CN113463398A - Preparation method of black hole external composite functional powder and textile after-finishing liquid - Google Patents

Preparation method of black hole external composite functional powder and textile after-finishing liquid Download PDF

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CN113463398A
CN113463398A CN202110760056.7A CN202110760056A CN113463398A CN 113463398 A CN113463398 A CN 113463398A CN 202110760056 A CN202110760056 A CN 202110760056A CN 113463398 A CN113463398 A CN 113463398A
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composite functional
combination
copper
functional powder
black hole
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张春明
冉伟
徐荣
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Juzhi Suzhou Nano Technology Co ltd
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Juzhi Suzhou Nano Technology Co ltd
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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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • D06M11/83—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 metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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    • 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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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D06M13/5135—Unsaturated compounds containing silicon atoms
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    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/02—Processes in which the treating agent is releasably affixed or incorporated into a dispensing means
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

Abstract

The invention provides a preparation method of black hole appearance composite functional powder and a textile after-finishing liquid. Manganese, copper and zinc compounds are prepared into a stable complex ion symbiont by using a high-efficiency complexing agent, and then grafted on the surface of a weak photocatalyst by using Schiff base ligand groups containing N, O and S to form composite functional powder with a black hole shape and a hollow interior; selecting a proper dispersing auxiliary agent, a viscosity reducing auxiliary agent and deionized water for premixing, dispersing by shearing force and centrifugal force of a grinding machine, and adding a special complex ion protection auxiliary agent when the average particle size reaches below 100nm to form a high-concentration water-based composite functional dispersion liquid with controllable particle size; mixing with special high molecular resin, silane coupling agent and surface tension promoter to obtain the final product with antibacterial and antiviral effects. The thin layer composite functional coating is solidified on the surface of the base materials such as fiber, fabric, non-woven fabric and the like by adopting a rolling drying process, and has good killing effect on bacteria and viruses.

Description

Preparation method of black hole external composite functional powder and textile after-finishing liquid
Technical Field
The invention belongs to the field of composite functional materials, and particularly relates to a preparation method of black hole shape composite functional powder and a textile after-finishing liquid.
Background
Photocatalysts, as a broad-spectrum antibacterial disinfectant, have been widely used in human production life because they can dissociate free-moving negatively-charged electrons while leaving positively-charged holes under the excitation of light. The cavity can activate oxygen in the air to become active oxygen, has strong chemical activity, and can generate oxidation reaction (including organic matters in bacteria and viruses) with various organic matters, thereby killing most of germs and viruses. Nevertheless, due to the superior transmission of the current variant new coronaviruses, their antibacterial and antiviral properties still do not meet the current needs.
Therefore, the invention grafts the manganese, copper and zinc compounds on the surface of the weak photocatalyst through Schiff base ligand groups containing N, O and S. However, it is known that it is difficult to complex the three metal ions of manganese, copper and zinc uniformly at the same time, which can seriously affect the sterilization effect of the final product. The invention creatively optimizes groups respectively suitable for complexing three metal ions, and achieves the effect of simultaneously complexing three metal ions of manganese, copper and zinc with high efficiency by synthesizing a high-molecular high-efficiency complexing agent.
Secondly, it is known that during the process of light sterilization, the photocatalyst is also easy to generate superoxide radical with strong oxidation capability, and the radical may cause the stability of the manganese-copper-zinc complex ion symbiont to be reduced, and finally the antibacterial and antivirus effects are affected. In order to solve the problem, the invention creatively synthesizes a complex ion protection auxiliary agent, an asymmetric vesicle formed by the protection auxiliary agent is utilized, and the asymmetric vesicle is utilized to coat the manganese-copper-zinc complex ion intergrowth to form a protective film with a core-shell structure, so that the manganese-copper-zinc complex ion intergrowth and the protective film are mutually independent and can mutually coexist, and the stability of the manganese-copper-zinc complex ion intergrowth can be improved under the condition of ensuring the sterilizing and disinfecting capability to be unchanged by utilizing the synergistic effect.
The black hole shape composite functional powder material and the special structure thereof developed by the patent have excellent capability of adsorbing bacteria and viruses, simultaneously initiate ROS and synergistic enhancement effect, generate high active oxygen and free radicals to be adhered to the surfaces of the viruses, destroy the structures and functions of virus proteins and nucleic acids, and can quickly inactivate the captured bacteria and viruses by a contact catalytic antibacterial antiviral mechanism. The textile after-finishing liquid developed by the material also has excellent sterilization and disinfection effects, and can be widely applied to the fields of disinfection, protection, construction, textile, plastics, medical treatment and the like.
Disclosure of Invention
The invention provides a preparation method of black hole shape composite functional powder and textile after-finishing liquid, which comprises the following steps:
(1) synthesizing an efficient metal ion complexing agent: weighing a certain amount of complexing agent precursor, dissolving the complexing agent precursor into deionized water, then adjusting the pH value of the solution by using a sodium hydroxide solution, and then adding a certain amount of copper sulfate into the mixed solution in the stirring process. After full reaction, adding a certain amount of aldehyde solution and sodium carbonate into the solution, and reacting for a period of time at a certain temperature in a water bath. Then adding a certain amount of alcohol solution into the reaction solution, standing for a period of time in a refrigerator, and separating out crystals, namely the high-efficiency metal ion complexing agent;
(2) preparing a complex ion symbiont: respectively weighing a certain amount of the high-efficiency metal ion complexing agent prepared in the step (1), a manganese compound, a copper compound, a zinc compound and deionized water, stirring and heating to prepare a stable complexing manganese-copper-zinc ion symbiont;
(3) preparing composite functional powder: weighing a certain amount of the steady-state complex manganese copper zinc ion intergrowth prepared in the step (2), Schiff base ligand groups containing N, O and S, weak photocatalyst powder (high-efficiency nano weak photocatalyst with tungsten zinc crystal lattices doped with each other, precious metal graphene-supported manganese zinc-based weak photocatalyst, porous graphene-supported weak photocatalyst and the like), deionized water, stirring, and spray drying to obtain black hole shape composite functional powder;
(4) pre-dispersing: weighing a certain amount of the composite functional powder prepared in the step (3), premixing the composite functional powder with a dispersing aid, a viscosity reduction aid and deionized water, and pre-dispersing by using the shearing force and the centrifugal force of zirconium beads in a grinding machine;
(5) preparing a complex ion protection auxiliary agent: a) adding a certain amount of sodium hydroxide, mercaptan, alkyl ammonium chloride and acetone into a jacket reactor, adding carbon disulfide and chloroform after the sodium hydroxide, the mercaptan, the alkyl ammonium chloride and the acetone are fully and uniformly mixed, and reacting for a period of time at a certain temperature under the protection of nitrogen. Adjusting the pH value of the solution by using hydrochloric acid, then distilling the solution under reduced pressure to remove acetone, and filtering the solution to obtain a crystal A; b) adding the prepared crystal A into dichloromethane, and adding polyalkyl ether, alkyl pyridine and alkyl imine into the solution. Stirring the mixture at a certain temperature for esterification reaction for a period of time, and filtering the mixture to obtain a solid B; c) and dissolving the prepared solid B and alkylamide into a certain amount of solvent, uniformly stirring, adding a certain amount of initiator, reacting for a period of time at a certain temperature in a water bath, evaporating the solvent to dryness, and preparing the complex ion protection auxiliary agent.
(6) Preparing a composite functional dispersion liquid: when the average particle size of the dispersion in the step (4) is less than 100nm, adding the complex ion protection auxiliary agent prepared in the step (5) to prepare stable high-concentration water-based composite functional dispersion with controllable particle size;
(7) and (4) mixing the aqueous composite functional dispersion liquid prepared in the step (6) with special high polymer resin, a silane coupling agent and a surface tension promoter according to a proportion, emulsifying and stirring to prepare the water-fast textile after-finishing liquid with the antibacterial and antiviral functions.
Preferably, the complexing agent precursor in the step (1) is one of N- (phosphonomethyl) glycine, ethyl thiooxamide, N-isovaleroacetic acid, glyphosate, ethyl thiooxamide, ethyl N-phenyl glycine ether, ethyl chlorohydroxyimino acetate or a combination thereof.
Preferably, the aldehyde solution in the step (1) is one of or a combination of an aqueous formaldehyde solution, an aqueous acetaldehyde solution, an alcoholic benzaldehyde solution, an alcoholic phenylacetaldehyde solution and an alcoholic lauraldehyde solution.
Preferably, the alcoholic solution in step (1) is one or a combination of ethanol, propanol, ethylene glycol and methanol.
Preferably, in the step (1), the complexing agent precursor: deionized water: copper sulfate: aldehyde solution: sodium carbonate: the mass ratio of the alcoholic solution is 1: (1-100): (0.1-10): (0.1-10): (0.1-10): (0.5 to 100).
Preferably, the pH value in the step (1) is 9-14.
Preferably, the reaction temperature of the water bath kettle in the step (1) is 65-95 ℃.
Preferably, the water bath reaction time in the step (1) is 1-10 h.
Preferably, the refrigerator standing temperature in the step (1) is 1-10 ℃.
Preferably, the standing time in the step (1) is 12-48 h.
Preferably, the manganese compound in the step (2) is one of manganese nitrate, manganous chloride, manganese sulfate and manganese oxide or a combination thereof.
Preferably, the copper compound in the step (2) is one of copper sulfate, copper chloride, copper (II) bis-oxime tetranuclear picrate, copper oxide, copper hydroxide, copper complex amino acid or a combination thereof.
Preferably, the zinc compound in the step (2) is one of zinc oxide, titanium-doped zinc oxide, aluminum-doped zinc oxide, silicon-doped zinc oxide or a combination thereof.
Preferably, the high-efficiency metal ion complexing agent in the step (2): a manganese compound: copper compound: a zinc compound: the mass ratio of the deionized water is (1-5): (0.01-1): (0.01-1): 1: (3-15).
Preferably, the heating temperature in the step (2) is 50-90 ℃.
Preferably, the Schiff base ligand containing N, O and S in step (3) is one or a combination of thiadiazole Schiff base, aminothiazole salicylaldehyde Schiff base, acetylthiophene Schiff base, thiosemicarbazide Schiff base, and triazole base thioether Schiff base.
Preferably, the steady-state complex manganese-copper-zinc ion symbiont in the step (3): schiff base ligand group containing N, O and S: weak light photocatalyst powder: the mass ratio of the deionized water is (0.5-1): (0.01-0.1): 1: (1-5).
Preferably, the spray drying temperature in the step (3) is 120-180 ℃.
Preferably, the dispersing aid in the step (4) is one or a combination of ECO-2300, BYK110, BYK-9077 and DISPERBYK-2008.
Preferably, the viscosity reduction auxiliary agent in the step (4) is one or a combination of BYK-1163, VISCOBYK-5130, BYK-1166 and VISCOBYK-4041.
Preferably, the functional powder is compounded in the step (4): dispersing auxiliary agent: viscosity reducing auxiliary agent: the mass ratio of the deionized water is 1: (0.01-0.1): (0.01-0.1): (1-2).
Preferably, the size of the zirconium beads in the step (4) is 0.3mm, 0.2mm, 0.1mm or 0.05 mm.
Preferably, the linear speed of the grinding machine in the step (4) is 6-14 m/s.
Preferably, the mercaptan in the step (5a) is one of tert-dodecyl mercaptan, tert-hexadecyl mercaptan, n-butyl mercaptan, trityl mercaptan, and octadecyl mercaptan or a combination thereof.
Preferably, the alkyl ammonium chloride in the step (5a) is one or a combination of trioctylmethyl ammonium chloride, tetraethyl ammonium chloride, benzyltriethyl ammonium chloride and decyltrimethyl ammonium chloride.
Preferably, the ratio of sodium hydroxide: mercaptan: alkyl ammonium chloride: acetone: carbon disulfide: the mass ratio of chloroform is 1: (0.1-10): (0.1-10): (1-100): (0.1-10): (0.1-10).
Preferably, the reaction temperature in the step (5a) is 5-45 ℃.
Preferably, the reaction time in the step (5a) is 5-36 h.
Preferably, the pH value in the step (5a) is 1-5.
Preferably, the polyalkyl ether in step (5b) is one or a combination of polyoxyethylene monomethyl ether, castor oil polyoxyethylene ether, nonylphenol polyoxyethylene ether and cetyl alcohol polyoxyethylene ether.
Preferably, the alkyl pyridine in the step (5b) is one of dimethylamino pyridine, dimethylamino pyridine tosylate, pyridine-3, 4-dicarboxylic anhydride, 3-pyridinemethylamine or a combination thereof.
Preferably, the alkyl imine in the step (5b) is one of dicyclohexyl carbodiimide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide, bis (trimethylsilyl) carbodiimide, or a combination thereof.
Preferably, in the step (5b), the ratio of crystal A: dichloromethane: polyalkyl ether: alkyl pyridine: the mass ratio of the alkyl imine is 1: (0.1-20): (0.1-10): (0.01-1): (0.1-10).
Preferably, the esterification reaction temperature in the step (5b) is 5-45 ℃.
Preferably, the esterification reaction time in the step (5b) is 12-72 h.
Preferably, the alkylamide in the step (5c) is one of N-isopropylacrylamide, methacrylamide, diacetone acrylamide, 2-acrylamido-2-methylpropanesulfonic acid or a combination thereof.
Preferably, the solvent in step (5c) is one of N, N-dimethylformamide, ethanol, acetone, ethylene glycol or a combination thereof.
Preferably, the initiator in step (5c) is one of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, tert-butyl peroxybenzoate or a combination thereof.
Preferably, the solid B in step (5 c): alkyl amide: solvent: the mass ratio of the initiator is 1: (1-100): (1-1000): (0.001-0.1).
Preferably, the reaction temperature in the step (5c) is 50-90 ℃.
Preferably, the reaction time in the step (5c) is 12-36 h.
Preferably, the addition amount of the complex ion protection auxiliary agent in the step (6) is 1-20% of the mass of the composite functional powder in the step (4).
Preferably, the special polymer resin in the step (7) is one or a combination of polyurethane, acrylic resin, silicone resin and pullulan.
Preferably, the silane coupling agent in the step (7) is one of or a combination of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane.
Preferably, the surface tension promoter in the step (7) is one of BYK-346, BYK301, Sago-3371 and Levaslip 410 or a combination thereof.
Preferably, the aqueous multifunctional dispersion in step (7): special high molecular resin: silane coupling agent: the surface tension promoter has a mass ratio of (0.05-1): 1: (0.01-0.1): (0.01-0.1).
Compared with the prior art, the invention has the following beneficial effects:
the invention aims to provide a preparation method of black hole shape composite functional powder and textile after-finishing liquid. Compared with the traditional technology:
1) the synthesized efficient complexing agent has good complexing effect on manganese ions, zinc ions and copper ions, can simultaneously and stably complex the three ions, and ensures subsequent antibacterial and antiviral properties;
2) the stable complex manganese-copper-zinc ion symbiont is mixed with Schiff base and a special weak photocatalyst material to prepare black hole-shaped high-efficiency composite antibacterial and antiviral powder, the composite material has the characteristics of a semiconductor, and meanwhile, the inner cavity has a bipolar electric field effect, so that bacteria and viruses are extremely easy to capture, and the special shape adsorbs and kills the bacteria and the viruses, thereby achieving the purpose of high-efficiency antibacterial disinfection;
3) a novel complexing protection auxiliary agent is prepared by a specific formula, and an asymmetric vesicle is formed to protect a stable complexing manganese-copper-zinc ion symbiont, Schiff base and special weak photocatalyst mixed antibacterial and antiviral composite material particle of the company, so that the stable complexing manganese-copper-zinc ion symbiont has excellent stability, ROS and a synergistic enhancement effect are initiated, high active oxygen and free radicals are generated to be adhered to the surface of a virus, the structures and functions of virus proteins and nucleic acid are damaged, the captured bacteria and virus can be quickly inactivated by a contact catalysis type antibacterial and antiviral mechanism, and the capability of killing the bacteria and the virus is maximized.
Drawings
FIG. 1 is an SEM photograph of black hole-shaped composite functional powder of example 1
FIG. 2 is an SEM photograph of black hole-shaped composite functional powder of example 2
FIG. 3 is an SEM image of the antibacterial and antiviral fabric in example 3
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
weighing a certain amount of N- (phosphonomethyl) glycine, dissolving the N- (phosphonomethyl) glycine in deionized water, adjusting the pH value to 12 by using a sodium hydroxide solution, and adding copper sulfate in the stirring process. Wherein N- (phosphonomethyl) glycine: deionized water: the mass ratio of the copper sulfate is 1: 10: 3. after the reaction is completed, the formaldehyde aqueous solution and the sodium carbonate are added into the solution, and the mixture reacts for 3 hours in a water bath kettle at 75 ℃. Then adding ethanol into the reaction solution, standing in a refrigerator (8 ℃) for 24 hours, and separating out crystals, namely the high-efficiency metal ion complexing agent. Wherein N- (phosphonomethyl) glycine: aqueous formaldehyde solution: sodium carbonate: the mass ratio of ethanol is 1: 5: 1: 20. and (3) stirring and heating the prepared high-efficiency metal ion complexing agent, manganese nitrate, copper sulfate, zinc oxide and deionized water to prepare a steady-state complexing manganese-copper-zinc ion symbiont. Wherein the high-efficiency metal ion complexing agent is as follows: manganese nitrate: copper sulfate: zinc oxide: the mass ratio of the deionized water is 1: 0.2: 0.1: 1: 7, the heating temperature is 70 ℃. And (3) stirring and spray-drying the steady-state complex manganese-copper-zinc ion symbiont, thiadiazole Schiff base, weak photocatalyst powder (a high-efficiency nano weak photocatalyst formed by mutually doping tungsten-zinc lattices in a poly-curing patent, a precious metal graphene-supported manganese-zinc-based weak photocatalyst and a porous graphene-supported weak photocatalyst) and deionized water to obtain black hole-shaped composite functional powder. Wherein, the steady-state complex manganese-copper-zinc ion symbiont comprises: thiadiazole Schiff base: weak light photocatalyst powder: the mass ratio of the deionized water is 0.6: 0.05: 1: 3, the temperature of spray drying is 160 ℃. Premixing the black hole shape composite functional powder with ECO-2300, BYK-1163 and deionized water, and pre-dispersing by the shearing force and the centrifugal force of zirconium beads in a grinding machine. Wherein the black hole shape composite functional powder: ECO-2300: BYK-1163: the mass ratio of the deionized water is 1: 0.03: 0.02: 1.5, the size of the zirconium beads is 0.2mm, and the linear velocity of the mill is 10 m/s. Meanwhile, the complex ion protection auxiliary agent is synthesized by the following steps of firstly adding sodium hydroxide, tert-dodecyl mercaptan, trioctyl methyl ammonium chloride and acetone into a jacket reactor, adding carbon disulfide and chloroform into the jacket reactor after the sodium hydroxide, tert-dodecyl mercaptan, trioctyl methyl ammonium chloride and acetone are fully and uniformly mixed, and reacting for 12 hours at 35 ℃ under the protection of nitrogen. Adjusting the pH value to 3 by adopting hydrochloric acid, then distilling off acetone under reduced pressure, and filtering to obtain a crystal A. Wherein the ratio of sodium hydroxide: tertiary dodecyl mercaptan: trioctylmethylammonium chloride: acetone: carbon disulfide: the mass ratio of chloroform is 1: 2: 0.8: 30: 1: 4. adding the prepared crystal A into dichloromethane, and adding polyoxyethylene monomethyl ether, dimethylaminopyridine and dicyclohexylcarbodiimide into the solution. The esterification reaction was stirred at 25 ℃ for 36h and then filtered to give solid B. Wherein the crystal A: dichloromethane: polyoxyethylene monomethyl ether: dimethylaminopyridine: the mass ratio of dicyclohexylcarbodiimide is 1: 3: 2: 0.3: 1. and dissolving the prepared solid B and N-isopropyl acrylamide into N, N-dimethylformamide, uniformly stirring, adding azobisisobutyronitrile, reacting for 24 hours in a water bath kettle at 80 ℃, evaporating the solvent to dryness, and preparing the complex ion protection auxiliary agent. Wherein the solid B: n-isopropylacrylamide: n, N-dimethylformamide: the mass ratio of the azodiisobutyronitrile is 1: 30: 100: 0.03. and (3) when the average particle size of the dispersion prepared in the previous step is less than 100nm, adding the complex ion protection auxiliary agent prepared in the previous step to prepare stable high-concentration water-based composite functional dispersion liquid with controllable particle size. Wherein the addition amount of the complex ion protection auxiliary agent is 5 percent of the mass of the composite functional powder. And mixing the aqueous composite functional dispersion with polyurethane, vinyl triethoxysilane and BYK-346 according to a certain proportion, emulsifying, and stirring to obtain the water-resistant textile after-finishing liquid with antibacterial and antiviral functions. Wherein the aqueous composite functional dispersion: polyurethane: vinyltriethoxysilane: the mass ratio of BYK-346 is 0.5: 1: 0.05: 0.03.
after the antibacterial, antiviral and water-fast textile after-finishing liquid is solidified on the polyester fabric through a rolling drying process, the antibacterial rate of the black hole exterior composite functional powder and the antibacterial and antiviral fabric to escherichia coli and the inactivation rate of H3N2 influenza virus are tested, and the results are shown in table 1 and table 2.
Example two:
weighing a certain amount of N-isovalerylaminoacetic acid, dissolving the N-isovalerylaminoacetic acid in deionized water, adjusting the pH value to 10 by adopting a sodium hydroxide solution, and then adding copper sulfate in the stirring process. Wherein the ratio of N-isovalerylaminoacetic acid: deionized water: the mass ratio of the copper sulfate is 1: 50: 3. after the reaction is completed, adding an acetaldehyde aqueous solution and sodium carbonate into the solution, and reacting for 2 hours at 80 ℃ in a water bath kettle. Then adding propanol into the reaction solution, standing in a refrigerator (10 ℃) for 36 hours, and separating out crystals, namely the high-efficiency metal ion complexing agent. Wherein the ratio of N-isovalerylaminoacetic acid: aqueous acetaldehyde solution: sodium carbonate: the mass ratio of the propyl alcohol is 1: 0.5: 0.3: 10. and (3) stirring and heating the prepared high-efficiency metal ion complexing agent, manganous chloride, dioxime tetranuclear copper picrate (II), titanium-doped zinc oxide and deionized water to prepare a steady-state complexing manganese-copper-zinc ion symbiont. Wherein the high-efficiency metal ion complexing agent is as follows: manganous chloride: copper (ii) bis-oxime tetranuclear picrate: titanium-doped zinc oxide: the mass ratio of the deionized water is 1: 0.1: 0.2: 1: 10, the heating temperature is 70 ℃. And (2) stirring, spraying and drying the steady-state complex manganese-copper-zinc ion symbiont, aminothiazole salicylaldehyde Schiff base, weak photocatalyst powder (a high-efficiency nano weak photocatalyst formed by mutually doping tungsten-zinc lattices in a poly-curing patent, a precious metal graphene-supported manganese-zinc-based weak photocatalyst and a porous graphene-supported weak photocatalyst) and deionized water to obtain black hole-shaped composite functional powder. Wherein, the steady-state complex manganese-copper-zinc ion symbiont comprises: aminothiazole salicylaldehyde Schiff base: weak light photocatalyst powder: the mass ratio of the deionized water is 0.6: 0.07: 1: 5, the temperature of spray drying is 180 ℃. Premixing the black hole shape composite functional powder with BYK110, VISCOBYK-5130 and deionized water, and pre-dispersing by the shearing force and centrifugal force of zirconium beads in a grinding machine. Wherein the black hole shape composite functional powder: BYK 110: VISCOBYK-5130: the mass ratio of the deionized water is 1: 0.02: 0.05: 2, the size of the zirconium beads was 0.1mm, and the linear velocity of the mill was 12 m/s. Meanwhile, the complex ion protection auxiliary agent is synthesized by the following steps of firstly adding sodium hydroxide, tert-hexadecyl mercaptan, tetraethyl ammonium chloride and acetone into a jacket reactor, adding carbon disulfide and chloroform into the jacket reactor after the sodium hydroxide, the tert-hexadecyl mercaptan, the tetraethyl ammonium chloride and the acetone are fully and uniformly mixed, and reacting for 24 hours at 35 ℃ under the protection of nitrogen. Adjusting the pH value to 2 by adopting hydrochloric acid, then distilling off acetone under reduced pressure, and filtering to obtain a crystal A. Wherein the ratio of sodium hydroxide: tertiary hexadecanethiol: tetraethylammonium chloride: acetone: carbon disulfide: the mass ratio of chloroform is 1: 3: 0.4: 20: 6: 3. adding the prepared crystal A into dichloromethane, and adding castor oil polyoxyethylene ether, dimethylamino pyridine tosylate and dicyclohexyl carbodiimide into the solution. The esterification reaction was stirred at 30 ℃ for 72h and then filtered to give solid B. Wherein the crystal A: dichloromethane: castor oil polyoxyethylene ether: dimethylamino pyridine tosylate: the mass ratio of dicyclohexylcarbodiimide is 1: 15: 7: 0.01: 0.3. and dissolving the prepared solid B and methacrylamide into ethanol, uniformly stirring, adding azobisisoheptonitrile, keeping the temperature of 90 ℃ in a water bath for reacting for 36 hours, evaporating the solvent to dryness, and preparing the complex ion protection auxiliary agent. Wherein the solid B: methacrylamide: ethanol: the mass ratio of the azodiisoheptanonitrile is 1: 30: 500: 0.005. and (3) when the average particle size of the dispersion prepared in the previous step is less than 100nm, adding the complex ion protection auxiliary agent prepared in the previous step to prepare stable high-concentration water-based composite functional dispersion liquid with controllable particle size. Wherein the addition amount of the complex ion protection auxiliary agent is 10 percent of the mass of the composite functional powder. And mixing the aqueous composite functional dispersion with acrylic resin, vinyl trimethoxy silane and BYK301 according to a proportion, emulsifying and stirring to prepare the water-fast textile after-finishing liquid with the antibacterial and antiviral functions. Wherein the aqueous composite functional dispersion: acrylic resin: vinyl trimethoxy silane: the mass ratio of BYK301 is 0.1: 1: 0.01: 0.03.
after the antibacterial, antiviral and water-fast textile after-finishing liquid is solidified on the polyester fabric through a rolling drying process, the antibacterial rate of the black hole exterior composite functional powder and the antibacterial and antiviral fabric to escherichia coli and the inactivation rate of H3N2 influenza virus are tested, and the results are shown in table 1 and table 2.
Example three:
weighing a certain amount of ethyl thiooxamide, dissolving the ethyl thiooxamide in deionized water, adjusting the pH value to 14 by using a sodium hydroxide solution, and then adding copper sulfate while stirring. Wherein ethyl thiooxamide: deionized water: the mass ratio of the copper sulfate is 1: 70: 8. after full reaction, adding phenylacetaldehyde alcoholic solution and sodium carbonate into the solution, and reacting for 6h at 90 ℃ in a water bath kettle. Then adding methanol into the reaction solution, standing in a refrigerator (2 ℃) for 48 hours, and separating out crystals, namely the high-efficiency metal ion complexing agent. Wherein ethyl thiooxamide: phenylacetaldehyde alcohol solution: sodium carbonate: the mass ratio of methanol is 1: 4: 0.2: 80. and (3) stirring and heating the prepared high-efficiency metal ion complexing agent, manganese oxide, composite amino acid copper, silicon-doped zinc oxide and deionized water to prepare a stable complexing manganese copper zinc ion symbiont. Wherein the high-efficiency metal ion complexing agent is as follows: manganese oxide: copper complex amino acid: silicon-doped zinc oxide: the mass ratio of the deionized water is 5: 0.2: 0.08: 1: 15, the heating temperature is 90 ℃. And (2) stirring and spray-drying the steady-state complex manganese-copper-zinc ion symbiont, triazole alkali sulfide Schiff alkali, weak photocatalyst powder (a high-efficiency nano weak photocatalyst formed by mutually doping tungsten-zinc lattices in a poly-curing patent, a precious metal graphene-supported manganese-zinc-based weak photocatalyst and a porous graphene-supported weak photocatalyst) and deionized water to obtain black hole-shaped composite functional powder. Wherein, the steady-state complex manganese-copper-zinc ion symbiont comprises: triazole base thioether Schiff base: weak light photocatalyst powder: the mass ratio of the deionized water is 1: 0.02: 1: 5, the temperature of spray drying is 120 ℃. Premixing the black hole shape composite functional powder with DISPERBYK-2008, BYK-1166 and deionized water, and pre-dispersing by the shearing force and the centrifugal force of zirconium beads in a grinding machine. Wherein the black hole shape composite functional powder: DISPERBYK-2008: BYK-1166: the mass ratio of the deionized water is 1: 0.03: 0.08: 1, the size of the zirconium beads was 0.05mm, and the linear velocity of the mill was 14 m/s. Meanwhile, the complex ion protection auxiliary agent is synthesized by the following steps of firstly adding sodium hydroxide, trithiol, decyl trimethyl ammonium chloride and acetone into a jacket reactor, adding carbon disulfide and chloroform into the jacket reactor after the sodium hydroxide, the trithiol, the decyl trimethyl ammonium chloride and the acetone are fully and uniformly mixed, and reacting for 36 hours at 15 ℃ under the protection of nitrogen. Adjusting the pH value to 2 by adopting hydrochloric acid, then distilling off acetone under reduced pressure, and filtering to obtain a crystal A. Wherein the ratio of sodium hydroxide: trithiol: decyl trimethyl ammonium chloride: acetone: carbon disulfide: the mass ratio of chloroform is 1: 1: 5: 20: 0.2: 4. adding the prepared crystal A into dichloromethane, and adding nonylphenol polyoxyethylene ether, 3-pyridylmethylamine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide into the solution. The esterification reaction was stirred at 20 ℃ for 48h and then filtered to give solid B. Wherein the crystal A: dichloromethane: polyoxyethylene nonyl phenyl ether: 3-pyridinemethylamine: the mass ratio of 1-ethyl- (3-dimethylaminopropyl) carbodiimide is 1: 15: 1: 0.07: 5. and dissolving the prepared solid B and 2-acrylamide-2-methylpropanesulfonic acid in ethylene glycol, uniformly stirring, adding dibenzoyl peroxide, reacting for 24 hours in a water bath kettle at 70 ℃, evaporating the solvent to dryness, and preparing the complex ion protection auxiliary agent. Wherein the solid B: 2-acrylamido-2-methylpropanesulfonic acid: ethylene glycol: the mass ratio of dibenzoyl peroxide is 1: 10: 150: 0.03. and (3) when the average particle size of the dispersion prepared in the previous step is less than 100nm, adding the complex ion protection auxiliary agent prepared in the previous step to prepare stable high-concentration water-based composite functional dispersion liquid with controllable particle size. Wherein the addition amount of the complex ion protection auxiliary agent is 3 percent of the mass of the composite functional powder. Mixing the aqueous composite functional dispersion liquid with pullulan polysaccharide, vinyl tri (beta-methoxyethoxy) silane and Sago-3371 according to a proportion, emulsifying and stirring to prepare the water-washable textile after-finishing liquid with the antibacterial and antiviral functions. Wherein the aqueous composite functional dispersion: pullulan polysaccharide: vinyltris (. beta. -methoxyethoxy) silane: the mass ratio of Sago-3371 is 0.3: 1: 0.05: 0.02.
after the antibacterial, antiviral and water-fast textile after-finishing liquid is solidified on the polyester fabric through a rolling drying process, the antibacterial rate of the black hole exterior composite functional powder and the antibacterial and antiviral fabric to escherichia coli and the inactivation rate of H3N2 influenza virus are tested, and the results are shown in table 1 and table 2.
TABLE 1 antibacterial ratio of black-hole-shaped complex-function powder to E.coli
Sample name Antibacterial rate
Example 1 composite functional powder ＞99％
Example 2 composite functional powder ＞99％
Example 3 composite functional powder ＞99％
TABLE 2 extermination rate of antibacterial, antiviral and water-fast textile after-finishing liquor finished polyester fabric against Escherichia coli and H3N2 influenza virus
Sample (I) Antibacterial rate Rate of killing virus
Example 1 afterfinish 99.1％ 99％
Example 2 afterfinish 99.9％ 99.9％
Example 3 afterfinish 99.5％ 99％

Claims (10)

1. A preparation method of black hole shape composite functional powder and textile after-finishing liquid is characterized by comprising the following specific steps:
(1) synthesizing an efficient metal ion complexing agent: weighing a certain amount of complexing agent precursor, dissolving the complexing agent precursor into deionized water, adjusting the pH value of the deionized water by using a sodium hydroxide solution, and then adding copper sulfate into the mixed solution in the stirring process;
after full reaction, adding aldehyde solution and sodium carbonate into the solution, reacting for a period of time at a certain temperature in a water bath, then adding alcohol solution into the reaction solution, and standing for a period of time in a refrigerator, wherein separated crystals are the high-efficiency metal ion complexing agent;
(2) preparing a complex ion symbiont: respectively weighing the high-efficiency metal ion complexing agent prepared in the step (1), a manganese compound, a copper compound, a zinc compound and deionized water, stirring, heating and complexing to prepare a stable complexing manganese-copper-zinc ion symbiont;
(3) preparing composite functional powder: weighing the steady-state complex manganese copper zinc ion intergrowth prepared in the step (2), Schiff base ligand groups containing N, O and S, weak photocatalyst powder (high-efficiency nano weak photocatalyst with tungsten-zinc crystal lattices doped mutually, precious metal graphene-supported manganese zinc-based weak photocatalyst, porous graphene-supported weak photocatalyst and the like), deionized water, stirring, and spray drying to obtain black hole shape composite functional powder;
(4) pre-dispersing: weighing the black hole shape composite functional powder prepared in the step (3), premixing the black hole shape composite functional powder with a dispersing aid, a viscosity reduction aid and deionized water, and pre-dispersing by using the shearing force and the centrifugal force of zirconium beads in a grinding machine;
(5) preparing a complex ion protection auxiliary agent:
a) adding a certain amount of sodium hydroxide, mercaptan, alkyl ammonium chloride and acetone into a jacket reactor, adding carbon disulfide and chloroform after the sodium hydroxide, the mercaptan, the alkyl ammonium chloride and the acetone are fully and uniformly mixed, reacting for a period of time at a certain temperature under the protection of nitrogen, regulating the pH value of the mixture by using hydrochloric acid, then distilling under reduced pressure to remove the acetone, and filtering to obtain crystals A;
b) adding the prepared crystal A into dichloromethane, and adding polyalkyl ether, alkyl pyridine and alkyl imine into the solution;
stirring the mixture at a certain temperature for esterification reaction for a period of time, and filtering the mixture to obtain a solid B;
c) dissolving the prepared solid B and alkylamide into a certain amount of solvent, uniformly stirring, adding a certain amount of initiator, reacting for a period of time at a certain temperature in a water bath kettle, evaporating the solvent to dryness, and preparing to obtain a complex ion protection auxiliary agent;
(6) preparing a composite functional dispersion liquid: when the average particle size of the dispersion in the step (4) is less than 100nm, adding the complex ion protection auxiliary agent prepared in the step (5) to prepare stable high-concentration water-based composite functional dispersion with controllable particle size;
(7) and (4) mixing the aqueous composite functional dispersion liquid prepared in the step (6) with special high polymer resin, a silane coupling agent and a surface tension promoter according to a proportion, emulsifying and stirring to prepare the water-fast textile after-finishing liquid with the antibacterial and antiviral functions.
2. The method for preparing black hole external composite functional powder and textile after-finishing liquid according to claim 1, wherein the complexing agent precursor in the step (1) is one or a combination of N- (phosphonomethyl) glycine, ethyl thiooxamide, N-isovaleroacetic acid, glycyrrhiza phosphine, ethyl thiooxamide, ethyl N-phenyl glycine ethyl ether and ethyl chlorooximidoacetate; the aldehyde solution is one or the combination of a formaldehyde aqueous solution, an acetaldehyde aqueous solution, a benzaldehyde alcohol solution and a lauraldehyde alcohol solution; the alcoholic solution is one or the combination of ethanol, propanol, glycol and methanol; the precursor of the complexing agent is as follows: deionized water: copper sulfate: aldehyde solution: sodium carbonate: the mass ratio of the alcoholic solution is 1: (1-100): (0.1-10): (0.1-10): (0.1-10): (0.5 to 100); the pH value is 9-14; the reaction temperature of the water bath is 65-95 ℃; the water bath reaction time is 1-10 h; the standing temperature of the refrigerator is 1-10 ℃; the standing time is 12-48 h.
3. The method for preparing black hole shape composite functional powder and textile after-finishing liquid according to claim 1, wherein the high-efficiency metal ion complexing agent in the step (2): a manganese compound: copper compound: a zinc compound: the mass ratio of the deionized water is (1-5): (0.01-1): (0.01-1): 1: (3-15); the manganese compound is one or the combination of manganese nitrate, manganous chloride, manganese sulfate and manganese oxide; the copper compound is one or the combination of copper sulfate, copper chloride, copper (II) bis-oxime tetranuclear picrate, copper oxide, copper hydroxide and compound copper amino acid; the zinc compound is one or the combination of zinc oxide, titanium-doped zinc oxide, aluminum-doped zinc oxide and silicon-doped zinc oxide; the heating temperature is 50-90 ℃.
4. The method for preparing black hole shape composite functional powder and textile after-finishing liquid according to claim 1, wherein the steady-state complexing manganese-copper-zinc ion symbiont in the step (3): schiff base ligand group containing N, O and S: weak light photocatalyst powder: the mass ratio of the deionized water is (0.5-1): (0.01-0.1): 1: (1-5); the Schiff base ligand containing N, O and S is one or a combination of thiadiazole Schiff base, aminothiazole salicylaldehyde Schiff base, acetylthiophene Schiff base, thiosemicarbazide Schiff base and triazole base thioether Schiff base; the spray drying temperature is 120-180 ℃.
5. The method for preparing black hole external composite functional powder and textile finishing liquid according to claim 1, wherein the composite functional powder in the step (4): dispersing auxiliary agent: viscosity reducing auxiliary agent: the mass ratio of the deionized water is 1: (0.01-0.1): (0.01-0.1): (1-2); the dispersing auxiliary agent is one or a combination of ECO-2300, BYK110, BYK-9077 and DISPERBYK-2008; the viscosity reduction auxiliary agent is one or a combination of BYK-1163, VISCOBYK-5130, BYK-1166 and VISCOBYK-4041; the size of the zirconium beads is 0.3mm, 0.2mm, 0.1mm or 0.05 mm; the linear speed of the grinding machine is 6-14 m/s.
6. The method for preparing black hole shape composite functional powder and textile after-finishing liquid according to claim 1, wherein the mercaptan in the step (5a) is one or a combination of tert-dodecyl mercaptan, tert-hexadecyl mercaptan, n-butyl mercaptan, trityl mercaptan and octadecyl mercaptan; the alkyl ammonium chloride is one or the combination of trioctylmethyl ammonium chloride, tetraethyl ammonium chloride, benzyltriethyl ammonium chloride and decyltrimethyl ammonium chloride; the sodium hydroxide: mercaptan: alkyl ammonium chloride: acetone: carbon disulfide: the mass ratio of chloroform is 1: (0.1-10): (0.1-10): (1-100): (0.1-10): (0.1 to 10); the reaction temperature in the step (5a) is 5-45 ℃; the reaction time is 5-36 h; the pH value is 1-5.
7. The method for preparing black hole external composite functional powder and textile finishing liquor according to claim 1, wherein the polyalkyl ether in the step (5b) is one or a combination of polyoxyethylene monomethyl ether, castor oil polyoxyethylene ether, nonylphenol polyoxyethylene ether and cetyl alcohol polyoxyethylene ether; the alkyl pyridine is one or the combination of dimethylamino pyridine, dimethylamino pyridine tosylate, pyridine-3, 4-dicarboxylic anhydride and 3-pyridinemethylamine; the alkyl imine is one or the combination of dicyclohexyl carbodiimide, 1-ethyl- (3-dimethyl amino propyl) carbodiimide and bis (trimethylsilyl) carbodiimide; the crystal A: dichloromethane: polyalkyl ether: alkyl pyridine: the mass ratio of the alkyl imine is 1: (0.1-20): (0.1-10): (0.01-1): (0.1 to 10); the esterification reaction temperature is 5-45 ℃; the esterification reaction time is 12-72 h.
8. The method for preparing black hole shape composite functional powder and textile after-finishing liquid according to claim 1, wherein in the step (5c), the alkyl amide is one or a combination of N-isopropyl acrylamide, methacrylamide, diacetone acrylamide and 2-acrylamide-2-methyl propane sulfonic acid; the solvent is one or the combination of N, N-dimethylformamide, ethanol, acetone and glycol; the initiator is one or the combination of azodiisobutyronitrile, azodiisoheptonitrile, dibenzoyl peroxide and tert-butyl peroxybenzoate; the solid B: alkyl amide: solvent: the mass ratio of the initiator is 1: (1-100): (1-1000): (0.001 to 0.1); the reaction temperature is 50-90 ℃; the reaction time is 12-36 h.
9. The method for preparing black hole shape composite functional powder and textile after-finishing liquid according to claim 1, wherein the addition amount of the complex ion protection auxiliary agent in the step (6) is 1-20% of the mass of the composite functional powder in the step (4).
10. The method for preparing black hole external composite functional powder and textile after-finishing liquid according to claim 1, wherein the aqueous composite functional dispersion in the step (7): special high molecular resin: silane coupling agent: the surface tension promoter has a mass ratio of (0.05-1): 1: (0.01-0.1): (0.01 to 0.1); the special high polymer resin is one or the combination of polyurethane, acrylic resin, organic silicon resin and pullulan; the silane coupling agent is one or the combination of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane; the surface tension promoter is one of BYK-346, BYK301, Sago-3371 and Levaslip 410 or a combination thereof.
CN202110760056.7A 2021-07-06 2021-07-06 Preparation method of black hole external composite functional powder and textile after-finishing liquid Pending CN113463398A (en)

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