CN107761372B - Long-acting antibacterial treatment fluid for textiles and preparation method thereof - Google Patents

Long-acting antibacterial treatment fluid for textiles and preparation method thereof Download PDF

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CN107761372B
CN107761372B CN201710879296.2A CN201710879296A CN107761372B CN 107761372 B CN107761372 B CN 107761372B CN 201710879296 A CN201710879296 A CN 201710879296A CN 107761372 B CN107761372 B CN 107761372B
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CN107761372A (en
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翁德喜
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Ruyu Deshui Hangzhou Soft Decoration Customization Co ltd
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Hangzhou Daoxian Intelligent 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
    • 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
    • D06M13/152—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 having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • D06M13/156—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 having a hydroxy group bound to a carbon atom of a six-membered aromatic ring containing halogen atoms
    • 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
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/345—Nitriles
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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
    • 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
    • D06M2101/10—Animal fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/38—Polyurethanes

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention relates to a textile long-acting antibacterial treatment solution, which comprises the following raw materials in percentage by weight: 84-97.5% of deionized water, 0.5-3.5% of Unined RM antibacterial agent, 1.5-11.5% of adhesive, 0.25-0.5% of dispersant and 0.25-0.5% of coupling agent. The antibacterial treatment fluid adopts various compounds, has good adhesion when being compounded with the wool, the cotton and the blended textile products, is added on the surfaces of the wool, the cotton and the blended textile products, has the effects of resisting common germs and inhibiting drug-resistant germs, is efficient and durable, has the effects of purifying the environment, eliminating peculiar smell, self-cleaning and health care, does not pollute the environment and has no side effect on human bodies, and is beneficial to people to obtain more health benefits.

Description

Long-acting antibacterial treatment fluid for textiles and preparation method thereof
Technical Field
The invention belongs to the field of functional new materials, and particularly relates to a long-acting antibacterial treatment fluid for textiles, which enables wool, cotton and blended textile products to have the advantages of common germ resistance, drug resistance germ inhibition, high efficiency, durability, no environmental pollution and no side effect on human bodies, and a preparation method thereof.
Background
Along with the progress of society, various wool, cotton and blended textile products have higher and higher use frequency and more varieties. However, these products have no bacteriostatic function, are easy to generate peculiar smell, and are easy to breed or propagate various harmful microorganisms such as bacteria, mold, viruses and the like, thereby becoming a public transmission source and bringing great trouble to the health of people.
In view of the above, in recent years, researches on antibacterial properties of wool, cotton and blended textile products are increasing at home and abroad, and the antibacterial properties are mainly obtained by adding a small amount of antibacterial agent. According to the searched literature, the current antibacterial agents are mainly divided into three series of single inorganic, organic and natural according to the structure.
The inorganic antibacterial agent is prepared by taking metal ions such as silver, copper, zinc and the like as an antibacterial agent and taking porous inorganic non-metallic materials such as phosphate, bentonite and the like as carriers, has strong heat resistance, but has high price, environmental protection and washing resistance, and can cause negative effects on the liver of a human body when being used for a long time and touching the product containing the metal ions such as silver, copper, zinc and the like.
The organic antibacterial agent comprises quaternary ammonium salts, imidazoles, pyridines, organic metals and the like, has high sterilization speed and obvious antibacterial effect, but is easy to generate drug resistance, has poor heat stability, short antibacterial persistence and higher toxicity, thereby bringing new health hidden troubles to people.
Compared with the prior art, the natural antibacterial agent is extracted from plants, animals or organisms, has wide sources and low cost, has the advantages of safety, no toxicity, rich nutrition and health care components, difficult generation of drug resistance, environmental friendliness and the like, and is more and more valued by people in application and research. However, natural antibacterial agents are usually extracted from a plant, an animal or a living being, and have the problems of single antibacterial component, narrow antibacterial range, agglomeration, uneven dispersion and the like, and the antibacterial component is easy to separate out in the use process, the antibacterial effect cannot be lasting, and the drug resistance of product germs is easy to be realized.
Disclosure of Invention
Aiming at the technical problems, the invention provides the textile long-acting antibacterial treatment fluid which enables the wool, cotton and blended textile products to have the functions of resisting common germs, inhibiting drug-resistant germs, being efficient and durable, not polluting the environment and having no side effect on human bodies and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to solve the technical problem of providing a long-acting antibacterial treatment solution for textiles.
The invention discloses a textile long-acting antibacterial treatment solution, which comprises the following raw materials in percentage by weight: 84-97.5% of deionized water, 0.5-3.5% of Unined RM antibacterial agent, 1.5-11.5% of adhesive, 0.25-0.5% of dispersant and 0.25-0.5% of coupling agent.
Preferably, the Unined RM antibacterial agent comprises, by weight, 10-15 parts of phenols, 1-3 parts of isoquercitrin, 2-4 parts of N, N-dihydroxyethylglycine, 3-5 parts of mercaptopyridine, 5-8 parts of dodecylbenzyldimethyl ammonium salt, 0.3-10 parts of a dispersing agent, 0.56-22 parts of acrylic acid and 10-15 parts of 2, 4, 5, 6-tetrachlorophthalonitrile.
The antibacterial mechanism of the organic antibacterial agent is mainly combined with anions on the cell membrane surface of the pathogenic microorganism or reacts with sulfydryl to destroy the structure of protein or influence the synthesis of the biological membrane, so that the propagation of the pathogenic microorganism is inhibited. In general, the mechanism of action of organic antibacterial agents is summarized as: 1. acting on protease or other bioactive substances required by biochemical reaction; 2. acting on the genetic material DNA or other genetic microparticulate structure; 3. acting on the biological membrane system or cell wall.
The invention adopts the synergistic cooperation of all the substances to adsorb pathogenic microorganisms with negative charges, destroys the cell wall mechanism of the microorganisms, leads the contents to leak and can inhibit the actions of pathogenic bacteria oxidase, dehydrogenase and the like; it can also remove lipid substances from pathogenic microbial membrane and denature protein; can also interfere the mitosis process of pathogenic microorganism, inhibit the formation of spindle and influence the cell division process of pathogenic microorganism.
Preferably, the phenols are one or a combination of more of isopropyl methyl phenol, triclosan, dichlorophen, chlorobenzol and chlorocresol.
Preferably, the preparation method of the Unined RM antibacterial agent comprises the following steps:
(1) mixing weighed phenols, isoquercitrin, N-dihydroxyethyl glycine, mercaptopyridine, dodecyl benzyl dimethyl ammonium salt and 2, 4, 5, 6-tetrachlorophthalonitrile at room temperature to form uniform suspension;
(2) adding a dispersing agent into the suspension obtained in the step (1), mixing for 10-12 hours, then adding acrylic acid, and mixing for 2-5 minutes to obtain the Unined RM antibacterial agent.
Preferably, the dispersant is sodium polyacrylate.
In some embodiments of the present invention, the dispersant sodium polyacrylate is a commercially available sodium polyacrylate, i.e., a11 nonionic dispersant.
In some embodiments of the present invention, the dispersant sodium polyacrylate is prepared by the following process:
mixing acrylic acid and isopropanol according to the mass ratio of 1 (0.9-1.2) to obtain a mixed solution A; ammonium persulfate and deionized water are mixed according to a solid-to-liquid ratio of 1: (20-25) (g/mL) to obtain a mixed solution B; n-dodecyl mercaptan, isopropanol and deionized water are mixed in a mass ratio of 1: (22-25): 7, uniformly mixing to obtain a mixed solution C, wherein the mass ratio of n-dodecyl mercaptan, acrylic acid and ammonium persulfate is 1: (20-25): 1; heating the mixed solution C to 80-85 ℃, and simultaneously dripping the mixed solution A and the mixed solution B at a dripping speed of 5-8 mu L/s; after the addition is finished, reacting for 2.5-3 hours at 80-85 ℃; after the reaction is finished, cooling the reaction liquid to 40-45 ℃, and adjusting the pH value of the reaction liquid to 7-8 by using a sodium hydroxide aqueous solution with the mass fraction of 25-30%; and distilling the reaction liquid under reduced pressure to remove isopropanol and water to obtain the dispersant sodium polyacrylate.
In some embodiments of the present invention, the dispersant sodium polyacrylate is prepared by the following process:
(1) sequentially adding n-dodecyl mercaptan, methyl trioctyl chloride and acetone into a reaction container, wherein the mass ratio of the n-dodecyl mercaptan to the methyl trioctyl chloride to the acetone is 1: 0.07 (3.2-3.5), introducing nitrogen, keeping the temperature of the reaction system at 2-5 ℃, and stirring at the rotation speed of 150-200 r/min for 2-3 min; adding 40-50% of sodium hydroxide aqueous solution by mass, wherein the mass ratio of the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is (0.4-0.5):1, and stirring at the rotation speed of 150-; then adding 25-30% of carbon disulfide acetone solution by mass, wherein the mass ratio of the carbon disulfide acetone solution to the n-dodecyl mercaptan is (1.3-1.4):1, and stirring at the rotation speed of 150-; and then sequentially adding chloroform and 40-50% by mass of sodium hydroxide aqueous solution, wherein the mass ratio of the chloroform to the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is (0.8-0.9): 2:1, stirring and reacting for 12-18 hours at the rotating speed of 150-; after the reaction is finished, adding deionized water, wherein the mass ratio of the deionized water to the n-dodecyl mercaptan is (30-40) to 1, mixing, adding 35-37% of hydrochloric acid by mass, and the volume ratio of the hydrochloric acid to the deionized water is 1: (20-25), stirring at the rotating speed of 150-; introducing nitrogen to remove acetone; filtering with 80-100 mesh filter cloth, and collecting filter cake; drying the filter cake for 8-10 hours at 50-60 ℃ and under the vacuum degree of 0.06-0.08MPa to obtain the chain transfer agent;
(2) adding acrylic acid, an initiator AIBN, tertiary butanol and a chain transfer agent into a reaction vessel, wherein the mass ratio of the acrylic acid to the initiator AIBN to the tertiary butanol to the chain transfer agent is 1: 0.002: (1.8-1.9): 0.4, introducing nitrogen, and mixing for 10-15 minutes; then heating the reaction solution to 75-80 ℃ and reacting for 7-8 hours; and distilling the reaction liquid under reduced pressure to remove tert-butyl alcohol to obtain the dispersant sodium polyacrylate.
The dispersant sodium polyacrylate obtained by the invention has low molecular weight and narrow molecular weight distribution range, and can effectively reduce material agglomeration and improve the dispersion effect.
Preferably, the adhesive is one or a mixture of polyacrylic acid adhesive, aqueous polyurethane adhesive and lactic acid-based polyester adhesive.
The preparation process of the lactic acid-based polyester adhesive comprises the following steps: adding DL-lactic acid, epsilon-caprolactone and stannous octoate into a reaction container, wherein the mass ratio of the DL-lactic acid to the epsilon-caprolactone to the stannous octoate is (90-94): (6-10): 0.1, stirring and heating to 140 ℃ at the stirring speed of 600 revolutions per minute of 400-; heating the reaction liquid to 160-180 ℃, and polymerizing for 4-8 hours; after the polymerization is finished, cooling the reaction liquid to room temperature, adding trichloromethane, wherein the volume ratio of the reaction liquid to the trichloromethane is 1: (0.6-0.8), stirring at the rotation speed of 200-300 revolutions per minute for 5-10 minutes; then adding methanol, wherein the volume ratio of the methanol to the reaction liquid is (5-6): 1, stirring at the rotating speed of 200-300 revolutions per minute for 10-15 minutes, and generating precipitates; centrifuging at the rotating speed of 1000-; and drying the bottom solid for 6-10 hours at 50-60 ℃ under the vacuum degree of 0.08-0.09MPa to obtain the lactic acid based polyester adhesive.
Polylactic acid has been widely used in medical treatment and as a degradable material due to its excellent biocompatibility and bioabsorbability. The invention adopts epsilon-caprolactone as a monomer polymerized with polylactic acid, the hardness of chain segments is improved, the flexibility is improved, and the copolymer of the epsilon-caprolactone and the polylactic acid is used for textile adhesives, has excellent adhesive property, can be biodegraded and is environment-friendly.
The inventors have experimentally found that when the binder is a mixture of a polyacrylic acid binder and a lactic acid-based polyester binder, the adhesive effect is more excellent. Preferably, the adhesive is a mixture of polyacrylic acid adhesive and lactic acid-based polyester adhesive, wherein the mass ratio of the polyacrylic acid adhesive to the lactic acid-based polyester adhesive is 1: (3-5).
The second technical problem to be solved by the invention is to provide a preparation method of the long-acting antibacterial treatment solution for textiles.
The preparation method of the textile long-acting antibacterial treatment liquid comprises the following steps: weighing the raw materials according to a formula; the raw materials are put into a high-speed mixer and stirred for 10 to 12 hours at the temperature of between 25 and 35 ℃ and the rotating speed of 100 and 200 revolutions per minute to obtain the long-acting antibacterial treatment fluid for textiles.
The invention has the beneficial effects that: the antibacterial treatment fluid adopts various compounds, has good adhesion when being compounded with wool, cotton and blended textile products, is added on the surfaces of the wool, the cotton and the blended textile products, ensures that the wool, the cotton and the blended textile products have the functions of resisting common germs and inhibiting drug-resistant germs, has high efficiency and durability, has the functions of purifying environment, eliminating peculiar smell, self-cleaning and health care, does not pollute the environment and has no side effect on human bodies, and is beneficial to obtaining more health benefits.
Detailed Description
Introduction of raw materials in the examples:
polyacrylic acid adhesive, purchased from Jiangyin fine chemical plant.
A11 nonionic dispersant, available from Changhao trade company, Changhao trade, Shunsha city, the specific component is sodium polyacrylate.
The coupling agent is purchased from Jinshui Jiaxuan chemical business of Zhengzhou city, and has the model number of KH 570.
Diclofenac, CAS number: 97-23-4, available from pharmaceutical chemical Limited of Julongtang, Hubei.
Isoquercitrin, CAS number: 21637-25-2, available from Nanjing Dolon Biotechnology Ltd.
N, N-dihydroxyethylglycine, CAS: 150-25-4, available from Shanghai Nouino industries, Inc.
3-mercaptopyridine, CAS: 16133-26-9, available from Shanghai Nuo chemical engineering, Inc.
Dodecyl dimethyl benzyl ammonium chloride, CAS: 139-07-1, available from Oaks chemical Co., Ltd, Shanghai.
Acrylic acid, available from Beijing Oriental subfamily, science and technology, Inc.
2, 4, 5, 6-tetrachlorophthalonitrile, CAS No.: 1897-45-6, available from Shanghai division of technologies, Inc., Yitai, Wuhan.
Isopropanol, CAS number: 67-63-0, available from Schopper Chemicals (Shanghai) Inc.
Ammonium persulfate, CAS No.: 7727-54-0, available from Schopper Chemicals (Shanghai) Inc.
N-dodecyl mercaptan, CAS number: 112-55-0, available from Liyang Rapu New materials, Inc.
Methyltrioctylammonium chloride, CAS number: 5137-55-3, available from Woodward chemical Co., Ltd.
Acetone, CAS No.: 67-64-1.
Carbon disulfide, CAS No.: 75-15-0, available from carbofuran technologies, inc.
Initiator AIBN, CAS number: 78-67-1, available from azobisisobutyronitrile, carbofuran technologies, Inc.
Tert-butanol, CAS number: 75-65-0, available from Jiayi Biotech GmbH, Kyoho.
DL-lactic acid, CAS No.: 598-82-3, available from Nanjing Kangman Lin chemical industry Co.
Epsilon-caprolactone, CAS number: 502-44-3, available from Jiayi Biotech, Inc., of the Zhuhai province.
Stannous octoate, CAS No.: 301-10-0, available from southeast Haoyanta chemical products, Inc.
Chloroform, CAS No.: 67-66-3, available from Nordo practice, Inc. of Shanghai.
The invention is further described below by means of specific embodiments.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
The specific procedure for the preparation of Unined RM antibacterial agent used in examples 1-3 was:
the Unined RM antibacterial agent comprises, by weight, 15 parts of dichlorophen, 3 parts of isoquercitrin, 4 parts of N, N-dihydroxyethyl glycine, 5 parts of mercaptopyridine, 8 parts of dodecyl benzyl dimethyl ammonium salt, 10 parts of A11 nonionic dispersing agent, 22 parts of acrylic acid and 15 parts of 2, 4, 5, 6-tetrachlorophthalonitrile.
The preparation method of the Unined RM antibacterial agent comprises the following steps:
(1) mixing the weighed dichlorophen, isoquercitrin, N-dihydroxyethyl glycine, mercaptopyridine and dodecyl benzyl dimethyl ammonium salt with 2, 4, 5, 6-tetrachlorophthalonitrile at room temperature to form uniform suspension;
(2) adding A11 nonionic dispersant into the suspension obtained in the step (1), stirring and mixing for 12 hours at the rotation speed of 500 r/min in a high-speed stirrer, adding acrylic acid, and continuing stirring and mixing for 5 minutes at the rotation speed of 500 r/min to obtain the Unined RM antibacterial agent.
Treatment solution experiment:
example 1
Raw materials: water: 97.5wt%, Unined RM antibacterial: 0.5wt%, polyacrylic acid binder: 1.5wt%, a11 nonionic dispersant: 0.25wt%, coupling agent: 0.25 wt%.
The preparation method of the long-acting antibacterial treatment solution for the textiles comprises the following steps: weighing the raw materials according to the formula; the raw materials are put into a high-speed mixer and stirred for 10 hours at the temperature of 30 ℃ and the rotating speed of 200 revolutions per minute, and the long-acting antibacterial treatment solution for the textiles is obtained.
Example 2
Raw materials: water: 84 wt%, Unined RM antimicrobial 3.5 wt%, polyacrylic acid binder: 11.5 wt%, a11 non-ionic dispersant: 0.5wt%, coupling agent: 0.5 wt%.
The preparation method of the long-acting antibacterial treatment solution for the textiles comprises the following steps: weighing the raw materials according to a formula; the raw materials are put into a high-speed mixer and stirred for 10 hours at the temperature of 30 ℃ and the rotating speed of 200 revolutions per minute, and the long-acting antibacterial treatment solution for the textiles is obtained.
Example 3
Raw materials: water: 90 wt%, Unined RM antibacterial agent 2 wt%, polyacrylic acid binder: 7.3 wt%, A11 nonionic dispersant 0.4 wt%, coupling agent: 0.3 wt%.
The preparation method of the long-acting antibacterial treatment solution for the textiles comprises the following steps: weighing the raw materials according to a formula; the raw materials are put into a high-speed mixer and stirred for 10 hours at the temperature of 30 ℃ and the rotating speed of 200 revolutions per minute, and the long-acting antibacterial treatment solution for the textiles is obtained.
The long-acting antibacterial performance of the textile long-acting antibacterial treatment liquid of example 1-2 was tested:
materials:
long-acting antibacterial treatment fluid for textiles
Textile 1: woolen baby tops (100% wool), commercially available.
Textile 2: pure cotton baby tops (100% combed cotton) are commercially available.
Textile 3: blended children's garments jacket (80% combed cotton, 17% polyester, 3% spandex), commercially available.
A machine: the antibacterial treatment production line for textiles comprises a washing, soaking and spin-drying device and a drying device.
The method comprises the following steps:
putting purchased textiles into an antibacterial treatment production line, and adding the treatment solution produced according to the embodiment, wherein the weight ratio of the treatment solution to the textiles is 10: 1; then stirring the mixture for 30 minutes at room temperature at a stirring speed of 60 revolutions per minute; then discharging the treatment solution for later use; the wet textile is put into a dryer to be dried for 1 hour after being dried in a spin dryer at high speed, and the temperature is raised to 120 ℃ for standby.
Textile 1, textile 2, and textile 3 treated with the antibacterial treatment solution of example 1 are designated as sample 1, sample 2, and sample 3, respectively.
Textile 1, textile 2, and textile 3 treated with the antibacterial treatment solution of example 2 were designated as sample 4, sample 5, and sample 6, respectively.
Antibacterial testing
The antibacterial test was carried out according to FZ/T73023-2006 standard. The species tested were E.coli (ATCC25922), methicillin-resistant Staphylococcus aureus (ATCC43300), Staphylococcus aureus (ATCC6538), Candida albicans (ATCC 10231).
Immersion washing experiment
The textile samples treated with the antibacterial treatment solution obtained above were washed according to FZ/T73023 standard, but the number of washes was 100 times instead of 50 times as required by the standard. The resulting textile was tested for antimicrobial activity.
TABLE 1. inhibition (%). of the textile swatches treated in example 1 after 100 washes
Experimental strains Sample No. 1 Sample No. 2 Sample No. 3
Escherichia coli 96.1 98.9 97.2
Staphylococcus aureus 99.3 99.2 98.3
Candida albicans 96.7 98.6 90.2
Methicillin-resistant staphylococcus aureus (MRSA) 99.8 99.2 99.1
As can be seen from Table 1, the textile treated in example 1 has a bacteriostatic rate of over 70% after 100 washes, which shows that the invention has practical bacteriostatic action.
TABLE 2. inhibition (%), after 100 washes of the textile swatches treated in example 2 (%)
Experimental strain Sample No. 4 Sample No. 5 Sample No. 6
Escherichia coli 99.9 99.9 98.5
Staphylococcus aureus 99.8 99.3 99.2
Candida albicans 98.9 99.1 95.1
Methicillin-resistant staphylococcus aureus 98.4 99.7 93.4
As can be seen from Table 2, the textile treated in example 2 has a bacteriostatic rate of over 70% after 100 washes, which shows that the invention has practical bacteriostatic action.
Example 4
Raw materials: water: 97.5wt%, Unined RM antibacterial: 0.5wt%, polyacrylic acid binder: 1.5wt%, dispersant sodium polyacrylate: 0.25wt%, coupling agent: 0.25 wt%.
The preparation method of the long-acting antibacterial treatment solution for the textiles comprises the following steps: weighing the raw materials according to a formula; the raw materials are put into a high-speed mixer and stirred for 10 hours at the temperature of 30 ℃ and the rotating speed of 200 revolutions per minute, and the long-acting antibacterial treatment solution for the textiles is obtained.
The specific preparation process of the Unined RM antibacterial agent adopted in example 4 is as follows:
the Unined RM antibacterial agent comprises, by weight, 15 parts of dichlorophen, 3 parts of isoquercitrin, 4 parts of N, N-dihydroxyethyl glycine, 5 parts of mercaptopyridine, 8 parts of dodecyl benzyl dimethyl ammonium salt, 10 parts of dispersant sodium polyacrylate, 22 parts of acrylic acid and 15 parts of 2, 4, 5, 6-tetrachlorophthalonitrile.
The preparation method of the Unined RM antibacterial agent comprises the following steps:
(1) mixing the weighed dichlorophen, isoquercitrin, N-dihydroxyethyl glycine, mercaptopyridine and dodecyl benzyl dimethyl ammonium salt with 2, 4, 5, 6-tetrachlorophthalonitrile at room temperature to form uniform suspension;
(2) and (2) adding a dispersant sodium polyacrylate into the suspension obtained in the step (1), stirring and mixing for 12 hours in a high-speed stirrer at the rotating speed of 500 revolutions per minute, adding acrylic acid, and continuing stirring and mixing for 5 minutes at the rotating speed of 500 revolutions per minute to obtain the Unined RM antibacterial agent.
The preparation process of the dispersant sodium polyacrylate comprises the following steps: mixing acrylic acid and isopropanol in a mass ratio of 1:1 to obtain a mixed solution A; ammonium persulfate and deionized water are mixed according to a solid-to-liquid ratio of 1: 25(g/mL) to obtain a mixed solution B; mixing n-dodecyl mercaptan, isopropanol and deionized water in a mass ratio of 1: 25: 7, uniformly mixing to obtain a mixed solution C, wherein the mass ratio of n-dodecyl mercaptan, acrylic acid and ammonium persulfate is 1: 22: 1; heating the mixed solution C to 85 ℃, and simultaneously dripping the mixed solution A and the mixed solution B at the dripping speed of 8 mu L/s; after the addition, the reaction is carried out for 3 hours at 85 ℃; after the reaction is finished, cooling the reaction liquid to 40 ℃, and adjusting the pH value of the reaction liquid to 7 by using a sodium hydroxide aqueous solution with the mass fraction of 30%; and distilling the reaction liquid under reduced pressure to remove isopropanol and water to obtain the dispersant sodium polyacrylate.
Example 5
Raw materials: water: 97.5wt%, Unined RM antibacterial: 0.5wt%, polyacrylic acid binder: 1.5wt%, dispersant sodium polyacrylate: 0.25wt%, coupling agent: 0.25 wt%.
The preparation method of the textile long-acting antibacterial treatment solution comprises the following steps: weighing the raw materials according to a formula; the raw materials are put into a high-speed mixer and stirred for 10 hours at the temperature of 30 ℃ and the rotating speed of 200 revolutions per minute, and the long-acting antibacterial treatment solution for the textiles is obtained.
The specific preparation process of the Unined RM antibacterial agent adopted in example 5 is as follows:
the Unined RM antibacterial agent comprises, by weight, 15 parts of dichlorophen, 3 parts of isoquercitrin, 4 parts of N, N-dihydroxyethyl glycine, 5 parts of mercaptopyridine, 8 parts of dodecyl benzyl dimethyl ammonium salt, 10 parts of dispersant sodium polyacrylate, 22 parts of acrylic acid and 15 parts of 2, 4, 5, 6-tetrachlorophthalonitrile.
The preparation method of the Unined RM antibacterial agent comprises the following steps:
(1) mixing the weighed dichlorophen, isoquercitrin, N-dihydroxyethyl glycine, mercaptopyridine and dodecyl benzyl dimethyl ammonium salt with 2, 4, 5, 6-tetrachlorophthalonitrile at room temperature to form uniform suspension;
(2) and (2) adding a dispersant sodium polyacrylate into the suspension obtained in the step (1), stirring and mixing for 12 hours in a high-speed stirrer at the rotating speed of 500 revolutions per minute, adding acrylic acid, and continuing stirring and mixing for 5 minutes at the rotating speed of 500 revolutions per minute to obtain the Unined RM antibacterial agent.
The preparation process of the dispersant sodium polyacrylate comprises the following steps: (1) sequentially adding n-dodecyl mercaptan, methyl trioctyl ammonium chloride and acetone into a reaction container, wherein the mass ratio of n-dodecyl mercaptan to methyl trioctyl chloride to acetone is 1: 0.07: 3.5, introducing nitrogen, keeping the temperature of the reaction system at 5 ℃ and stirring for 3 minutes at the rotating speed of 180 revolutions per minute; adding a sodium hydroxide aqueous solution with the mass fraction of 40%, wherein the mass ratio of the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is 0.4:1, and stirring at the rotating speed of 180 revolutions per minute for 20 minutes; then adding 25% by mass of carbon disulfide acetone solution, wherein the mass ratio of the carbon disulfide acetone solution to the n-dodecyl mercaptan is 1.4:1, and stirring at the rotating speed of 180 revolutions per minute for 10 minutes; and then sequentially adding chloroform and a 40% sodium hydroxide aqueous solution by mass, wherein the mass ratio of the chloroform to the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is 0.9: 2:1, stirring and reacting for 16 hours at the rotating speed of 180 revolutions per minute; after the reaction is finished, adding deionized water, wherein the mass ratio of the deionized water to the n-dodecyl mercaptan is 30:1, mixing, and adding hydrochloric acid with the mass fraction of 36%, wherein the volume ratio of the hydrochloric acid to the deionized water is 1: 20, stirring at the rotating speed of 180 revolutions per minute for 25 minutes; introducing nitrogen to evaporate acetone; filtering with 80 mesh filter cloth, and collecting filter cake; drying the filter cake for 8 hours at the temperature of 55 ℃ and the vacuum degree of 0.07MPa to obtain a chain transfer agent; (2) adding acrylic acid, an initiator AIBN, tertiary butanol and a chain transfer agent into a reaction vessel, wherein the mass ratio of the acrylic acid to the initiator AIBN to the tertiary butanol to the chain transfer agent is 1: 0.002: 1.8: 0.4, introducing nitrogen, and mixing for 15 minutes; then heating the reaction solution to 80 ℃ and reacting for 7 hours; and distilling the reaction liquid under reduced pressure to remove tert-butyl alcohol to obtain the dispersant sodium polyacrylate.
The dispersing properties of the dispersants of examples 1, 4 and 5 were determined: cutting glass fiber with diameter of 6 μm (purchased from Yongxing glass fiber factory of Ningqiu city) into segments with length of 5cm, pulping in a beater (purchased from Taisite test equipment Co., Ltd., type PL4-00) at a rotation speed of 500 r/min for 10-20 min, rapidly cutting the glass fiber into flocculent state, and drying at 60 deg.C for 8 hr; 200mL of water, 4g of glass fiber and 0.4g of a dispersant were dispersed with a stirrer (purchased from Hai mechanical Co., Ltd., Nanan, Fujian province) at a rotation speed of 200 rpm for 10 minutes, and then the state of the dispersion was observed while measuring the settling time.
The specific test results are shown in table 3.
TABLE 3 Dispersion Performance test results Table
Figure BDA0001418763010000121
Example 6
Raw materials: water: 97.5wt%, Unined RM antibacterial: 0.5wt%, lactic acid-based polyester binder: 1.5wt%, dispersant sodium polyacrylate: 0.25wt%, coupling agent: 0.25 wt%.
The preparation method of the textile long-acting antibacterial treatment solution comprises the following steps: weighing the raw materials according to a formula; the raw materials are put into a high-speed mixer and stirred for 10 hours at the temperature of 30 ℃ and the rotating speed of 200 revolutions per minute, and the long-acting antibacterial treatment solution for the textiles is obtained.
The specific preparation process of the Unined RM antibacterial agent adopted in example 6 is as follows:
the Unined RM antibacterial agent comprises, by weight, 15 parts of dichlorophen, 3 parts of isoquercitrin, 4 parts of N, N-dihydroxyethyl glycine, 5 parts of mercaptopyridine, 8 parts of dodecyl benzyl dimethyl ammonium salt, 10 parts of dispersant sodium polyacrylate, 22 parts of acrylic acid and 15 parts of 2, 4, 5, 6-tetrachlorophthalonitrile.
The preparation method of the Unined RM antibacterial agent comprises the following steps:
(1) mixing the weighed dichlorophen, isoquercitrin, N-dihydroxyethyl glycine, mercaptopyridine and dodecyl benzyl dimethyl ammonium salt with 2, 4, 5, 6-tetrachlorophthalonitrile at room temperature to form uniform suspension;
(2) and (2) adding a dispersant sodium polyacrylate into the suspension obtained in the step (1), stirring and mixing for 12 hours in a high-speed stirrer at the rotating speed of 500 revolutions per minute, adding acrylic acid, and continuing stirring and mixing for 5 minutes at the rotating speed of 500 revolutions per minute to obtain the Unined RM antibacterial agent.
The preparation process of the dispersant sodium polyacrylate comprises the following steps: (1) sequentially adding n-dodecyl mercaptan, methyl trioctyl ammonium chloride and acetone into a reaction container, wherein the mass ratio of n-dodecyl mercaptan to methyl trioctyl chloride to acetone is 1: 0.07: 3.5, introducing nitrogen, keeping the temperature of the reaction system at 5 ℃ and stirring for 3 minutes at the rotating speed of 180 revolutions per minute; adding a sodium hydroxide aqueous solution with the mass fraction of 40%, wherein the mass ratio of the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is 0.4:1, and stirring at the rotating speed of 180 revolutions per minute for 20 minutes; then adding 25% by mass of acetone solution of carbon disulfide, wherein the mass ratio of the acetone solution of carbon disulfide to n-dodecyl mercaptan is 1.4:1, and stirring at the rotating speed of 180 revolutions per minute for 10 minutes; and then sequentially adding chloroform and a 40% sodium hydroxide aqueous solution by mass, wherein the mass ratio of the chloroform to the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is 0.9: 2:1, stirring and reacting for 16 hours at the rotating speed of 180 revolutions per minute; after the reaction is finished, adding deionized water, wherein the mass ratio of the deionized water to the n-dodecyl mercaptan is 30:1, mixing, adding hydrochloric acid with the mass fraction of 36%, and the volume ratio of the hydrochloric acid to the deionized water is 1: 20, stirring at the rotating speed of 180 revolutions per minute for 25 minutes; introducing nitrogen to evaporate and exhaust the acetone; filtering with 80 mesh filter cloth, and collecting filter cake; drying the filter cake for 8 hours at the temperature of 55 ℃ and the vacuum degree of 0.07MPa to obtain the chain transfer agent; (2) adding acrylic acid, an initiator AIBN, tertiary butanol and a chain transfer agent into a reaction vessel, wherein the mass ratio of the acrylic acid to the initiator AIBN to the tertiary butanol to the chain transfer agent is 1: 0.002: 1.8: 0.4, introducing nitrogen and mixing for 15 minutes; then heating the reaction solution to 80 ℃ and reacting for 7 hours; and distilling the reaction liquid under reduced pressure to remove tert-butyl alcohol to obtain the dispersant sodium polyacrylate.
The preparation process of the lactic acid-based polyester adhesive comprises the following steps: adding DL-lactic acid, epsilon-caprolactone and stannous octoate into a reaction container, wherein the mass ratio of the DL-lactic acid to the epsilon-caprolactone to the stannous octoate is 90: 10: 0.1, stirring and heating to 120 ℃ at the stirring speed of 500 revolutions per minute, and reacting for 3 hours to remove water in a reaction system; heating the reaction solution to 160 ℃, and polymerizing for 8 hours; after the reaction is finished, cooling the reaction liquid to room temperature, adding trichloromethane, wherein the volume ratio of the reaction liquid to the trichloromethane is 1: 0.8, stirring for 5 minutes at the rotating speed of 300 revolutions per minute; then adding methanol, wherein the volume ratio of the methanol to the reaction liquid is 6: 1, stirring at the rotating speed of 200-300 revolutions per minute for 10-15 minutes, and generating precipitates; centrifuging at the rotating speed of 1000 rpm for 15 minutes, and removing supernatant to obtain a bottom solid; and drying the bottom solid for 10 hours at the temperature of 55 ℃ and under the vacuum degree of 0.08MPa to obtain the lactic acid-based polyester adhesive.
Example 7
Raw materials: water: 97.5wt%, Unined RM antibacterial: 0.5wt%, binder: 1.5wt%, dispersant sodium polyacrylate: 0.25wt%, coupling agent: 0.25 wt%.
The adhesive is a mixture of a polyacrylic acid adhesive and a lactic acid-based polyester adhesive, wherein the mass ratio of the polyacrylic acid adhesive to the lactic acid-based polyester adhesive is 1: 3.
the preparation method of the long-acting antibacterial treatment solution for the textiles comprises the following steps: weighing the raw materials according to a formula; and (3) putting the raw materials into a high-speed mixer, and stirring at the rotating speed of 200 revolutions per minute for 10 hours at the temperature of 30 ℃ to obtain the long-acting antibacterial treatment solution for the textiles.
The specific preparation process of the Unined RM antibacterial agent adopted in the example 7 comprises the following steps:
the Unined RM antibacterial agent comprises, by weight, 15 parts of dichlorophen, 3 parts of isoquercitrin, 4 parts of N, N-dihydroxyethyl glycine, 5 parts of mercaptopyridine, 8 parts of dodecyl benzyl dimethyl ammonium salt, 10 parts of dispersant sodium polyacrylate, 22 parts of acrylic acid and 15 parts of 2, 4, 5, 6-tetrachlorophthalonitrile.
The preparation method of the Unined RM antibacterial agent comprises the following steps:
(1) mixing the weighed dichlorophen, isoquercitrin, N-dihydroxyethyl glycine, mercaptopyridine and dodecyl benzyl dimethyl ammonium salt with 2, 4, 5, 6-tetrachlorophthalonitrile at room temperature to form uniform suspension;
(2) and (2) adding a dispersant sodium polyacrylate into the suspension obtained in the step (1), stirring and mixing for 12 hours in a high-speed stirrer at the rotating speed of 500 revolutions per minute, adding acrylic acid, and continuing stirring and mixing for 5 minutes at the rotating speed of 500 revolutions per minute to obtain the Unined RM antibacterial agent.
The preparation process of the dispersant sodium polyacrylate comprises the following steps: (1) sequentially adding n-dodecyl mercaptan, methyl trioctyl ammonium chloride and acetone into a reaction container, wherein the mass ratio of n-dodecyl mercaptan to methyl trioctyl chloride to acetone is 1: 0.07: 3.5, introducing nitrogen, keeping the temperature of the reaction system at 5 ℃ and stirring for 3 minutes at the rotating speed of 180 revolutions per minute; adding a sodium hydroxide aqueous solution with the mass fraction of 40%, wherein the mass ratio of the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is 0.4:1, and stirring at the rotating speed of 180 revolutions per minute for 20 minutes; then adding 25% by mass of acetone solution of carbon disulfide, wherein the mass ratio of the acetone solution of carbon disulfide to n-dodecyl mercaptan is 1.4:1, and stirring at the rotating speed of 180 revolutions per minute for 10 minutes; and then sequentially adding chloroform and a 40% sodium hydroxide aqueous solution by mass, wherein the mass ratio of the chloroform to the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is 0.9: 2:1, stirring and reacting for 16 hours at the rotating speed of 180 revolutions per minute; after the reaction is finished, adding deionized water, wherein the mass ratio of the deionized water to the n-dodecyl mercaptan is 30:1, mixing, adding hydrochloric acid with the mass fraction of 36%, and the volume ratio of the hydrochloric acid to the deionized water is 1: 20, stirring at the rotating speed of 180 revolutions per minute for 25 minutes; introducing nitrogen to evaporate and exhaust the acetone; filtering with 80 mesh filter cloth, and collecting filter cake; drying the filter cake for 8 hours at the temperature of 55 ℃ and the vacuum degree of 0.07MPa to obtain the chain transfer agent; (2) adding acrylic acid, an initiator AIBN, tertiary butanol and a chain transfer agent into a reaction vessel, wherein the mass ratio of the acrylic acid to the initiator AIBN to the tertiary butanol to the chain transfer agent is 1: 0.002: 1.8: 0.4, introducing nitrogen and mixing for 15 minutes; then heating the reaction solution to 80 ℃ and reacting for 7 hours; and (3) distilling the reaction liquid under reduced pressure to remove tert-butyl alcohol to obtain the dispersant sodium polyacrylate.
The preparation process of the lactic acid-based polyester adhesive comprises the following steps: adding DL-lactic acid, epsilon-caprolactone and stannous octoate into a reaction container, wherein the mass ratio of the DL-lactic acid to the epsilon-caprolactone to the stannous octoate is 90: 10: 0.1, stirring and heating to 120 ℃ at the stirring speed of 500 revolutions per minute, and reacting for 3 hours to remove water in a reaction system; heating the reaction solution to 160 ℃, and polymerizing for 8 hours; after the reaction is finished, cooling the reaction liquid to room temperature, adding trichloromethane, wherein the volume ratio of the reaction liquid to the trichloromethane is 1: 0.8, stirring for 5 minutes at the rotating speed of 300 revolutions per minute; then adding methanol, wherein the volume ratio of the methanol to the reaction liquid is 6: 1, stirring at the rotating speed of 200-300 revolutions per minute for 10-15 minutes, and generating precipitates; centrifuging at the rotating speed of 1000 rpm for 15 minutes, and removing supernatant to obtain a bottom solid; and drying the bottom solid for 10 hours at the temperature of 55 ℃ and under the vacuum degree of 0.08MPa to obtain the lactic acid-based polyester adhesive.
The adhesive properties of the adhesives of examples 5-7 were determined by the following specific test procedures:
(1) preparing slurry: weighing 25g of adhesive, adding 100mL of distilled water, mixing for 10 minutes, heating to 95 ℃, and preserving heat for 1 hour to obtain slurry;
(2) dipping pure cotton roving (purchased from Weifang Runfang Runflat textile Limited) wound on a metal frame in the serous fluid for 5 minutes, taking out the roving frame, hanging and drying, and shearing the light pulp roving strips for later use;
(3) after the light pulp roving is dried in the air, the light pulp roving is balanced for 24 hours under the environment that the temperature is 20 ℃ and the relative humidity is 65%, and then the maximum strength and the breaking work of the light pulp roving are tested by adopting a universal material testing machine (purchased from Shanghai cast gold analytical instrument Co., Ltd., model number: zwick).
And (3) testing conditions are as follows: the tensile rate was 50mm/min, the distance between the sample chucks was 100mm, the test temperature was 20 ℃ and the relative humidity was 65%, and 20 samples were tested for each example. After removing abnormal values, taking the average value as the test result.
The specific test results are shown in table 4.
Table 4: adhesion Performance test results Table
Maximum strength (N) Break work (J)
Example 5 58.3 0.215
Example 6 66.2 0.279
Example 7 72.8 0.302
The above description is only an embodiment of the present invention, and is not intended to limit the present invention in any way, and simple modifications, equivalent changes and modifications may be made without departing from the technical solutions of the present invention, and the protection scope of the present invention is also included in the present invention.

Claims (6)

1. The long-acting antibacterial treatment solution for the textiles is characterized by comprising the following raw materials in percentage by weight: 84-97.5% of deionized water, 0.5-3.5% of Unined RM antibacterial agent, 1.5-11.5% of adhesive, 0.25-0.5% of dispersant and 0.25-0.5% of coupling agent;
the Unined RM antibacterial agent comprises, by weight, 10-15 parts of phenols, 1-3 parts of isoquercitrin, 2-4 parts of N, N-dihydroxyethylglycine, 3-5 parts of mercaptopyridine, 5-8 parts of dodecyl benzyl dimethyl ammonium salt, 0.3-10 parts of a dispersing agent, 0.56-22 parts of acrylic acid and 10-15 parts of 2, 4, 5, 6-tetrachloroisophthalonitrile;
the dispersing agent is sodium polyacrylate, and the preparation process of the sodium polyacrylate comprises the following steps:
(1) sequentially adding n-dodecyl mercaptan, methyl trioctyl ammonium chloride and acetone into a reaction container, wherein the mass ratio of the n-dodecyl mercaptan to the methyl trioctyl ammonium chloride to the acetone is 1: 0.07 (3.2-3.5), introducing nitrogen, keeping the temperature of the reaction system at 2-5 ℃, and stirring at the rotation speed of 150-; adding 40-50% of sodium hydroxide aqueous solution by mass, wherein the mass ratio of the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is (0.4-0.5):1, and stirring at the rotation speed of 150-; then adding 25-30% of carbon disulfide acetone solution by mass, wherein the mass ratio of the carbon disulfide acetone solution to the n-dodecyl mercaptan is (1.3-1.4):1, and stirring at the rotation speed of 150-; and then sequentially adding chloroform and 40-50% by mass of sodium hydroxide aqueous solution, wherein the mass ratio of the chloroform to the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is (0.8-0.9): 2:1, stirring and reacting for 12-18 hours at the rotating speed of 150-; after the reaction is finished, adding deionized water, wherein the mass ratio of the deionized water to the n-dodecyl mercaptan is (30-40) to 1, mixing, adding 35-37% of hydrochloric acid by mass, and the volume ratio of the hydrochloric acid to the deionized water is 1: (20-25), stirring at the rotating speed of 150-; introducing nitrogen to remove acetone; filtering with 80-100 mesh filter cloth, and collecting filter cake; drying the filter cake for 8-10 hours at 50-60 ℃ and under the vacuum degree of 0.06-0.08MPa to obtain the chain transfer agent;
(2) adding acrylic acid, an initiator AIBN, tertiary butanol and the chain transfer agent into a reaction vessel, wherein the mass ratio of the acrylic acid to the initiator AIBN to the tertiary butanol to the chain transfer agent is 1: 0.002: (1.8-1.9): 0.4, introducing nitrogen, and mixing for 10-15 minutes; then heating the reaction solution to 75-80 ℃ and reacting for 7-8 hours; distilling the reaction liquid under reduced pressure to remove tert-butyl alcohol to obtain the sodium polyacrylate;
the adhesive is a mixture of a polyacrylic acid adhesive and a lactic acid-based polyester adhesive, wherein the mass ratio of the polyacrylic acid adhesive to the lactic acid-based polyester adhesive is 1: (3-5).
2. The long-acting antibacterial treatment solution for textiles according to claim 1, wherein the phenols are one or a combination of isopropyl methylphenol, triclosan, dichlorophen, chlorobenzyl phenol and chlorocresol.
3. The long-acting antibacterial treating fluid for textiles according to claim 1, wherein the Unined RM antibacterial agent is prepared by the following steps:
(1) mixing weighed phenols, isoquercitrin, N-dihydroxyethyl glycine, mercaptopyridine, dodecyl benzyl dimethyl ammonium salt and 2, 4, 5, 6-tetrachloroisophthalonitrile at room temperature to form uniform suspension;
(2) adding a dispersing agent into the suspension obtained in the step (1), mixing for 10-12 hours, then adding acrylic acid, and mixing for 2-5 minutes to obtain the Unined RM antibacterial agent.
4. The long-acting antibacterial treatment fluid for textiles according to claim 1, wherein the lactic acid-based polyester binder is prepared by the following steps: adding DL-lactic acid, epsilon-caprolactone and stannous octoate into a reaction container, wherein the mass ratio of the DL-lactic acid to the epsilon-caprolactone to the stannous octoate is (90-94): (6-10): 0.1, stirring and heating to 140 ℃ at the stirring speed of 600 revolutions per minute of 400-; heating the reaction solution to 160-180 ℃, and polymerizing for 4-8 hours; after the polymerization is finished, cooling the reaction liquid to room temperature, adding trichloromethane, wherein the volume ratio of the reaction liquid to the trichloromethane is 1: (0.6-0.8), stirring at the rotating speed of 200-300 revolutions per minute for 5-10 minutes; then adding methanol, wherein the volume ratio of the methanol to the reaction liquid is (5-6): 1, stirring at the rotation speed of 200-300 revolutions per minute for 10-15 minutes to generate precipitates; centrifuging at the rotation speed of 1000-2000 rpm for 10-15 minutes, and removing the supernatant to obtain a bottom solid; and drying the bottom solid for 6-10 hours at 50-60 ℃ under the vacuum degree of 0.08-0.09MPa to obtain the lactic acid based polyester adhesive.
5. The long-acting antibacterial treatment fluid for the textiles is characterized by comprising the following raw materials in percentage by weight: deionized water: 97.5wt%, Unined RM antibacterial agent: 0.5wt%, binder: 1.5wt%, dispersant sodium polyacrylate: 0.25wt%, coupling agent: 0.25 wt%;
the adhesive is a mixture of a polyacrylic acid adhesive and a lactic acid-based polyester adhesive, and the mass ratio of the polyacrylic acid adhesive to the lactic acid-based polyester adhesive is 1: 3;
the Unined RM antibacterial agent comprises, by weight, 15 parts of dichlorophen, 3 parts of isoquercitrin, 4 parts of N, N-dihydroxyethyl glycine, 5 parts of mercaptopyridine, 8 parts of dodecyl benzyl dimethyl ammonium salt, 10 parts of dispersant sodium polyacrylate, 22 parts of acrylic acid and 15 parts of 2, 4, 5, 6-tetrachloroisophthalonitrile;
the preparation method of the Unined RM antibacterial agent comprises the following steps:
(1) mixing the weighed dichlorophen, isoquercitrin, N-dihydroxyethyl glycine, mercaptopyridine, dodecyl benzyl dimethyl ammonium salt and 2, 4, 5, 6-tetrachloroisophthalonitrile at room temperature to form uniform suspension;
(2) adding a dispersant sodium polyacrylate into the suspension obtained in the step (1), stirring and mixing for 12 hours in a high-speed stirrer at the rotating speed of 500 revolutions per minute, adding acrylic acid, and continuing stirring and mixing for 5 minutes at the rotating speed of 500 revolutions per minute to obtain the Unined RM antibacterial agent;
the preparation process of the dispersant sodium polyacrylate comprises the following steps: (1) sequentially adding n-dodecyl mercaptan, methyl trioctyl ammonium chloride and acetone into a reaction container, wherein the mass ratio of the n-dodecyl mercaptan to the methyl trioctyl ammonium chloride to the acetone is 1: 0.07: 3.5, introducing nitrogen, keeping the temperature of the reaction system at 5 ℃ and stirring for 3 minutes at the rotating speed of 180 revolutions per minute; adding a sodium hydroxide aqueous solution with the mass fraction of 40%, wherein the mass ratio of the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is 0.4:1, and stirring at the rotating speed of 180 revolutions per minute for 20 minutes; then adding 25% by mass of carbon disulfide acetone solution, wherein the mass ratio of the carbon disulfide acetone solution to the n-dodecyl mercaptan is 1.4:1, and stirring at the rotating speed of 180 revolutions per minute for 10 minutes; and then sequentially adding chloroform and a 40% sodium hydroxide aqueous solution by mass, wherein the mass ratio of the chloroform to the sodium hydroxide aqueous solution to the n-dodecyl mercaptan is 0.9: 2:1, stirring and reacting for 16 hours at the rotating speed of 180 revolutions per minute; after the reaction is finished, adding deionized water, wherein the mass ratio of the deionized water to the n-dodecyl mercaptan is 30:1, mixing, adding hydrochloric acid with the mass fraction of 36%, and the volume ratio of the hydrochloric acid to the deionized water is 1: 20, stirring at the rotating speed of 180 revolutions per minute for 25 minutes; introducing nitrogen to evaporate and exhaust the acetone; filtering with 80 mesh filter cloth, and collecting filter cake; drying the filter cake for 8 hours at the temperature of 55 ℃ and the vacuum degree of 0.07MPa to obtain a chain transfer agent; (2) adding acrylic acid, an initiator AIBN, tertiary butanol and the chain transfer agent into a reaction vessel, wherein the mass ratio of the acrylic acid to the initiator AIBN to the tertiary butanol to the chain transfer agent is 1: 0.002: 1.8: 0.4, introducing nitrogen and mixing for 15 minutes; then heating the reaction solution to 80 ℃ and reacting for 7 hours; distilling the reaction liquid under reduced pressure to remove tert-butyl alcohol to obtain the dispersant sodium polyacrylate;
the preparation process of the lactic acid-based polyester adhesive comprises the following steps: adding DL-lactic acid, epsilon-caprolactone and stannous octoate into a reaction container, wherein the mass ratio of the DL-lactic acid to the epsilon-caprolactone to the stannous octoate is 90: 10: 0.1, stirring and heating to 120 ℃ at the stirring speed of 500 revolutions per minute, and reacting for 3 hours to remove water in a reaction system; heating the reaction solution to 160 ℃, and polymerizing for 8 hours; after the reaction is finished, cooling the reaction liquid to room temperature, adding trichloromethane, wherein the volume ratio of the reaction liquid to the trichloromethane is 1: 0.8, stirring for 5 minutes at the rotating speed of 300 revolutions per minute; then adding methanol, wherein the volume ratio of the methanol to the reaction liquid is 6: 1, stirring at the rotation speed of 200-300 revolutions per minute for 10-15 minutes to generate precipitates; centrifuging at the rotating speed of 1000 rpm for 15 minutes, and removing supernatant to obtain a bottom solid; and drying the bottom solid for 10 hours at the temperature of 55 ℃ and the vacuum degree of 0.08MPa to obtain the lactic acid-based polyester adhesive.
6. A method of preparing a long-acting antimicrobial treatment solution for textiles according to any of claims 1 to 5, comprising the steps of: weighing the raw materials according to a formula; the raw materials are put into a high-speed mixer and stirred for 10 to 12 hours at the temperature of between 25 and 35 ℃ and the rotating speed of 100 and 200 revolutions per minute to obtain the long-acting antibacterial treatment fluid for textiles.
CN201710879296.2A 2017-09-26 2017-09-26 Long-acting antibacterial treatment fluid for textiles and preparation method thereof Active CN107761372B (en)

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