride: adding 120-240mL of tetrahydrofuran solvent, 25-45g of polyhexamethylene diamido guanidine hydrochloride (PHMG), 20-40g of epichlorohydrin and 0.3-0.6g of boron trifluoride diethyl ether complex into a reactor, stirring until the mixture is completely dissolved, reacting for 4-8 hours at 50-70 ℃, adding 10-30g of sodium ethoxide into the system after the reaction is complete, continuously reacting for 6-12 hours at 20-30 ℃, filtering, washing and drying the product to obtain the epoxidized PHMG;
(4) PET grafted TiO 2 Preparation of PHMG composite master batch: adding PET grafted titanium dioxide and epoxidized PHMG with the dosage ratio of 10g to 0.04-0.08g into a reactor, fully and uniformly mixing, transferring into a torque rheometer, raising the temperature to 260-280 ℃ and reacting for 4-8min to obtain PET grafted TiO 2 -PHMG composite master batch;
(5)TiO 2 preparation of PHMG composite modified PET antibacterial fabric: adding PET grafted TiO into melt spinning equipment 2 PHMG composite master batch, setting screw section temperature to 280-285 ℃, 300-310 ℃, 290-295 ℃ and 290-295 ℃ respectively, metering pump temperature to 290-300 ℃, die temperature to 300-310 ℃ and traction speed to 900-1200m/min, spinning to obtain TiO 2 -PHMG composite modified PET antibacterial fabric.
Example 1
(1) Preparation of acid chloride titanium dioxide: adding 120mL of dichloromethane solvent and 4g of nano titanium dioxide into a reactor, carrying out ultrasonic dispersion uniformly, continuously adding 12g of trimesoyl chloride and 2mL of triethylamine, stirring uniformly, transferring into an oil bath kettle, reacting for 20h at 30 ℃, decompressing and distilling to remove the solvent after the reaction is finished, washing with dichloromethane, placing into a vacuum drying oven, and drying for 1h at 20 ℃ to obtain acyl chloride titanium dioxide;
(2) Preparation of polyethylene terephthalate (PET) grafted titanium dioxide: adding 60mL of dichloroethane solvent and 0.02g of titanium dioxide acyl chloride into a reactor, uniformly dispersing by ultrasonic, continuously adding 10g of PET, uniformly stirring by magnetic force, transferring into an oil bath kettle, reacting at 70 ℃ for 48 hours under the protection of nitrogen, and carrying out reduced pressure distillation, washing and drying after the reaction is finished to obtain PET grafted titanium dioxide;
(3) Preparation of epoxidized polyhexamethylene diamido guanidine hydrochloride: adding 120mL of tetrahydrofuran solvent, 25g of polyhexamethylene diamido guanidine hydrochloride (PHMG), 20g of epichlorohydrin and 0.3g of boron trifluoride diethyl ether complex into a reactor, stirring until the mixture is completely dissolved, reacting for 4 hours at 50 ℃, adding 10g of sodium ethoxide into a system after the reaction is complete, continuously reacting for 6 hours at 20 ℃, filtering, washing and drying the product to obtain epoxidized PHMG;
(4) PET grafted TiO 2 Preparation of PHMG composite master batch: adding 10g of PET grafted titanium dioxide and 0.04g of epoxidized PHMG into a reactor, fully and uniformly mixing, transferring into a torque rheometer, raising the temperature to 260 ℃, and reacting for 4min to obtain PET grafted TiO 2 -PHMG composite master batch;
(5)TiO 2 preparation of PHMG composite modified PET antibacterial fabric: adding PET grafted TiO into melt spinning equipment 2 PHMG composite master batch, setting the temperature of a screw section to 280 ℃, 300 ℃, 290 ℃ and 290 ℃, the temperature of a metering pump to 295 ℃, setting the temperature of a die to 300 ℃, setting the traction speed to 900m/min, and spinning to obtain TiO 2 -PHMG composite modified PET antibacterial fabric.
Example 2
(1) Preparation of acid chloride titanium dioxide: adding 150mL of dichloromethane solvent and 5g of nano titanium dioxide into a reactor, carrying out ultrasonic dispersion uniformly, continuously adding 15g of trimesoyl chloride and 3mL of triethylamine, stirring uniformly, transferring into an oil bath kettle, reacting for 22h at 35 ℃, decompressing and distilling to remove the solvent after the reaction is finished, washing with dichloromethane, placing into a vacuum drying box, and drying for 2h at 25 ℃ to obtain acyl chloride titanium dioxide;
(2) Preparation of polyethylene terephthalate (PET) grafted titanium dioxide: adding 70mL of dichloroethane solvent and 0.04g of titanium dioxide acyl chloride into a reactor, uniformly dispersing by ultrasonic, continuously adding 10g of PET, uniformly stirring by magnetic force, transferring into an oil bath kettle, reacting at 75 ℃ for 52 hours under the protection of nitrogen, and carrying out reduced pressure distillation, washing and drying after the reaction is finished to obtain PET grafted titanium dioxide;
(3) Preparation of epoxidized polyhexamethylene diamido guanidine hydrochloride: 150mL of tetrahydrofuran solvent, 30g of polyhexamethylene diamido guanidine hydrochloride (PHMG), 25g of epoxy chloropropane and 0.38g of boron trifluoride diethyl etherate are added into a reactor, after the mixture is stirred to be completely dissolved, the mixture is reacted for 5 hours at 55 ℃, 15g of sodium ethoxide is added into the system after the reaction is complete, the mixture is continuously reacted for 8 hours at 22 ℃, and the product is filtered, washed and dried to obtain epoxidized PHMG;
(4) PET grafted TiO 2 Preparation of PHMG composite master batch: adding 10g of PET grafted titanium dioxide and 0.05g of epoxidized PHMG into a reactor, fully and uniformly mixing, transferring into a torque rheometer, raising the temperature to 265 ℃, and reacting for 5min to obtain PET grafted TiO 2 -PHMG composite master batch;
(5)TiO 2 preparation of PHMG composite modified PET antibacterial fabric: adding PET grafted TiO into melt spinning equipment 2 PHMG composite master batch, setting the screw section temperature at 282 ℃, 305 ℃, 292 ℃ and 292 ℃, the metering pump temperature at 295 ℃, the die temperature at 305 ℃ and the traction speed at 1000m/min, spinning to obtain TiO 2 -PHMG composite modified PET antibacterial fabric.
Example 3
(1) Preparation of acid chloride titanium dioxide: adding 180mL of dichloromethane solvent and 6g of nano titanium dioxide into a reactor, carrying out ultrasonic dispersion uniformly, continuously adding 18g of trimesoyl chloride and 4mL of triethylamine, stirring uniformly, transferring into an oil bath kettle, reacting at 40 ℃ for 25 hours, decompressing and distilling to remove the solvent after the reaction is finished, washing with dichloromethane, placing into a vacuum drying oven, and drying at 30 ℃ for 2 hours to obtain acyl chloride titanium dioxide;
(2) Preparation of polyethylene terephthalate (PET) grafted titanium dioxide: adding 80mL of dichloroethane solvent and 0.06g of titanium dioxide acyl chloride into a reactor, uniformly dispersing by ultrasonic, continuously adding 10g of PET, uniformly stirring by magnetic force, transferring into an oil bath kettle, reacting at 80 ℃ for 60 hours under the protection of nitrogen, and carrying out reduced pressure distillation, washing and drying after the reaction is finished to obtain PET grafted titanium dioxide;
(3) Preparation of epoxidized polyhexamethylene diamido guanidine hydrochloride: 180mL of tetrahydrofuran solvent, 35g of polyhexamethylene diamido guanidine hydrochloride (PHMG), 30g of epoxy chloropropane and 0.45g of boron trifluoride diethyl ether complex are added into a reactor, after the mixture is stirred to be completely dissolved, the mixture is reacted for 6 hours at 60 ℃, 20g of sodium ethoxide is added into the system after the reaction is complete, the mixture is continuously reacted for 9 hours at 25 ℃, and the product is filtered, washed and dried to obtain epoxidized PHMG;
(4) PET grafted TiO 2 Preparation of PHMG composite master batch: adding PET grafted titanium dioxide and 0.06g of epoxidized PHMG into a reactor, fully and uniformly mixing, transferring into a torque rheometer, raising the temperature to 270 ℃, and reacting for 6min to obtain PET grafted TiO 2 -PHMG composite master batch;
(5)TiO 2 preparation of PHMG composite modified PET antibacterial fabric: adding PET grafted TiO into melt spinning equipment 2 PHMG composite master batch, setting screw section temperature to 283 ℃, 305 ℃, 293 ℃ and 293 ℃, metering pump temperature to 295 ℃, die temperature to 305 ℃, traction speed to 1000m/min, spinning to obtain TiO 2 -PHMG composite modified PET antibacterial fabric.
Example 4
(1) Preparation of acid chloride titanium dioxide: adding 210mL of dichloromethane solvent and 7g of nano titanium dioxide into a reactor, carrying out ultrasonic dispersion uniformly, continuously adding 21g of trimellitic chloride and 5mL of triethylamine, uniformly stirring, transferring into an oil bath, reacting at 45 ℃ for 28h, decompressing and distilling to remove the solvent after the reaction is finished, washing with dichloromethane, placing into a vacuum drying oven, and drying at 35 ℃ for 2h to obtain acyl chloride titanium dioxide;
(2) Preparation of polyethylene terephthalate (PET) grafted titanium dioxide: adding 90mL of dichloroethane solvent and 0.08g of titanium dioxide acyl chloride into a reactor, uniformly dispersing by ultrasonic, continuously adding 10g of PET, uniformly stirring by magnetic force, transferring into an oil bath kettle, reacting at 85 ℃ for 70 hours under the protection of nitrogen, and carrying out reduced pressure distillation, washing and drying after the reaction is finished to obtain PET grafted titanium dioxide;
(3) Preparation of epoxidized polyhexamethylene diamido guanidine hydrochloride: adding 210mL of tetrahydrofuran solvent, 40g of polyhexamethylene diamido guanidine hydrochloride (PHMG), 35g of epichlorohydrin and 0.52g of boron trifluoride diethyl ether complex into a reactor, stirring until the mixture is completely dissolved, reacting for 7 hours at 65 ℃, adding 25g of sodium ethoxide into a system after the reaction is complete, continuously reacting for 10 hours at 28 ℃, filtering, washing and drying the product to obtain epoxidized PHMG;
(4) PET grafted TiO 2 Preparation of PHMG composite master batch: adding PET grafted titanium dioxide and 0.07g of epoxidized PHMG into a reactor, fully and uniformly mixing, transferring into a torque rheometer, raising the temperature to 275 ℃, and reacting for 7min to obtain PET grafted TiO 2 -PHMG composite master batch;
(5)TiO 2 preparation of PHMG composite modified PET antibacterial fabric: adding PET grafted TiO into melt spinning equipment 2 PHMG composite master batch, setting the screw section temperature at 282 ℃, 305 ℃, 292 ℃ and 292 ℃, the metering pump temperature at 295 ℃, the die temperature at 305 ℃ and the traction speed at 1100m/min, spinning to obtain TiO 2 -PHMG composite modified PET antibacterial fabric.
Example 5
(1) Preparation of acid chloride titanium dioxide: adding 240mL of dichloromethane solvent and 8g of nano titanium dioxide into a reactor, carrying out ultrasonic dispersion uniformly, continuously adding 24g of trimesoyl chloride and 6mL of triethylamine, stirring uniformly, transferring into an oil bath kettle, reacting for 30h at 50 ℃, decompressing and distilling to remove the solvent after the reaction is finished, washing with dichloromethane, placing into a vacuum drying box, and drying for 3h at 40 ℃ to obtain acyl chloride titanium dioxide;
(2) Preparation of polyethylene terephthalate (PET) grafted titanium dioxide: adding 100mL of dichloroethane solvent and 0.1g of titanium dioxide acyl chloride into a reactor, uniformly dispersing by ultrasonic, continuously adding 10g of PET, uniformly stirring by magnetic force, transferring into an oil bath kettle, reacting at 90 ℃ for 76h under the protection of nitrogen, and carrying out reduced pressure distillation, washing and drying after the reaction is finished to obtain PET grafted titanium dioxide;
(3) Preparation of epoxidized polyhexamethylene diamido guanidine hydrochloride: adding 240mL of tetrahydrofuran solvent, 45g of polyhexamethylene diamido guanidine hydrochloride (PHMG), 40g of epichlorohydrin and 0.6g of boron trifluoride diethyl ether complex into a reactor, stirring until the mixture is completely dissolved, reacting for 8 hours at 70 ℃, adding 30g of sodium ethoxide into a system after the reaction is complete, continuously reacting for 12 hours at 30 ℃, filtering, washing and drying the product to obtain epoxidized PHMG;
(4) PET grafted TiO 2 Preparation of PHMG composite master batch: adding 10g of PET grafted titanium dioxide and 0.08g of epoxidized PHMG into a reactor, fully and uniformly mixing, transferring into a torque rheometer, raising the temperature to 280 ℃, and reacting for 8min to obtain PET grafted TiO 2 -PHMG composite master batch;
(5)TiO 2 preparation of PHMG composite modified PET antibacterial fabric: adding PET grafted TiO into melt spinning equipment 2 PHMG composite master batch, setting screw section temperature to 285 ℃, 310 ℃, 295 ℃ and 295 ℃, metering pump temperature to 300 ℃, die temperature to 310 ℃, traction speed to 1200m/min, spinning to obtain TiO 2 -PHMG composite modified PET antibacterial fabric.
Comparative example 1
(1) Preparation of acid chloride titanium dioxide: adding 90mL of dichloromethane solvent and 3g of nano titanium dioxide into a reactor, carrying out ultrasonic dispersion uniformly, continuously adding 9g of trimesoyl chloride and 1mL of triethylamine, stirring uniformly, transferring into an oil bath kettle, reacting for 15h at 25 ℃, decompressing and distilling to remove the solvent after the reaction is finished, washing with dichloromethane, placing into a vacuum drying box, and drying for 1h at 20 ℃ to obtain acyl chloride titanium dioxide;
(2)TiO 2 preparation of PHMG composite modified PET antibacterial fabric: 100g of PET and 0.1g of TiO were fed into a melt spinning apparatus 2 And 0.01g PHMG, setting screw section temperature to 270 ℃, 290 ℃, 280 ℃ and 280 ℃, metering pump temperature to 280 ℃, die temperature to 290 ℃, traction speed to 800m/min, spinning to obtain TiO 2 -PHMG composite modified PET antibacterial fabric.
The antibacterial fabrics of examples and comparative examples were cut into rectangular pieces of 6cm by 8cm in size and added to a sample containing 12mL of the antibacterial fabric at a concentration of 10 6 cfu/mL of E.coli bacterial suspension in the culture dish, placing the culture dish in a constant temperature incubator containing ultraviolet rays at 37 ℃, culturing for 15 hours, observing the colony count, and calculating the antibacterial rate, wherein an antibacterial fabric is not used as a blank control experiment.
Claims (7)
1. TiO (titanium dioxide) 2 -a preparation method of PHMG composite modified PET antibacterial fabric, which is characterized by comprising the following steps:
(1) Preparation of acid chloride titanium dioxide: adding nano titanium dioxide into a dichloromethane solvent, performing ultrasonic dispersion to be uniform, continuously adding trimesoyl chloride and triethylamine, stirring to be uniform, transferring into an oil bath, reacting for 20-30h at 30-50 ℃, performing reduced pressure distillation to remove the solvent after the reaction is finished, washing with dichloromethane, placing into a vacuum drying oven, and drying for 1-3h at 20-40 ℃ to obtain the acyl chloride titanium dioxide;
(2) Preparation of polyethylene terephthalate (PET) grafted titanium dioxide: adding titanium dioxide acyl chloride into dichloroethane solvent, dispersing uniformly by ultrasonic, continuously adding PET, stirring uniformly by magnetic force, transferring into an oil bath, raising the temperature for reaction, and carrying out reduced pressure distillation, washing and drying after the reaction is finished to obtain PET grafted titanium dioxide;
(3) Preparation of epoxidized polyhexamethylene diamido guanidine hydrochloride: adding 25-45g of polyhexamethylene diamido guanidine hydrochloride (PHMG), 20-40g of epoxy chloropropane and 0.3-0.6g of boron trifluoride diethyl etherate into 120-240mL of tetrahydrofuran solvent, stirring until the mixture is completely dissolved, reacting for 4-8 hours at 50-70 ℃, adding 10-30g of sodium ethoxide into the system after the reaction is complete, continuously reacting for 6-12 hours at 20-30 ℃, filtering, washing and drying the product to obtain the epoxidized PHMG;
(4) PET grafted TiO 2 Preparation of PHMG composite master batch: fully and uniformly mixing PET grafted titanium dioxide and epoxidized PHMG, adding the mixture into a torque rheometer, and raising the temperature to react to obtain PET grafted TiO 2 -PHMG composite master batch;
(5)TiO 2 preparation of PHMG composite modified PET antibacterial fabric: adding PET grafted TiO into melt spinning equipment 2 PHMG composite master batch, spinning after setting spinning parameters, obtaining TiO 2 -PHMG composite modified PET antibacterial fabric.
2. A TiO according to claim 1 2 -PHMG composite modified PET antibacterial fabric, characterized in that: the dosage ratio of the dichloromethane solvent, the nano titanium dioxide, the trimesoyl chloride and the triethylamine in the step (1) is 120-240mL, 4-8g, 12-24g and 2-6mL.
3. A TiO according to claim 1 2 -PHMG composite modified PET antibacterial fabric, characterized in that: the dosage ratio of the dichloroethane solvent, the titanium dioxide acyl chloride and the PET in the step (2) is 60-100mL:0.02-0.1g:10g.
4. A TiO according to claim 1 2 -PHMG composite modified PET antibacterial fabric, characterized in that: the temperature of the reaction in the step (2) is 70-90 ℃, and the reaction is carried out for 48-76h under the protection of nitrogen.
5. A TiO according to claim 1 2 -PHMG composite modified PET antibacterial fabric, characterized in that: the dosage ratio of the PET grafted titanium dioxide to the epoxidized PHMG in the step (4) is 10g:0.04-0.08g.
6. A TiO according to claim 1 2 -PHMG composite modified PET antibacterial fabric, characterized in that: the reaction temperature in the step (4) is 260-280 ℃ and the reaction time is 4-8min.
7. A TiO according to claim 1 2 -PHMG composite modified PET antibacterial fabric, characterized in that: the temperature of the screw section is set to 280-285 ℃, 300-310 ℃, 290-295 ℃ and 290-295 ℃ in the step (4), the temperature of the metering pump is set to 290-300 ℃, the temperature of the die is set to 300-310 ℃, and the traction speed is set to 900-1200m/min.
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