CN109610165B - Preparation method of antibacterial photocatalytic fibrilia - Google Patents
Preparation method of antibacterial photocatalytic fibrilia Download PDFInfo
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- CN109610165B CN109610165B CN201811191669.8A CN201811191669A CN109610165B CN 109610165 B CN109610165 B CN 109610165B CN 201811191669 A CN201811191669 A CN 201811191669A CN 109610165 B CN109610165 B CN 109610165B
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 43
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011941 photocatalyst Substances 0.000 claims abstract description 51
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 33
- 240000007817 Olea europaea Species 0.000 claims abstract description 32
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 32
- 229960003638 dopamine Drugs 0.000 claims abstract description 30
- 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 26
- 238000000034 method Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 73
- 239000000243 solution Substances 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 35
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 235000012239 silicon dioxide Nutrition 0.000 claims description 31
- 239000002105 nanoparticle Substances 0.000 claims description 28
- 238000002791 soaking Methods 0.000 claims description 21
- 239000004593 Epoxy Substances 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 15
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 230000010355 oscillation Effects 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000000835 fiber Substances 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 28
- 239000004408 titanium dioxide Substances 0.000 description 15
- 229920002521 macromolecule Polymers 0.000 description 9
- 239000005543 nano-size silicon particle Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical group 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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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
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/2246—Esters of unsaturated carboxylic acids
-
- 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
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the technical field of fibrilia, solves the problems of poor fiber photocatalytic performance and short service life of the fiber caused by oxidative degradation of a photocatalyst on the fiber, and discloses a preparation method of an antibacterial photocatalytic fibrilia. The method comprises the steps of firstly carrying out steam opening treatment on fibrilia, then immersing the fibrilia into an olive polyphenol extract solution, taking out the fibrilia, immersing the fibrilia into a dopamine solution to carry out a crosslinking reaction to form a layer of three-dimensional crosslinked reticular structure on the surface of the fibrilia, then immersing the fibrilia into a trimesoyl chloride solution, hydrolyzing the trimesoyl chloride to introduce carboxyl, and connecting the fibrilia on the surface of the fibrilia by utilizing the coordination effect of the carboxyl and a photocatalyst. The fibrilia prepared by the invention has stronger photocatalytic performance, the photocatalyst can not cause oxidation damage to the fibrilia, and the service life is longer.
Description
Technical Field
The invention relates to the technical field of fibrilia, in particular to a preparation method of antibacterial photocatalytic fibrilia.
Background
The photocatalysis is a method for degrading pollutants with energy saving, which can completely and effectively degrade pollutants by using sunlight, the photocatalysis material is a substance which can be excited by surrounding oxygen and water molecules into free negative ions with high oxidizing capability and can promote chemical reaction without changing the photocatalysis material, and the photocatalysis material has the functions of antibacterial property, air purification, deodorization, mildew prevention, algae prevention, antifouling and self cleaning, and can almost decompose all organic substances harmful to human body, namely part of inorganic substances. Meanwhile, the photocatalytic material has extremely high safety and can even be used as a food and drug additive, and meanwhile, the photocatalytic material only provides a reaction site, does not participate in chemical reaction and has good durability. In the prior art, substances with photocatalytic function are combined with fibers, and the fibers are used as carriers to catalyze and degrade pollutants, for example, Chinese patent publication No. CN106012071 discloses continuous cellulose/TiO with photocatalytic performance2Preparing cellulose into spinning solution, adding titanium dioxide photocatalyst, adding acid solution, ethanol solution or acetone solution as coagulating bath into coagulating bath, adding the spinning solution with titanium dioxide photocatalyst into the coagulating bath, wet spinning to obtain cellulose gel fiber containing titanium dioxide photocatalyst, winding the fiber, immersing in aging solution, aging at normal temperature, and removingWashing the seed with water to neutrality, then carrying out solvent replacement, and drying to obtain the product. In the technical scheme that this patent is disclosed, directly mix into the spinning solution with titanium dioxide of photocatalytic performance, then through the spinning, the solidification shaping, because most titanium dioxide is located fibrous inside in the shaping back fibre, the titanium dioxide volume on fibre surface is less, not only fibre photocatalytic performance is not good, still extravagant more titanium dioxide raw materials, in addition because titanium dioxide has extremely strong oxidation behavior under the illumination, titanium dioxide and fibre direct contact can cause fibrous oxidation, the fracture of the inside chemical bond of fibre, thereby lead to fibrous mechanical properties to worsen, shorten fibrous life.
Disclosure of Invention
The invention aims to solve the problems of poor fiber photocatalytic performance and short service life of fibers caused by oxidative degradation of a photocatalyst on the fibers in the prior art, and provides a preparation method of antibacterial photocatalytic fibrilia.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of antibacterial photocatalytic fibrilia comprises the following steps:
1) adding dopamine and ammonium persulfate into a Tris-HCl buffer solution with the pH value of 8.2-8.5 according to the mass ratio of 1:0.2-0.5, and stirring and dissolving to obtain a dopamine solution for later use;
2) dissolving the olive polyphenol extract in 60-85% ethanol water solution to obtain olive polyphenol extract solution;
3) soaking fibrilia in water for 2-5h, performing high temperature steam treatment for 10-20min, immediately soaking the fibrilia in olive polyphenol extract solution after distillation treatment is finished, performing ultrasonic oscillation for 5-10min, taking out the fibrilia, soaking the fibrilia in dopamine solution, and reacting at 50-65 ℃ for 5-10h to obtain fibrilia a;
4) immersing the fibrilia a into a trimesoyl chloride solution with the mass concentration of 0.4-0.8%, and reacting for 1-2min to obtain fibrilia b;
5) adding the modified titanium dioxide photocatalyst and the dispersing agent into water, stirring uniformly to form a dispersion liquid, then immersing the fibrilia b into the dispersion liquid, reacting for 3-5h at 40-50 ℃, taking out, washing with deionized water, and drying to obtain the antibacterial photocatalytic fibrilia.
The invention firstly carries out steam opening treatment on the fibrilia to destroy the surface structure of the fibrilia, so that the olive polyphenol extract enters the interior of the fibrilia and is attached to the surface of the fibrilia under the action of ultrasonic waves, and then the fibrilia is immersed in a dopamine solution, because dopamine has more active group amino groups and more active phenolic hydroxyl groups on molecules of the olive polyphenol extract, the dopamine is subjected to self-polymerization and cross-linking with molecules of the olive polyphenol extract under the action of an oxidant ammonium sulfate, so that a layer of three-dimensional cross-linked network structure macromolecules is polymerized on the surface of the fibrilia, the three-dimensional cross-linked network structure macromolecules have stronger stability, stronger stability and better heat resistance and antioxidation effects, are not easy to degrade under the action of a photocatalyst, and are not easy to fall off from the surface of the fibrilia even if partial degradation occurs, the fibrilia is subjected to steam treatment before the fibrilia is modified, so that the fibrilia is in a loose state, the olive polyphenol extract enters the interior of the fibrilia, and after the olive polyphenol extract and dopamine are polymerized and crosslinked, a part of polymer is embedded into the interior of the fibrilia, so that the bonding strength of three-dimensional crosslinked network structure macromolecules and the fibrilia is increased, and the fibrilia is not easy to fall off from the surface of the fibrilia; on the other hand, the olive polyphenol extract has higher activity and stronger bactericidal action, and inhibits the growth and the reproduction of bacteria on fibers, thereby preventing the decomposition and the damage of the bacteria on the fibers and polymers.
The three-dimensional cross-linked network structure molecules generated by the reaction of the olive polyphenol extract and dopamine have more amino groups and hydroxyl groups with stronger activity, the amino groups and the hydroxyl groups can perform affinity substitution reaction with acyl chloride groups on trimesoyl chloride, the trimesoyl chloride is grafted to the three-dimensional cross-linked network structure molecules, and the unreacted acyl chloride groups in the trimesoyl chloride are hydrolyzed in waterActing to generate carboxyl which can react with Ti in the photocatalyst titanium dioxide4+The coordination action is generated, so that the photocatalyst is connected to the surface of the fibrilia, and the fibrilia has the photocatalytic performance. Compared with the prior art (introduced in the background technology), because the photocatalyst is connected to the surface of the fibrilia, compared with the method that the photocatalyst is mixed in the fiber and embedded into the surface of the fiber, the contact area of the photocatalyst and air is greatly increased, so that the photocatalytic efficiency is increased, and the dosage of the photocatalyst is saved. In addition, the three-dimensional cross-linked network-structure macromolecules generated by the reaction of the olive polyphenol extract and dopamine have high stability, and the surface of the fibrilia can be used as a layer of protective film to prevent the photocatalyst from contacting the fibrilia, so that the oxidative degradation of the fibrilia is prevented, and the service life of the fibrilia is prolonged.
Preferably, the solubility of the dopamine solution in the step 1) is 2-5 wt%.
Preferably, the concentration of the olive polyphenol extract solution in the step 2) is 5-15 wt%.
Preferably, the ultrasonic oscillation power in the step 3) is 100-200W.
Preferably, the solvent in the trimesoyl chloride solution in the step 4) is one of n-hexane, toluene and cyclohexane.
Preferably, in the step 5), the addition amount of the modified titanium dioxide photocatalyst is 5-10wt% of water, and the addition amount of the dispersant is 0.5-1wt% of water.
Preferably, the dispersant in the step 5) is at least one of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and water glass.
Preferably, the preparation method of the modified titanium dioxide photocatalyst in the step 5) comprises the following steps:
adding rod-shaped silicon dioxide nano particles into water, stirring and mixing uniformly to form a suspension, adding titanium sulfate into the suspension, wherein the mass ratio of the titanium sulfate to the rod-shaped silicon dioxide nano particles is 1:0.3-0.6, stirring and reacting for 2-5h at the temperature of 80-85 ℃, then adding an epoxy silane coupling agent, stirring for 10-20min, standing for 30-50min, evaporating at the temperature of 85-95 ℃, and drying to obtain the modified titanium dioxide photocatalyst.
Titanium sulfate is heated in water to generate nano titanium dioxide precipitate, so that nano titanium dioxide is combined on the surface of rodlike nano silicon dioxide, the rodlike nano silicon dioxide is used as a secondary carrier of photocatalyst titanium dioxide, the rodlike nano silicon dioxide is an inorganic material, the oxidability of the photocatalyst can not damage the rodlike nano silicon dioxide, then the rodlike nano silicon dioxide is connected to macromolecules of a three-dimensional cross-linked net structure on the surface of fibrilia by using an epoxy silane coupling agent (the alkoxy of the epoxy silane coupling agent is connected with the rodlike nano silicon dioxide, the open loop of an epoxy group at the other end reacts with carboxyl generated by hydrolysis of trimesoyl chloride on the macromolecules of the three-dimensional cross-linked net structure, so that the photocatalyst is connected to the fibrilia), and at the moment, the: firstly, the direct bonding function of the epoxy silane coupling agent; second, Ti in titanium dioxide4+The coordination function is formed by carboxyl generated by the hydrolysis of trimesoyl chloride on macromolecules with a three-dimensional cross-linked network structure on the surface of the fibrilia; thereby greatly improving the binding force between the photocatalyst and the fibrilia and ensuring that the photocatalyst is not easy to fall off from the fiber. Because the titanium dioxide is attached to the rodlike nano silicon dioxide, the contact between titanium dioxide particles and macromolecules of the three-dimensional cross-linked network structure is reduced, the oxidation effect of the photocatalyst on the three-dimensional cross-linked network structure is weakened, and the stability of the whole body is further improved; it should be noted that the technical effect of the present invention cannot be achieved by using nano-silica with other shapes, such as granular nano-silica, as the secondary carrier of the photocatalyst, because the titanium dioxide on the granular nano-silica carrier is easy to contact with the macromolecules of the three-dimensional cross-linked network structure, thereby having a certain influence on the stability of the three-dimensional cross-linked network structure.
Preferably, the amount of the silica nanoparticles added is 15 to 20wt% of water.
Preferably, the mass ratio of the epoxy silane coupling agent to the rod-shaped silica nanoparticles is 1: 15-20.
Therefore, the invention has the following beneficial effects:
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
The preparation method of the modified titanium dioxide photocatalyst comprises the following steps:
adding rod-shaped silicon dioxide nano particles into water, stirring and mixing uniformly to form a suspension, adding the rod-shaped silicon dioxide nano particles in an amount which is 18 wt% of the water, then adding titanium sulfate into the suspension, wherein the mass ratio of the titanium sulfate to the rod-shaped silicon dioxide nano particles is 1:0.45, stirring and reacting for 3 hours at 83 ℃, adding an epoxy silane coupling agent according to the mass ratio of the epoxy silane coupling agent to the rod-shaped silicon dioxide nano particles which is 1:18, stirring for 15 minutes, standing for 40 minutes, evaporating at 90 ℃, and drying to obtain the modified titanium dioxide photocatalyst.
A preparation method of antibacterial photocatalytic fibrilia comprises the following steps:
1) adding dopamine and ammonium persulfate into a Tris-HCl buffer solution with the pH value of 8.3 according to the mass ratio of 1:0.4, stirring and dissolving to obtain a dopamine solution with the solubility of 3.5 wt% for later use;
2) dissolving the olive polyphenol extract in 70% ethanol water solution to prepare 10wt% olive polyphenol extract solution for later use;
3) soaking fibrilia in water for 3h, then performing high-temperature steam treatment for 15min, immediately soaking the fibrilia in an olive polyphenol extract solution after the distillation treatment is finished, performing ultrasonic oscillation for 8min at the power of 150W, taking out the fibrilia, soaking the fibrilia in a dopamine solution, and reacting for 8h at the temperature of 60 ℃ to obtain fibrilia a;
4) dissolving trimesoyl chloride in a normal hexane solvent to prepare a 0.6 wt% trimesoyl chloride solution, immersing the fibrilia a in the trimesoyl chloride solution, and reacting for 1.5min to obtain fibrilia b;
5) adding a modified titanium dioxide photocatalyst and a dispersant sodium tripolyphosphate into water, wherein the addition amount of the modified titanium dioxide photocatalyst is 8 wt% of the water, the addition amount of the dispersant is 0.7 wt% of the water, uniformly stirring to form a dispersion solution, then immersing the fibrilia b into the dispersion solution, reacting for 4 hours at 45 ℃, taking out, washing with deionized water, and drying to obtain the antibacterial photocatalytic fibrilia.
Example 2
The preparation method of the modified titanium dioxide photocatalyst comprises the following steps:
adding rod-shaped silicon dioxide nano particles into water, stirring and mixing uniformly to form a suspension, adding the rod-shaped silicon dioxide nano particles in an amount of 16 wt% of the water, then adding titanium sulfate into the suspension, wherein the mass ratio of the titanium sulfate to the rod-shaped silicon dioxide nano particles is 1:0.35, stirring and reacting for 2.5 hours at 81 ℃, adding an epoxy silane coupling agent according to the mass ratio of the epoxy silane coupling agent to the rod-shaped silicon dioxide nano particles of 1:16, stirring for 12 minutes, standing for 35 minutes, evaporating at 86 ℃, and drying to obtain the modified titanium dioxide photocatalyst.
A preparation method of antibacterial photocatalytic fibrilia comprises the following steps:
1) adding dopamine and ammonium persulfate into a Tris-HCl buffer solution with the pH value of 8.2 according to the mass ratio of 1:0.25, stirring and dissolving to obtain a dopamine solution with the solubility of 2.5 wt% for later use;
2) dissolving the olive polyphenol extract in 70% ethanol water solution to prepare 6 wt% olive polyphenol extract solution for later use;
3) soaking fibrilia in water for 2.5h, then performing high-temperature steam treatment for 12min, immediately soaking the fibrilia in an olive polyphenol extract solution after the distillation treatment is finished, performing ultrasonic oscillation for 6min at the power of 100W, taking out the fibrilia, soaking the fibrilia in a dopamine solution, and reacting at 52 ℃ for 6h to obtain fibrilia a;
4) dissolving trimesoyl chloride in a toluene solvent to prepare 0.5 wt% of trimesoyl chloride solution, immersing the fibrilia a in the trimesoyl chloride solution, and reacting for 1.5min to obtain fibrilia b;
5) adding a modified titanium dioxide photocatalyst and a dispersing agent sodium hexametaphosphate into water, wherein the addition amount of the modified titanium dioxide photocatalyst is 6 wt% of the water, the addition amount of the dispersing agent is 0.6 wt% of the water, uniformly stirring to form a dispersion liquid, then immersing the fibrilia b into the dispersion liquid to react for 3.5h at 41 ℃, taking out, washing with deionized water, and drying to obtain the antibacterial photocatalytic fibrilia.
Example 3
The preparation method of the modified titanium dioxide photocatalyst comprises the following steps:
adding rod-shaped silicon dioxide nano particles into water, stirring and mixing uniformly to form a suspension, adding the rod-shaped silicon dioxide nano particles in an amount which is 18 wt% of the water, then adding titanium sulfate into the suspension, wherein the mass ratio of the titanium sulfate to the rod-shaped silicon dioxide nano particles is 1:0.5, stirring and reacting for 4.5 hours at 84 ℃, adding an epoxy silane coupling agent according to the mass ratio of the epoxy silane coupling agent to the rod-shaped silicon dioxide nano particles which is 1:19, stirring for 18 minutes, standing for 45 minutes, evaporating at 92 ℃, and drying to obtain the modified titanium dioxide photocatalyst.
A preparation method of antibacterial photocatalytic fibrilia comprises the following steps:
1) adding dopamine and ammonium persulfate into a Tris-HCl buffer solution with the pH value of 8.4 according to the mass ratio of 1:0.45, stirring and dissolving to obtain a dopamine solution with the solubility of 4.5 wt% for later use;
2) dissolving the olive polyphenol extract in 70% ethanol water solution to prepare 12 wt% olive polyphenol extract solution for later use;
3) soaking fibrilia in water for 4.5h, then performing high-temperature steam treatment for 18min, immediately soaking the fibrilia in an olive polyphenol extract solution after the distillation treatment is finished, performing ultrasonic oscillation for 9min at the power of 180W, taking out the fibrilia, soaking the fibrilia in a dopamine solution, and reacting at 63 ℃ for 8h to obtain fibrilia a;
4) dissolving trimesoyl chloride in a cyclohexane solvent to prepare 0.7 wt% of trimesoyl chloride solution, immersing the fibrilia a in the trimesoyl chloride solution, and reacting for 2min to obtain fibrilia b;
5) adding a modified titanium dioxide photocatalyst and a dispersant sodium pyrophosphate into water, wherein the addition amount of the modified titanium dioxide photocatalyst is 9 wt% of the water, the addition amount of the dispersant is 0.8 wt% of the water, uniformly stirring to form a dispersion solution, then immersing the fibrilia b into the dispersion solution, reacting for 4.5h at 48 ℃, taking out, washing with deionized water, and drying to obtain the antibacterial photocatalytic fibrilia.
Example 4
The preparation method of the modified titanium dioxide photocatalyst comprises the following steps:
adding rod-shaped silicon dioxide nano particles into water, stirring and mixing uniformly to form a suspension, adding the rod-shaped silicon dioxide nano particles in an amount which is 20wt% of the water, then adding titanium sulfate into the suspension, wherein the mass ratio of the titanium sulfate to the rod-shaped silicon dioxide nano particles is 1: 0.6, stirring and reacting for 5 hours at 85 ℃, adding an epoxy silane coupling agent according to the mass ratio of the epoxy silane coupling agent to the rod-shaped silicon dioxide nano particles which is 1:20, stirring for 20 minutes, standing for 50 minutes, evaporating at 95 ℃, and drying to obtain the modified titanium dioxide photocatalyst.
A preparation method of antibacterial photocatalytic fibrilia comprises the following steps:
1) adding dopamine and ammonium persulfate into a Tris-HCl buffer solution with the pH value of 8.5 according to the mass ratio of 1:0.5, stirring and dissolving to obtain a dopamine solution with the solubility of 5wt% for later use;
2) dissolving the olive polyphenol extract in 85% ethanol water solution to prepare 15wt% olive polyphenol extract solution for later use;
3) soaking fibrilia in water for 5h, then performing high-temperature steam treatment for 20min, immediately soaking the fibrilia in an olive polyphenol extract solution after the distillation treatment is finished, performing ultrasonic oscillation for 10min at the power of 200W, taking out the fibrilia, soaking the fibrilia in a dopamine solution, and reacting for 10h at 65 ℃ to obtain fibrilia a;
4) dissolving trimesoyl chloride in a normal hexane solvent to prepare a 0.8 wt% trimesoyl chloride solution, immersing fibrilia a in the trimesoyl chloride solution, and reacting for 2min to obtain fibrilia b;
5) adding a modified titanium dioxide photocatalyst and a dispersant water glass into water, wherein the addition amount of the modified titanium dioxide photocatalyst is 10wt% of the water, the addition amount of the dispersant is 1wt% of the water, uniformly stirring to form a dispersion solution, then immersing the fibrilia b into the dispersion solution, reacting for 5 hours at 50 ℃, taking out, washing with deionized water, and drying to obtain the antibacterial photocatalytic fibrilia.
Example 5
The preparation method of the modified titanium dioxide photocatalyst comprises the following steps:
adding rod-shaped silicon dioxide nano particles into water, stirring and mixing uniformly to form a suspension, adding the rod-shaped silicon dioxide nano particles in an amount of 15wt% of the water, then adding titanium sulfate into the suspension, wherein the mass ratio of the titanium sulfate to the rod-shaped silicon dioxide nano particles is 1:0.3, stirring and reacting for 2 hours at 80 ℃, adding an epoxy silane coupling agent according to the mass ratio of the epoxy silane coupling agent to the rod-shaped silicon dioxide nano particles of 1:15, stirring for 10 minutes, standing for 30 minutes, evaporating at 85 ℃, and drying to obtain the modified titanium dioxide photocatalyst.
A preparation method of antibacterial photocatalytic fibrilia comprises the following steps:
1) adding dopamine and ammonium persulfate into a Tris-HCl buffer solution with the pH value of 8.2 according to the mass ratio of 1:0.2, stirring and dissolving to obtain a dopamine solution with the solubility of 2 wt% for later use;
2) dissolving the olive polyphenol extract in 60% ethanol water solution to prepare 5wt% olive polyphenol extract solution for later use;
3) soaking fibrilia in water for 2h, then performing high-temperature steam treatment for 10min, immediately soaking the fibrilia in an olive polyphenol extract solution after the distillation treatment is finished, performing ultrasonic oscillation for 5min at the power of 100W, taking out the fibrilia, soaking the fibrilia in a dopamine solution, and reacting for 5h at 50 ℃ to obtain fibrilia a;
4) dissolving trimesoyl chloride in a toluene solvent to prepare 0.4 wt% of trimesoyl chloride solution, immersing the fibrilia a in the trimesoyl chloride solution, and reacting for 1min to obtain fibrilia b;
5) adding a modified titanium dioxide photocatalyst and a dispersant sodium tripolyphosphate into water, wherein the addition amount of the modified titanium dioxide photocatalyst is 5wt% of the water, the addition amount of the dispersant is 0.5 wt% of the water, uniformly stirring to form a dispersion solution, then immersing the fibrilia b into the dispersion solution, reacting for 3 hours at 40 ℃, taking out, washing with deionized water, and drying to obtain the antibacterial photocatalytic fibrilia.
Test and test:
respectively irradiating rhodamine B dye and methylene blue dye with the dye concentration of 6ppm for 1h by using ultraviolet radiation, and then detecting the degradation efficiency of pollutants, wherein the wavelength of the used ultraviolet is 365nm, and the radiation flux density is 7.6mw/cm2The amount of the fiber photocatalyst used was 1 g/L.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the antibacterial photocatalytic fibrilia is characterized by comprising the following steps of:
1) adding dopamine and ammonium persulfate into a Tris-HCl buffer solution with the pH value of 8.2-8.5 according to the mass ratio of 1:0.2-0.5, and stirring and dissolving to obtain a dopamine solution for later use;
2) dissolving the olive polyphenol extract in 60-85% ethanol water solution to obtain olive polyphenol extract solution;
3) soaking fibrilia in water for 2-5h, performing high temperature steam treatment for 10-20min, immediately soaking the fibrilia in olive polyphenol extract solution after distillation treatment is finished, performing ultrasonic oscillation for 5-10min, taking out the fibrilia, soaking the fibrilia in dopamine solution, and reacting at 50-65 ℃ for 5-10h to obtain fibrilia a;
4) immersing the fibrilia a into a trimesoyl chloride solution with the mass concentration of 0.4-0.8%, and reacting for 1-2min to obtain fibrilia b;
5) adding the modified titanium dioxide photocatalyst and the dispersing agent into water, stirring uniformly to form a dispersion liquid, then immersing the fibrilia b into the dispersion liquid, reacting for 3-5h at 40-50 ℃, taking out, washing with deionized water, and drying to obtain the antibacterial photocatalytic fibrilia.
2. The method for preparing antibacterial photocatalytic fibrilia according to claim 1, wherein the solubility of the dopamine solution in step 1) is 2-5 wt%.
3. The method for preparing antibacterial photocatalytic fibrilia as claimed in claim 1, wherein the concentration of the olive polyphenol extract solution in the step 2) is 5-15 wt%.
4. The method for preparing antibacterial photocatalytic fibrilia as claimed in claim 1, wherein the ultrasonic oscillation power in step 3) is 100-200W.
5. The method for preparing antibacterial photocatalytic fibrilia according to claim 1, wherein the solvent in the trimesoyl chloride solution in the step 4) is one of n-hexane, toluene and cyclohexane.
6. The method for preparing antibacterial photocatalytic fibrilia as claimed in claim 1, wherein in the step 5), the addition amount of the modified titanium dioxide photocatalyst is 5-10wt% of water, and the addition amount of the dispersant is 0.5-1wt% of water.
7. The method for preparing antibacterial photocatalytic fibrilia as claimed in claim 1, wherein the dispersant in step 5) is at least one of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and water glass.
8. The method for preparing antibacterial photocatalytic fibrilia as claimed in claim 1, wherein the method for preparing the modified titanium dioxide photocatalyst in step 5) comprises the following steps:
adding rod-shaped silicon dioxide nano particles into water, stirring and mixing uniformly to form a suspension, adding titanium sulfate into the suspension, wherein the mass ratio of the titanium sulfate to the rod-shaped silicon dioxide nano particles is 1:0.3-0.6, stirring and reacting for 2-5h at the temperature of 80-85 ℃, then adding an epoxy silane coupling agent, stirring for 10-20min, standing for 30-50min, evaporating at the temperature of 85-95 ℃, and drying to obtain the modified titanium dioxide photocatalyst.
9. The method for preparing antibacterial photocatalytic fibrilia as claimed in claim 8, wherein the rod-like silica nanoparticles are added in an amount of 15-20wt% based on water.
10. The preparation method of the antibacterial photocatalytic fibrilia as claimed in claim 8, wherein the mass ratio of the epoxy silane coupling agent to the rod-like silica nanoparticles is 1: 15-20.
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| CN106215717A (en) * | 2016-08-05 | 2016-12-14 | 浙江理工大学 | A kind of preparation method of compound PVDF ultrafiltration membrane |
| CN108380063A (en) * | 2018-02-27 | 2018-08-10 | 天津大学 | A kind of preparation method of nano titanium dioxide hybrid composite nanometer filtering film |
| CN109012188A (en) * | 2018-09-09 | 2018-12-18 | 郑州成济堂生物科技有限公司 | A kind of preparation method of high-flux composite nanofiltration membrane |
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| CN102153779A (en) * | 2011-03-04 | 2011-08-17 | 浙江理工大学 | Anti-aging method for polymer materials |
| CN106215717A (en) * | 2016-08-05 | 2016-12-14 | 浙江理工大学 | A kind of preparation method of compound PVDF ultrafiltration membrane |
| CN108380063A (en) * | 2018-02-27 | 2018-08-10 | 天津大学 | A kind of preparation method of nano titanium dioxide hybrid composite nanometer filtering film |
| CN109012188A (en) * | 2018-09-09 | 2018-12-18 | 郑州成济堂生物科技有限公司 | A kind of preparation method of high-flux composite nanofiltration membrane |
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