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CN110734518A - non-silicon fluorine-free waterproof agent, preparation method thereof and waterproof fabric - Google Patents

non-silicon fluorine-free waterproof agent, preparation method thereof and waterproof fabric Download PDF

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Publication number
CN110734518A
CN110734518A CN201911106282.2A CN201911106282A CN110734518A CN 110734518 A CN110734518 A CN 110734518A CN 201911106282 A CN201911106282 A CN 201911106282A CN 110734518 A CN110734518 A CN 110734518A
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China
Prior art keywords
fabric
waterproof
free
agent
fluorine
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CN201911106282.2A
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Chinese (zh)
Inventor
董锋
周宁
姜兴盛
托马斯·沃尔特施密特
张俊峰
李天源
卓丽琼
吴建通
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FUJIAN HUAFENG NEW MATERIALS Co Ltd
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FUJIAN HUAFENG NEW MATERIALS Co Ltd
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Priority to CN201911106282.2A priority Critical patent/CN110734518A/en
Publication of CN110734518A publication Critical patent/CN110734518A/en
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    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • 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
    • D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The non-silicon and fluorine-containing waterproof agents comprise, by mass, 20-30 parts of acrylic acid, 20-30 parts of glycidyl acrylate, 10-20 parts of diacetone acrylamide, 1-10 parts of stearic acid and 1-10 parts of a cross-linking agent, and the pH value of the non-silicon and fluorine-free waterproof agent is 5-7.

Description

non-silicon fluorine-free waterproof agent, preparation method thereof and waterproof fabric
Technical Field
The invention relates to the field of textiles, in particular to non-silicon fluorine-free waterproof agents, a preparation method thereof and waterproof fabrics.
Background
Perfluorooctane sulfonyl compounds (PFOS) and perfluorooctanoic acid (PFOA) are trace substances existing in C8 waterproof agents, have difficult degradation, bioaccumulation and various toxicities, and have common characteristics of all persistent organic pollutants, so that the PFOA and PFOA are strictly limited, and the PFOA and PFOS mainly exist in fabrics treated by fluorine-containing waterproof and oilproof finishing agents in the textile industry.
Disclosure of Invention
In view of the problems in the background art, the invention aims to provide kinds of silicon-free and fluorine-free waterproof agents and a preparation method thereof, wherein the waterproof agents are good in waterproof performance, environment-friendly, simple in production process and low in manufacturing cost, and can be applied to industrial production in a large scale to prepare fabrics using the waterproof agents.
In order to achieve the above object, in th aspect of the present invention, the inventors provide kinds of non-silicon fluorine-free water repellent, which comprises, by mass, 20 to 30 parts of acrylic acid, 20 to 30 parts of glycidyl acrylate, 10 to 20 parts of diacetone acrylamide, 1 to 10 parts of stearic acid, and 1 to 10 parts of a crosslinking agent, and has a pH of 5 to 7.
In a second aspect of the present invention, the inventors provide a method for preparing non-silicon fluorine-free water repellents, comprising the steps of:
firstly, putting water into a reaction kettle, then putting acrylic acid, glycidyl acrylate and a cross-linking agent into the reaction kettle, uniformly mixing, and reacting for 2-6 hours at the temperature of 80-110 ℃; cooling to 40-45 ℃, adding diacetone acrylamide and stearic acid, mixing uniformly, and reacting for 1-3 hours at 80-110 ℃; finally, adding an organic solvent for assisting dissolution to obtain an emulsion, and adjusting the pH value of the emulsion to 5-7 to obtain a non-silicon fluorine-free waterproof agent;
the mass ratio of the acrylic acid to the glycidyl acrylate to the cross-linking agent to the diacetone acrylamide to the stearic acid to the water is 20-30: 20-30: 1-10: 10-20:1-10: 200-300, wherein the content of the organic solvent is 10-15g/L of non-silicon fluorine-free waterproof agent.
In a third aspect of the present invention, the inventors provide waterproof fabrics treated with the non-silicon, fluorine-free water repellant provided by aspect of the present invention.
The waterproof agents without silicon and fluorine and the preparation method thereof have the advantages of good waterproof performance, capability of fully permeating fabric fibers, environmental friendliness, simple production process and low cost, and can be applied to industrial production on a large scale, and the waterproof grade of the fabric using the waterproof agent can reach 5 grade.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the technical means in detail, the following detailed description is given with reference to specific embodiments.
Diacetone acrylamide has two reactive groups: n-substituted amide and ketone are easy to copolymerize with other ethylene and monomer, so that ketone carbonyl group is introduced into polymer, and the chemical property of ketone carbonyl group can make polymer produce cross-linking grafting reaction.
First, parts by mass of a non-silicon fluorine-free water repellent according to of the present invention, which comprises 20 to 30 parts by mass of acrylic acid, 20 to 30 parts by mass of glycidyl acrylate, 10 to 20 parts by mass of diacetone acrylamide, 1 to 10 parts by mass of stearic acid, and 1 to 10 parts by mass of a crosslinking agent, and has a pH of 5 to 7, will be described.
Preferably, the water-free fluorine-free water repellent further comprises 200-300 parts by mass of water and an organic solvent, wherein the content of the organic solvent is 10-15g/L of the non-silicon fluorine-free water repellent.
The water content in the waterproof agent is increased or decreased according to the needs, so that the components can be emulsified. The organic solvent is used for assisting dissolution.
Preferably, the crosslinking agent is an isocyanate.
Preferably, the pH of the emulsion is adjusted using citric acid, sodium hydroxide, or sodium citrate solutions.
Next, a description will be given of a method for producing kinds of non-silicon fluorine-free water repellent according to a second aspect of the present invention, comprising the steps of:
firstly, putting water into a reaction kettle, then putting acrylic acid, glycidyl acrylate and a cross-linking agent into the reaction kettle, continuously stirring, and reacting for 2-6 hours at the temperature of 80-110 ℃; cooling to 40-45 ℃, adding diacetone acrylamide and stearic acid, continuously stirring, and reacting for 1-3 hours at 80-110 ℃; finally, adding an organic solvent for assisting dissolution to obtain an emulsion, and adjusting the pH value of the emulsion to 5-7 to obtain a non-silicon fluorine-free waterproof agent;
the mass ratio of the acrylic acid to the glycidyl acrylate to the cross-linking agent to the diacetone acrylamide to the stearic acid to the water is 20-30: 20-30: 1-10: 10-20:1-10: 200-300, wherein the content of the organic solvent is 10-15g/L of non-silicon fluorine-free waterproof agent.
Preferably, the organic solvent is ethanol.
Preferably, the crosslinking agent is an isocyanate.
Next, kinds of waterproof fabrics according to the third aspect of the present invention are described, which are subjected to a waterproof treatment with the non-silicon fluorine-free waterproofing agent according to the aspect of the present invention.
The preparation method of the waterproof fabric comprises the following steps:
working solution preparation, namely diluting the non-silicon fluorine-free water repellent prepared by the aspect of the invention into working solution with the concentration of 10-40g/L,
dipping rolling, namely soaking the fabric in the working solution for 10 to 90s and then rolling the fabric for times by using a padder, wherein the pressure of the padder is 1 to 2Kg/cm2The liquid carrying rate is 65-100%,
and (3) drying, namely drying the dipped padded fabric for 60-180 seconds at 150-180 ℃ to obtain the waterproof fabric.
The water-proof function of the fabric is determined by the surface appearance and the surface energy of the fabric, the surface roughness of the fabric is low, the liquid contact angle of the surface of the fabric is increased, the retention time and the residual amount of liquid on the surface of the fabric can be reduced from to a certain extent, the free energy of the surface of the fabric is low, the adhesive force is small, and the contact angle of the liquid on the solid surface is larger.
Meanwhile, the waterproof agent can fully permeate into the fabric fiber, and the waterproof performance is improved.
Preferably, the fabric is a chemical fiber fabric.
The concentration of the working solution is controlled to be 10-40g/L, and the inventor finds that when the concentration is more than 40g/L, the waterproof agent can form a coating on the surface of the fabric, so that the softness of the fabric is influenced; the concentration is less than 10g/L, the content of the waterproof agent in the fabric is too small, and a good waterproof effect cannot be achieved.
Example 1 preparation of 1 non-silicon fluorine-free water repellents:
60kg of acrylic acid, 60kg of glycidyl acrylate and 20kg of cross-linking agent (isocyanate) are taken and put into a reaction kettle containing 600kg of water, the mixture is continuously stirred, the temperature of the reaction kettle is raised to 100 ℃, the temperature is reduced to 40 ℃ after 4 hours of reaction, 40kg of diacetone acrylamide and 20kg of stearic acid are continuously added into the reaction kettle, the mixture is continuously stirred, the temperature is raised to 100 ℃, the mixture is cooled to room temperature after 2 hours of reaction, ethanol is added into the reaction kettle, the amount of the ethanol is 10g/L, emulsion is obtained, and the pH value of the emulsion is adjusted to 6, so that the non-silicon fluorine-free waterproof agent is obtained.
EXAMPLE 2 preparation of 2 non-silicon fluorine-free Water repellent
Adding 8kg of acrylic acid, 8kg of glycidyl acrylate and 3kg of cross-linking agent (isocyanate) into a reaction kettle containing 70kg of water, continuously stirring, heating to 110 ℃ of temperature of 100-.
EXAMPLE 3 preparation of 3 non-silicon fluorine-free Water repellent
20kg of acrylic acid, 20kg of glycidyl acrylate and 1kg of cross-linking agent (isocyanate) are put into a reaction kettle containing 200kg of water, continuously stirred, heated to 100 ℃, reacted for 4 hours, cooled to 40 ℃, continuously added with 10kg of diacetone acrylamide and 1kg of stearic acid, continuously stirred, heated to 100 ℃, reacted for 2 hours, cooled to room temperature, added with ethanol in an amount of 15g/L, and the pH value of the emulsion is adjusted to 7, so that the non-silicon fluorine-free waterproof agent is obtained.
EXAMPLE 4 preparation of 4 non-silicon fluorine-free Water repellent
30kg of acrylic acid, 30kg of glycidyl acrylate and 10kg of cross-linking agent (isocyanate) are taken and put into a reaction kettle containing 300kg of water, the mixture is continuously stirred, the temperature is increased to 110 ℃, the reaction is carried out for 2 hours, after the temperature is reduced to 45 ℃, 20kg of diacetone acrylamide and 10kg of stearic acid are continuously added into the reaction kettle, the mixture is continuously stirred, the temperature is increased to 80 ℃, after the reaction is carried out for 3 hours, the mixture is cooled to the room temperature, ethanol is added into the reaction kettle, the amount of the ethanol is 15g/L, and the pH value of the emulsion is adjusted to 5, so that the non-silicon fluorine-free waterproof agent is obtained.
EXAMPLE 5 preparation of 5 non-silicon fluorine-free Water repellent
30kg of acrylic acid, 20kg of glycidyl acrylate and 5kg of cross-linking agent (isocyanate) are put into a reaction kettle containing 250kg of water, continuously stirred, heated to 100 ℃, reacted for 4 hours, cooled to 43 ℃, continuously added with 15kg of diacetone acrylamide and 2kg of stearic acid, continuously stirred, heated to 100 ℃, reacted for 6 hours, cooled to room temperature, added with ethanol in an amount of 12g/L, and adjusted to pH 6 to obtain the non-silicon fluorine-free waterproof agent.
EXAMPLE 6 preparation of 6 non-silicon fluorine-free Water repellent
Adding 25kg of acrylic acid, 25kg of glycidyl acrylate and 3kg of cross-linking agent (isocyanate) into a reaction kettle containing 250kg of water, continuously stirring, heating to 80 ℃, reacting for 6 hours, cooling to 40 ℃, continuously adding 16kg of diacetone acrylamide and 3kg of stearic acid into the reaction kettle, continuously stirring, heating to 110 ℃, reacting for 1 hour, cooling to room temperature, adding ethanol into the reaction kettle, adding 14g/L of ethanol, and adjusting the pH of the emulsion to 7 to obtain the non-silicon fluorine-free waterproof agent.
EXAMPLE 11 preparation of 11 Water repellent fabrics
Preparing a working solution: the non-silicon fluorine-free water repellent prepared in example 1 was diluted to a working solution having a concentration of 30g/L,
dipping rolling, namely dipping the chemical fiber fabric in the working solution for 10-90s and rolling the chemical fiber fabric for times by using a padder, wherein the pressure of the padder is 1-2Kg/cm2The liquid carrying rate is 65-100%,
and (3) drying, namely drying the dipped padded chemical fiber fabric for 60-180 seconds at 150-180 ℃ to obtain the waterproof fabric.
EXAMPLE 12 preparation of 12 Water repellent Fabric
Preparing a working solution: the non-silicon fluorine-free water repellent prepared in example 2 was diluted to a working solution having a concentration of 30g/L,
dipping rolling, namely dipping the chemical fiber fabric in the working solution for 10-90s and rolling the chemical fiber fabric for times by using a padder, wherein the pressure of the padder is 1-2Kg/cm2The liquid carrying rate is 65-100%,
and (3) drying, namely drying the dipped padded chemical fiber fabric for 60-180 seconds at 150-180 ℃ to obtain the waterproof fabric.
EXAMPLE 13 preparation of 13 Water repellent Fabric
Preparing a working solution: preparing a working solution: the non-silicon fluorine-free water repellent prepared in example 1 was diluted to a working solution having a concentration of 10g/L,
dipping rolling, namely dipping the chemical fiber fabric in the working solution for 10-90s and rolling the chemical fiber fabric for times by using a padder, wherein the pressure of the padder is 1-2Kg/cm2The liquid carrying rate is 65-100%,
and (3) drying, namely drying the dipped padded chemical fiber fabric for 60-180 seconds at 150-180 ℃ to obtain the waterproof fabric.
EXAMPLE 14 preparation of 14 Water repellent fabrics
Preparing a working solution: the non-silicon fluorine-free water repellent prepared in example 2 was diluted to a working solution having a concentration of 40g/L,
dipping rolling, namely soaking the chemical fiber fabric in the working solution for 90s and then rolling the chemical fiber fabric for times by using a padder, wherein the pressure of the padder is 1-2Kg/cm2The liquid carrying rate is 65-100%,
and (3) drying, namely drying the dipped padded chemical fiber fabric for 60-180 seconds at 150-180 ℃ to obtain the waterproof fabric.
EXAMPLE 15 preparation of 15 Water repellent fabrics
Preparing a working solution: the non-silicon fluorine-free water repellent prepared in example 2 was diluted to a working solution having a concentration of 20g/L,
dipping rolling, namely dipping the chemical fiber fabric in the working solution for 60s and then rolling the chemical fiber fabric for times by using a padder, wherein the pressure of the padder is 1-2Kg/cm2The liquid carrying rate is 65-100%,
and (3) drying, namely drying the dipped padded chemical fiber fabric for 60-180 seconds at 150-180 ℃ to obtain the waterproof fabric.
EXAMPLE 16 preparation of 16 Water-repellent Fabric
Preparing a working solution: the non-silicon fluorine-free water repellent prepared in example 3 was diluted to a working solution having a concentration of 30g/L,
dipping rolling, namely soaking the chemical fiber fabric in the working solution for 50s and then rolling the chemical fiber fabric for times by using a padder, wherein the pressure of the padder is 1-2Kg/cm2The liquid carrying rate is 65-100%,
and (3) drying, namely drying the dipped padded chemical fiber fabric for 60-180 seconds at 150-180 ℃ to obtain the waterproof fabric.
Comparative example 1 preparation of 1 non-silicon fluorine-free waterproofing agents
Comparative example 1 differs from example 1 in that 50kg of acrylic acid and 90kg of glycidyl acrylate were added to comparative example 1.
Comparative example 2 preparation of 2 non-silicon fluorine-free Water repellent
Comparative example 2 differs from example 2 in that in comparative example 2, 90kg of acrylic acid and 50kg of glycidyl acrylate are used.
Comparative examples 3 to 4 preparation of 4 kinds of waterproof fabrics
Comparative examples 3 to 4 differ from example 11 in that the preparation of waterproof fabrics was carried out using the non-silicon fluorine-free water repellent agents prepared in comparative examples 1 and 2, respectively.
Examples 11, 12, comparative examples 3, 4, untreated chemical fiber fabrics were subjected to the textile water repellency test, test methods and results as follows:
the test method for the waterproofness of the fabric is as follows: the waterproof performance of the fabric is tested according to the AATCC-22 spray test: the sample with constant temperature and pressure is arranged on a sample frame clamp, is arranged on a fixed base horizontally forming an angle of 45 degrees, 250ml of distilled water or deionized water (the temperature is 20 +/-2 ℃ or 27 +/-2 ℃) is quickly and stably injected into a funnel, and is uniformly and continuously sprayed towards the center of the sample within 24-30 seconds through a spray head specified with the center of the sample. The fabrics after the test were rated.
The fabric water resistance rating was rated according to AATCC-22 rating standard:
100(ISO5) -wetted surface did not wet nor bead
90(ISO4) -wetted surface not wetted but stained with water droplets
80(ISO3) -wetted surfaces are wetted only at the point of spraying
70(ISO2) -drenched surface with only partial wetting
60(ISO1) -Total wetting of the drenched surface
0- -the surfaces to be showered and the other surfaces were all wetted
Numbering Untreated Example 1 Example 2 Comparative example 1 Comparative example 2
Water resistance rating ISO1 ISO5 ISO5 ISO4 ISO3
The test results show that the waterproof agent of the invention can improve the waterproof performance of the fabric, and the addition ratio of the acrylic acid and the glycidyl acrylate influences the waterproof performance of the waterproof agent.
It should be noted that, in this document, relational terms such as , second, and the like are only used to distinguish entities or operations from another entities or operations, and no necessarily requires or implies that any such actual relationship or order exists between the entities or operations, furthermore, the terms "include", or any other variation thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that includes series of elements includes not only those elements but also other elements not explicitly listed or inherent to such process, method, article, or terminal.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein or by using equivalent structures or equivalent processes performed in the present specification, and are included in the scope of the present invention.

Claims (10)

  1. The non-silicon fluorine-free waterproof agent is characterized by comprising, by mass, 20-30 parts of acrylic acid, 20-30 parts of glycidyl acrylate, 10-20 parts of diacetone acrylamide, 1-10 parts of stearic acid and 1-10 parts of a crosslinking agent, wherein the pH value of the non-silicon fluorine-free waterproof agent is 5-7.
  2. 2. The non-silicon fluorine-free waterproofing agent according to claim 1, further comprising 200-300 parts by mass of water and an organic solvent, wherein the content of the organic solvent is 10-15 g/L.
  3. 3. The non-silicon, fluorine-free water repellent agent according to claim 1, wherein said crosslinking agent is isocyanate.
  4. The preparation method of non-silicon fluorine-free waterproof agents is characterized by comprising the following steps:
    firstly, putting water into a reaction kettle, then putting acrylic acid, glycidyl acrylate and a cross-linking agent into the reaction kettle, continuously stirring, and reacting for 2-6 hours at the temperature of 80-110 ℃; then cooling to 40-45 ℃, adding diacetone acrylamide and stearic acid, continuously stirring, and reacting for 1-3 hours at 80-110 ℃; finally adding an organic solvent for assisting dissolution to obtain an emulsion, and adjusting the pH value of the emulsion to 5-7 to obtain a non-silicon fluorine-free waterproof agent;
    the mass ratio of the acrylic acid to the glycidyl acrylate to the cross-linking agent to the diacetone acrylamide to the stearic acid to the water is 20-30: 20-30: 1-10: 10-20:1-10: 200-300, wherein the content of the organic solvent is 10-15g/L of non-silicon fluorine-free waterproof agent.
  5. 5. The method of claim 4, wherein the organic solvent is ethanol.
  6. 6. The method of claim 4, wherein the cross-linking agent is an isocyanate.
  7. 7. The method of claim 4, wherein the pH of the emulsion is adjusted using a solution of citric acid, sodium hydroxide, or sodium citrate.
  8. A waterproof fabric of , wherein said waterproof fabric is waterproofed with the non-silicon, fluorine-free waterproofing agent of any of claims 1 to 3 to .
  9. 9. The waterproof fabric of claim 8, wherein the waterproof fabric is prepared by the steps of:
    working solution is prepared by diluting the non-silicon fluorine-free water repellent of any in claims 1-3 to 10-40g/L,
    dipping rolling, namely soaking the fabric in the working solution for 10 to 90s and then rolling the fabric for times by using a padder, wherein the pressure of the padder is 1 to 2Kg/cm2The liquid carrying rate is 65-100%,
    and (3) drying, namely drying the dipped padded fabric for 60-180 seconds at 150-180 ℃ to obtain the waterproof fabric.
  10. 10. The waterproof fabric of claim 7, wherein said fabric is a chemical fiber fabric.
CN201911106282.2A 2019-11-13 2019-11-13 non-silicon fluorine-free waterproof agent, preparation method thereof and waterproof fabric Pending CN110734518A (en)

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CN111364251A (en) * 2020-04-23 2020-07-03 莆田达凯新材料有限公司 Hand feeling improver, preparation method thereof and waterproof fabric
CN111535035A (en) * 2020-04-28 2020-08-14 贵州省化工研究院 Fluorine-free waterproof agent and preparation method thereof
CN117295860A (en) * 2021-04-08 2023-12-26 拉莫拉尔控股有限公司 Method for imparting durable water repellency to woven or nonwoven fabrics and water repellency composition

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CN109988264A (en) * 2017-12-29 2019-07-09 乳源东阳光氟有限公司 A kind of no fluoro water proofing agent and its preparation method and application

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CN111364251A (en) * 2020-04-23 2020-07-03 莆田达凯新材料有限公司 Hand feeling improver, preparation method thereof and waterproof fabric
CN111535035A (en) * 2020-04-28 2020-08-14 贵州省化工研究院 Fluorine-free waterproof agent and preparation method thereof
CN111535035B (en) * 2020-04-28 2022-12-13 贵州省化工研究院 A kind of fluorine-free waterproofing agent and preparation method thereof
CN117295860A (en) * 2021-04-08 2023-12-26 拉莫拉尔控股有限公司 Method for imparting durable water repellency to woven or nonwoven fabrics and water repellency composition

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Application publication date: 20200131