WO2025092014A1 - Agent imperméable à l'eau exempt de fluorure d'origine biologique, son procédé de préparation et son utilisation - Google Patents

Agent imperméable à l'eau exempt de fluorure d'origine biologique, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2025092014A1
WO2025092014A1 PCT/CN2024/104593 CN2024104593W WO2025092014A1 WO 2025092014 A1 WO2025092014 A1 WO 2025092014A1 CN 2024104593 W CN2024104593 W CN 2024104593W WO 2025092014 A1 WO2025092014 A1 WO 2025092014A1
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WIPO (PCT)
Prior art keywords
bio
waterproofing agent
fluorine
oil
natural
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Pending
Application number
PCT/CN2024/104593
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English (en)
Chinese (zh)
Inventor
周长年
储鑫
华燕
朱佳
徐有琦
黄婧
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Jiangsu New Reba Biotechnology Inc
Wuxi Colotex Bio-Technology Co Ltd
Original Assignee
Jiangsu New Reba Biotechnology Inc
Wuxi Colotex Bio-Technology Co Ltd
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Publication of WO2025092014A1 publication Critical patent/WO2025092014A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • 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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • 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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/17—Natural resins, resinous alcohols, resinous acids, or derivatives 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
    • 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
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

Definitions

  • the present application belongs to the field of textile printing and dyeing technology in the printing and dyeing production of the textile industry, and in particular relates to a bio-based fluorine-free waterproofing agent and a preparation method and application thereof.
  • the complete equipment includes at least assault jackets, tents, thermal insulation clothes, waterproof shoes, waterproof raincoats, etc., and these equipment have been waterproofed.
  • the so-called waterproof means that after the fabric has been specially treated, water droplets will fall on the fabric, form beads and slide off. The water droplets will not spread or even penetrate the fabric, thereby wetting the fabric.
  • waterproofing agents mainly quaternary ammonium pyridinium salts, hydroxymethyl melamine derivatives, silicone waterproofing agents, etc., which have good waterproofing effects but average hand feel; fluorocarbon waterproof and oil-proof agents have good spinning effects, good hand feel, and are resistant to washing, but perfluorocarbon compounds contain PFOA, PFOS and APEO, which are currently difficult to degrade in the environment, are bioaccumulative and have multiple toxicities, and have the common characteristics of persistent organic pollutants. They are considered to be new persistent environmental pollutants that are the focus of research in the 21st century and do not meet the development trends and requirements of the textile industry.
  • the present application provides a bio-based fluorine-free waterproofing agent and a preparation method and application thereof.
  • Fluorine waterproofing agent has good stability and no odor. After the fabric is treated, the color change is small, the binding fastness is good, the hand feel is tough, and there is no crease. At the same time, the fluorine-free waterproofing agent is natural, degradable and pollution-free to the environment.
  • the finished fabric can directly contact the human body, has no cytotoxicity, no irritation to the skin, and is suitable for a wide range of applications.
  • the present application provides a bio-based fluorine-free waterproofing agent, wherein the raw materials of the fluorine-free waterproofing agent include a bio-based monomer, a base monomer, a functional monomer, an initiator, a bio-based emulsifier, a natural oil sulfonated oil, a rosin-based amino acid surfactant, a lignin-furfural bio-based resin, a pH regulator, a defoamer and deionized water;
  • the raw materials of the fluorine-free waterproofing agent include a bio-based monomer, a base monomer, a functional monomer, an initiator, a bio-based emulsifier, a natural oil sulfonated oil, a rosin-based amino acid surfactant, a lignin-furfural bio-based resin, a pH regulator, a defoamer and deionized water;
  • Rosin-based amino acid surfactant 1%-5%
  • pH adjuster 0.01%-1%
  • the bio-based monomer is at least one of bio-based octadecyl methacrylate or bio-based octadecyl acrylate;
  • the monomer is at least one of butyl methacrylate, methyl methacrylate, alkyl ketene dimer or dodecyl acrylate;
  • the functional monomer is at least one of methacrylamide, hydroxyethyl methacrylate, methacryl morpholine or hydroxyethyl acrylate;
  • the initiator is at least one of azobisisobutylamidine hydrochloride, ammonium persulfate or potassium persulfate;
  • the bio-based emulsifier is at least one of cardanol polyoxyethylene ether NSS 1305, NSS 1305A, NSS 1308 or octadecyl trimethyl ammonium bromide;
  • the natural oil sulfonated oil is natural sulfonated rapeseed oil, natural sulfonated castor oil or sulfated natural At least one of neatsfoot oil;
  • the pH regulator is at least one of ammonia water, liquid alkali or sodium carbonate;
  • the defoaming agent is at least one of polyoxypropyl polyoxyethyl glycerol ether and polyether modified polysiloxane.
  • the present application provides a method for preparing a bio-based fluorine-free waterproofing agent, which comprises the following steps:
  • step (2) (4) adding the remaining portion of the mixture A obtained in step (1) and the initiator aqueous solution in step (2) dropwise to the reaction kettle described in step (2) respectively;
  • the stirring speed is 800-1500 rpm, and the stirring time is 45-60 min.
  • the monomer is uniformly dispersed in water with the help of the emulsifying effect of the emulsifier.
  • the stirring speed is 50-200 rpm.
  • the dropping time is 120-180 min, and the temperature is kept at 78-82° C. for 150-200 min.
  • the dropping speed of the polymerization reaction cannot be too fast. If it is too fast, the polymerization reaction temperature may rise instantly and exceed the upper limit, and then the temperature drops back. The temperature fluctuation will produce filter residue.
  • step (5) stirring is performed during mixing, and the stirring time is 15-30 minutes;
  • step (6) stirring is performed during mixing, the stirring speed is 20-50 rpm, and the stirring time is 10-30 min.
  • the bio-based monomer is selected to be 15%-25%. When the bio-based monomer is lower than 15%, the film-forming fluorine-free waterproofing agent is too soft and does not meet the use requirements; when the bio-based monomer is greater than 25%, the film-forming fluorine-free waterproofing agent is too brittle and easily forms a crust and slag.
  • bio-based octadecyl methacrylate and bio-based octadecyl acrylate are obtained by chemical esterification of bio-based acrylic acid or bio-based methacrylic acid and bio-based octadecyl alcohol, and bio-based octadecyl alcohol is obtained by hydrogenation of bio-based stearic acid under the catalysis of copper chromate. Therefore, the raw materials of bio-based octadecyl methacrylate and bio-based octadecyl acrylate are derived from bio-based raw materials.
  • the functional monomer is at least one or any combination of methacrylamide, hydroxyethyl methacrylate, methacryl morpholine or hydroxyethyl acrylate;
  • methacrylamide has excellent cross-linking performance, and the fluorine-free waterproofing agent produced has good waterproof performance, but the product has poor permeability and average hydrophilicity; hydroxyethyl methacrylate has average cross-linking performance, but good hydrophilicity and average waterproof performance; when the two are used in combination, the product can obtain suitable hydrophilicity and waterproof effect.
  • the initiator is at least one of azobisisobutylamidine hydrochloride, ammonium persulfate or potassium persulfate, preferably azobisisobutylamidine hydrochloride;
  • the azobisisobutylamidine hydrochloride is a low-temperature initiator, which can decompose at about 45°C to generate free radicals and promote polymerization.
  • the dosage of the initiator is 0.01%-0.4%. When the initiator is less than 0.01%, the reaction speed is slow and the heating and insulation time is prolonged; when the initiator is greater than 0.4%, the reaction speed is too fast and difficult to control, and implosion is easy to occur during the reaction.
  • the bio-based emulsifier is at least one of cardanol polyoxyethylene ether NSS 1305, NSS 1305A, NSS 1308 or octadecyl trimethyl ammonium bromide;
  • cardanol polyoxyethylene ether is a good bio-based non-ionic emulsifier
  • octadecyltrimethylammonium bromide is a bio-based anionic emulsifier.
  • the combined effect of anionic and non-ionic emulsifiers is beneficial to the stability of the monomer emulsion.
  • the natural oil sulfonated oil is at least one of natural sulfonated rapeseed oil, natural sulfonated castor oil or sulfated natural neatsfoot oil, preferably natural sulfonated rapeseed oil;
  • the natural sulfonated rapeseed oil is an anionic surfactant, which works synergistically with the above-mentioned bio-based emulsifier non-ionic surfactant cardanol polyoxyethylene ether to make the monomer evenly and stably dispersed in the emulsion.
  • the mass ratio of natural sulfonated rapeseed oil to NSS 1305 is 1: (1.1-1.3).
  • the pH regulator is at least one of aqueous ammonia, liquid alkali or sodium carbonate, preferably liquid alkali;
  • the liquid caustic soda will not generate ammonia smell during high-temperature setting in the preparation process to pollute the working environment.
  • the mass percentage of NaOH in the liquid caustic soda is 32.5%.
  • the defoaming agent is at least one of polyoxypropyl polyoxyethyl glycerol ether or polyether-modified polysiloxane, preferably polyether-modified polysiloxane CD-1116M;
  • the polyether-modified polysiloxane CD-1116M can quickly penetrate into the foam in a high-temperature foaming system, destroying the stability of the foam, thereby achieving a defoaming effect.
  • the present application provides an application of a bio-based fluorine-free waterproofing agent, wherein the bio-based fluorine-free waterproofing agent is applied to the finishing of fabrics, which comprises the following steps:
  • step S2 The fabric is padded in the working solution obtained in step S1, with the liquid carrying rate being 60-80%, and then dried and shaped.
  • the padding treatment is one dip and one padding
  • the roller pressure is 0.15-0.25Mpa
  • the drying and shaping temperature is 150-180°C
  • the drying and shaping time is 60-120s;
  • the fabric is at least one of pure cotton fabric, blended fabric of cotton and polyamide fiber, blended fabric of cotton and polyester fiber or Tencel, preferably pure cotton woven fabric.
  • the present application provides a bio-based fluorine-free waterproofing agent, which is prepared using the raw materials and preparation method described in the present application.
  • the present application provides an application of a bio-based fluorine-free waterproofing agent, wherein the bio-based fluorine-free waterproofing agent described in the present application or the bio-based fluorine-free waterproofing agent prepared by any method of the present application is used for finishing of textiles.
  • This application adds bio-based monomers to replace traditional fossil carbon-based acrylic compounds.
  • Bio-based monomers are produced using plant carbon, thereby increasing the renewable carbon content.
  • the product has excellent properties such as ultra-low odor, low VOC (volatile organic compounds), environmental protection and safety.
  • rosin-based amino acid surfactant which is a bio-based amphoteric surfactant.
  • Rosin is a renewable resource abundant in nature. Its main component is resin acid. The huge non-polar tricyclic structure in its molecular structure has good hydrophobicity, while the polar carboxyl part has hydrophilicity.
  • a series of rosin acid-N-acyl amino acid surfactants are synthesized by embedding natural glutamic acid, sarcosine and polypeptides. They have good stain resistance, hard water resistance, acid and alkali stability, and have bactericidal, antiseptic, antistatic and other properties.
  • the present application adds natural oil sulfonated oil, which is an anionic sulfonated oil fatliquor made from natural oil as the main raw material, modified by sulfur trioxide gas sulfonation process, and then compounded with other necessary components. It is an excellent anionic surfactant with excellent penetration performance, improved hydrophilicity and antistatic properties; it can reduce the friction between fabrics and between fibers, and at the same time improve the feel of the fabric.
  • lignin-furfural bio-based resin which is a furfural-based bio-based resin.
  • Furfural is an important chemical raw material that can be prepared by biomass conversion.
  • Lignin is a biopolymer obtained from agricultural or forestry residues or paper pulping wastewater, and is the only aromatic natural biopolymer. Through enzymatic hydrolysis of lignin, the methoxy groups in lignin are demethylated and converted into phenolic hydroxyl products to obtain highly reactive nano-lignin.
  • Furfural is used to completely replace formaldehyde and react with highly reactive nano-lignin to synthesize lignin-furfural bio-based resin.
  • This resin resin can cross-link the network film-forming function on the fiber surface, so that the fiber surface is wrapped with a wear-resistant resin film, which reduces the slippage between fibers and has a good yarn binding effect; at the same time, the resin is evenly cross-linked and condensed on the surface of the yarn, so that the fiber ends adhere to the yarn and are not easy to pilling during friction. It helps acrylic resin to form a film on the surface of the fabric, improving the fabric's wrinkle resistance, anti-static and waterproof properties.
  • bio-based monomers, bio-based emulsifiers, natural oil sulfonated oils, rosin-based amino acid surfactants and lignin-furfural bio-based resins used in this application are all derived from nature, are non-toxic and harmless, and biodegrade quickly and thoroughly, without polluting the environment; at the same time, the products are mild in effect, and textiles are less damaged after treatment, thus achieving green and sustainable development of the industry.
  • the raw materials of the fluorine-free waterproofing agent prepared in the present application are derived from bio-based products, which can be completely biodegraded in the natural environment, are environmentally friendly and safe, and enhance the renewable and environmentally friendly value of the product, thus having significant social benefits and broad market prospects.
  • This embodiment provides a fluorine-free waterproofing agent, and the preparation method thereof is as follows:
  • This embodiment provides a fluorine-free waterproofing agent, and the preparation method thereof is as follows:
  • the evaluation of the quality of fluorine-free waterproofing agents mainly focuses on the waterproof performance and wash fastness of the fabric. A comprehensive evaluation is also required on product stability, the effect on fabric color and anti-yellowing performance.
  • No. 3 waterproofing agent is a commonly used waterproofing agent on the market.
  • the bio-based fluorine-free waterproofing agent product prepared by the present application is stable, high in content, and safe. It is a finishing agent that can be used for textile processing, has high safety, and has good application prospects.
  • bio-based fluorine-free waterproofing agents prepared in the above Examples 1-3 and the commercially commonly used waterproofing agent Comparative Example 1 were subjected to comparative tests.
  • bio-based fluorine-free waterproofing agent prepared in Examples 1-3 and a commercially available waterproofing agent were mixed with water to obtain a working solution having a concentration of 80 g/L;
  • step S2 The fabric is dipped and rolled in the working solution obtained in step S1, with a liquid rate of 60-80%, and then dried at 160°C for 90s;
  • Hand feel evaluation The two fabric samples were evaluated by hand touch method, with the original fabric hand feel rated as level 1 and the best hand feel rated as level 5. The larger the value, the better the hand feel.
  • the test results are shown in Table 2.
  • the test was conducted using a Datacolor colorimeter. The whiteness of the treated fabric was compared with that of the untreated fabric. The greater the whiteness change, the greater the yellowing. The test results are shown in Table 2.
  • the present application provides a bio-based fluorine-free waterproofing agent and a preparation method thereof.
  • a bio-based monomer is added to the reaction to replace the traditional fossil carbon-based acrylic compound;
  • a rosin-based amino acid surfactant is introduced, which is a bio-based amphoteric surfactant with good stain resistance, hard water resistance, acid and alkali stability, and bactericidal, antiseptic, antistatic and other properties;
  • a lignin-furfural bio-based resin is added after the reaction. This is a new type of furfural bio-based resin.
  • the resin will be evenly cross-linked on the surface of the yarn so that the fiber ends adhere to the yarn, and the strong adhesion of the resin can bond the fibers to restrict their movement. After washing, the fabric does not fall off or break.
  • the fabric treated with the waterproofing agent has less yellowing, good waterproof performance, and a soft and non-rough feel.
  • the raw materials of the fluorine-free waterproofing agent made in the present application are derived from bio-based products, which can be completely biodegraded in the natural environment. It is environmentally friendly and safe, and improves the recyclability of the product. Life and environmental friendly values,
  • the present application uses the above-mentioned embodiments to illustrate the bio-based fluorine-free waterproofing agent and its preparation method and application, but the present application is not limited to the above-mentioned detailed method, that is, it does not mean that the present application must rely on the above-mentioned detailed method to be implemented.
  • the technicians in the relevant technical field should understand that any improvement to the present application, the equivalent replacement of the raw materials of the present application product, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present application.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

La présente invention concerne un agent imperméable à l'eau exempt de fluorure d'origine biologique, son procédé de préparation et son utilisation. Dans la présente demande, tout d'abord, un monomère d'origine biologique est ajouté dans une réaction ; deuxièmement, un tensioactif d'acide aminé à base de colophane est introduit, qui est un tensioactif ampholytique d'origine biologique, présente les avantages d'une bonne décontamination, d'une résistance à l'eau dure et d'être stable à un acide et à un alcali et présente les performances de stérilisation, de prévention de la corrosion, de résistance à l'électricité statique, etc ; et enfin, une résine d'origine biologique de lignine-furfural est ajoutée après la réaction, laquelle résine est une nouvelle résine d'origine biologique de furfural, peut être uniformément réticulée sur la couche de surface d'un fil pour faire adhérer des extrémités de fibre au fil, et a une force adhésive relativement forte, de telle sorte que la résine peut lier les fibres, limitant ainsi le mouvement des fibres. Les matières premières de l'agent imperméable à l'eau exempt de fluorure préparé dans la présente demande sont dérivées de produits d'origine biologique et sont complètement biodégradables dans l'environnement naturel, de telle sorte que l'agent imperméable à l'eau exempt de fluorure est respectueux de l'environnement et sûr, ce qui permet d'augmenter les valeurs régénératives et respectueuses de l'environnement du produit et ayant des avantages sociaux significatifs et de vastes perspectives de marché.
PCT/CN2024/104593 2023-11-03 2024-07-10 Agent imperméable à l'eau exempt de fluorure d'origine biologique, son procédé de préparation et son utilisation Pending WO2025092014A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202311456375.4A CN117552238A (zh) 2023-11-03 2023-11-03 一种生物基无氟防水剂及其制备方法和应用
CN202311456375.4 2023-11-03

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CN120776591A (zh) * 2025-09-11 2025-10-14 杭州悦创未来新材料科技有限公司 一种有机硅防水整理剂及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116084178A (zh) * 2023-01-04 2023-05-09 江苏新瑞贝科技股份有限公司 一种生物基魔术贴背涂胶及其制备方法和应用
CN117552238A (zh) * 2023-11-03 2024-02-13 江苏新瑞贝生物科技股份有限公司 一种生物基无氟防水剂及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090256103A1 (en) * 2008-04-10 2009-10-15 Punjab University Aqueous water and oil repellent composition
KR20180127895A (ko) * 2017-05-22 2018-11-30 주식회사 마이폴리머 비불소계 아크릴 공중합체를 함유한 발수코팅액의 제조방법 및 그를 이용한 발수처리된 섬유제품
KR20210000413A (ko) * 2019-06-25 2021-01-05 ㈜대동켐텍 폴리아크릴레이트계 발수제 및 그를 이용한 발수성 섬유제품
CN114409853A (zh) * 2022-02-07 2022-04-29 湖南隆森化工有限公司 一种无氟防水剂及其制备方法
CN116084178A (zh) * 2023-01-04 2023-05-09 江苏新瑞贝科技股份有限公司 一种生物基魔术贴背涂胶及其制备方法和应用
CN116084162A (zh) * 2023-01-04 2023-05-09 江苏新瑞贝科技股份有限公司 一种生物基抗起毛球整理剂及其制备方法和应用
CN117552238A (zh) * 2023-11-03 2024-02-13 江苏新瑞贝生物科技股份有限公司 一种生物基无氟防水剂及其制备方法和应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090256103A1 (en) * 2008-04-10 2009-10-15 Punjab University Aqueous water and oil repellent composition
KR20180127895A (ko) * 2017-05-22 2018-11-30 주식회사 마이폴리머 비불소계 아크릴 공중합체를 함유한 발수코팅액의 제조방법 및 그를 이용한 발수처리된 섬유제품
KR20210000413A (ko) * 2019-06-25 2021-01-05 ㈜대동켐텍 폴리아크릴레이트계 발수제 및 그를 이용한 발수성 섬유제품
CN114409853A (zh) * 2022-02-07 2022-04-29 湖南隆森化工有限公司 一种无氟防水剂及其制备方法
CN116084178A (zh) * 2023-01-04 2023-05-09 江苏新瑞贝科技股份有限公司 一种生物基魔术贴背涂胶及其制备方法和应用
CN116084162A (zh) * 2023-01-04 2023-05-09 江苏新瑞贝科技股份有限公司 一种生物基抗起毛球整理剂及其制备方法和应用
CN117552238A (zh) * 2023-11-03 2024-02-13 江苏新瑞贝生物科技股份有限公司 一种生物基无氟防水剂及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIU JUN, HUANG SHANGDONG, YULIANG GUO: "Preparation of Washing-resistant Fluorine-free Water Repellent Agent", TEXTILE AUXILIARIES, vol. 26, no. 2, 1 February 2019 (2019-02-01), pages 26 - 29, XP093309544 *
LIU, XIMENG: "Preparation and Application of Polyacrylate Fluorine-free Water Repellent", TEXTILE AUXILIARIES, vol. 38, no. 9, 1 September 2021 (2021-09-01), pages 17 - 21, XP093309554 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120776591A (zh) * 2025-09-11 2025-10-14 杭州悦创未来新材料科技有限公司 一种有机硅防水整理剂及其制备方法

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