阅读说明：本技术 一种用于纺织品的高浓度含氟拒水拒油剂及其制备方法 (High-concentration fluorine-containing water and oil repellent agent for textiles and preparation method thereof ) 是由 芮燕芳 于 2019-11-14 设计创作，主要内容包括：一种用于纺织品的高浓度含氟拒水拒油剂及其制备方法。该含氟拒水拒油剂为高分子聚合物液体,由下列重量份的原料配比制成：<Image he="423" wi="700" file="DDA0002273153990000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本发明制备的含氟拒水拒油剂具有优异、耐久的拒水拒油性能,适用于长丝、短纤及各种特殊面料防水整理。(A high-concentration fluorine-containing water and oil repellent agent for textiles and a preparation method thereof. The fluorine-containing water and oil repellent agent is a high molecular polymer liquid and is prepared from the following raw materials in parts by weight: prepared by the inventionThe fluorine-containing water and oil repellent agent has excellent and durable water and oil repellent performance and is suitable for water-proof finishing of filaments, staple fibers and various special fabrics.)

1. A high-concentration fluorine-containing water and oil repellent agent for textiles is characterized by being high-molecular polymer liquid and prepared from the following raw materials in parts by weight:

2. the high-concentration fluorine-containing water and oil repellent agent for textiles according to claim 1, wherein the weight ratio of the two in the mixture of n-butyl acrylate and vinyl formic acid is 1: 1.5.

3. The high-concentration fluorine-containing water and oil repellent agent for textiles according to any one of claims 1 to 2, wherein the weight ratio of the sodium lauryl sulfate to the stearyl trimethyl ammonium chloride in the mixture is 2: 1.

4. The high-concentration fluorine-containing water and oil repellent agent for textiles according to any one of claims 1 to 3, wherein the solid content of the high molecular polymer liquid is 30.0 ± 1.0%, the molecular weight of the polymer is 150000 to 200000, the pH value is 2.5 to 4.0, and the specific gravity is 1.1 ± 0.02 g/ml.

5. A method for producing a high-concentration fluorine-containing water-and oil-repellent agent for textiles, characterized in that the water-and oil-repellent agent is the high-concentration fluorine-containing water-and oil-repellent agent for textiles according to any one of claims 1 to 4, the method comprising the steps of:

(1) mixing half of dibenzoyl peroxide and half of ultrapure water with the whole amount of fluorine-containing acrylate, heating to 70-80 ℃ in an argon environment, and reacting for 1.5-3 hours to obtain a product for later use;

(2) adding a mixture of n-butyl acrylate and vinyl formic acid, 2-hydroxyethyl acrylate, acetylacetone acrylamide, a mixture of sodium lauryl sulfate and stearyl trimethyl ammonium chloride, and n-dodecyl mercaptan into the rest ultrapure water, and homogenizing and stirring for 25-30 min to obtain a pre-emulsion;

(3) adding 1/5 of the pre-emulsion into a reactor provided with a stirrer, a thermometer and a condenser, introducing nitrogen to remove oxygen, stirring and heating, heating to 60-70 ℃, adding the residual 1/4 of dibenzoyl peroxide, reacting for 1 hour, then respectively dropwise adding the residual pre-emulsion and dibenzoyl peroxide, continuing to react for 4-5 hours after 4 hours of dropwise addition is completed, and cooling to obtain a mixed liquid material;

(4) and (3) adding the product obtained in the step (1) into the mixed liquid material obtained in the step (3), and performing dispersion treatment by using ultrasonic waves, wherein the ultrasonic treatment frequency is 60-80 KHz, the treatment time is 3-5 min, and the pH value is adjusted to 2.5-4.0, so as to obtain a high polymer liquid, namely the high-concentration fluorine-containing water-repellent oil-repellent agent.

6. The method for producing a high-concentration fluorine-containing water and oil repellent agent for textiles according to claim 5, wherein the fluorine-containing acrylate is produced by the steps of:

(1) adding 100 parts by weight of nonafluoro-4-iodobutane, 15-20 parts by weight of diisopropanolamine and 0.5-1 part by weight of azobisisobutyronitrile into a reactor, heating to 62-65 ℃, introducing ethylene at 0.6-0.8 MPa, controlling the reaction temperature at 60-65 ℃, stopping the reaction until the pressure is not reduced any more, and obtaining a first product;

(2) adding the first product into another reactor, stirring and heating to 125-130 ℃, controlling the pressure to be 0.5-1 MPa, adding 1-methyl-2-pyrrolidone with the weight 1.5-2 times of that of the first product, continuously reacting for 30-35 hours, and neutralizing and separating to obtain a second product;

(3) and adding a catalyst accounting for 1-1.5% of the weight of the second product and methacrylic acid accounting for 20-25% of the weight of the second product, fully stirring and heating to 100-110 ℃, reacting for 3-4 hours, and separating and purifying to obtain the fluorine-containing acrylate.

7. The method for producing a high-concentration fluorine-containing water-and oil-repellent agent for textiles according to any of claims 5 to 6, characterized in that the acetylacetonatoacrylamide is produced by the steps of:

(1) mixing dimethyl ketone and cyanoethylene and concentrated sulfuric acid according to a molar ratio of 3: 2: 4, stirring, and reacting at 45-50 ℃ for 1-1.5 hours to obtain a first product;

(2) adding methyl acetate into the first product for crystallization, wherein the volume ratio of the methyl acetate to the first product is 3:1, and then carrying out solid-liquid separation and water washing to obtain a solid product;

(3) and (3) dissolving the solid product into water to obtain an aqueous solution, wherein the mass ratio of the solid product to the water is 1:10, and then treating the aqueous solution by a dialysis device to obtain the final acetylacetone acrylamide.

Technical Field

The invention belongs to the technical field of textile chemistry, and particularly relates to a high-concentration fluorine-containing water-repellent oil-repellent agent for textiles and a preparation method thereof.

Background

At present, along with the development of textiles at home and abroad and the improvement of the living standard of people, functional finishing textiles are widely applied to markets at home and abroad, wherein the demand of the functional textiles which are water-repellent, oil-repellent and easy-to-clean finishing in international markets is continuously increased, so that people have higher and higher call for developing novel and efficient textile finishing agents, and the investment on the development of novel textile fluorine-containing water-repellent and oil-repellent agents is also increased.

The essence of water-repellent, oil-repellent and easy-to-clean finishing is that a layer of substance is adsorbed on the surface of the textile, so that the high-energy surface of the textile is changed into a low-energy surface, thereby obtaining the textile with the effects of water-repellent, oil-repellent and easy-to-clean, and the smaller the surface energy, the better the effect. At present, in the field of low surface energy resin, fluorocarbon resin and fluorinated acrylic resin prepared by fluorinated ethylene monomers are researched most actively. The surface tension of the fluorine-containing acrylate copolymer emulsion can be as low as 10-15 dyn/cm, so that the organic fluorine textile finishing agent has excellent water-repellent, oil-repellent and anti-fouling performances, and simultaneously, as the electronegativity of an F atom is large and the diameter is small, a C-F bond can be shielded, and the organic fluorine textile finishing agent can show high stability under the environments of strong acid, strong alkali, high temperature and high radiation. However, the fluorine-containing monomer is expensive, so that the fluorine-containing acrylate homopolymer is too high in cost and is difficult to apply to the industrial production of textiles. In addition, the durability of the fluorine-containing water-and oil-repellent agent existing in the prior art is yet to be further improved.

Therefore, how to reduce the content of volatile organic solvent in the fluorine-containing textile finishing agent and improve the durability of the finishing agent for water and oil repellency becomes the current development direction.

Disclosure of Invention

In order to solve the problems, the invention provides a high-concentration fluorine-containing water-repellent oil-repellent agent for textiles and a preparation method thereof. The fluorine-containing water and oil repellent agent prepared by the invention has excellent and durable water and oil repellent performance and is suitable for water-proof finishing of filaments, staple fibers and various special fabrics.

The invention adopts the technical scheme that the high-concentration fluorine-containing water-repellent oil-repellent agent for textiles is high-molecular polymer liquid and is prepared from the following raw materials in parts by weight:

preferably, the weight ratio of the two in the mixture of n-butyl acrylate and vinyl formic acid is 1: 1.5.

In any of the above embodiments, it is preferred that the weight ratio of the sodium lauryl sulfate to the stearyl trimethyl ammonium chloride is 2: 1.

In any of the above embodiments, the solid content of the high molecular polymer liquid is preferably 30.0 ± 1.0%, the molecular weight of the polymer is 150000 to 200000, the pH is 2.5 to 4.0, and the specific gravity is preferably 1.1 ± 0.02 g/ml.

Another technical solution adopted by the present invention to solve the above technical problems is a method for preparing a high concentration fluorine-containing water and oil repellent agent for textiles, comprising the steps of:

(1) mixing half of dibenzoyl peroxide and half of ultrapure water with the whole amount of fluorine-containing acrylate, heating to 70-80 ℃ in an argon environment, and reacting for 1.5-3 hours to obtain a product for later use;

(2) adding a mixture of n-butyl acrylate and vinyl formic acid, 2-hydroxyethyl acrylate, acetylacetone acrylamide, a mixture of sodium lauryl sulfate and stearyl trimethyl ammonium chloride, and n-dodecyl mercaptan into the rest ultrapure water, and homogenizing and stirring for 25-30 min to obtain a pre-emulsion;

(3) adding 1/5 of the pre-emulsion into a reactor provided with a stirrer, a thermometer and a condenser, introducing nitrogen to remove oxygen, stirring and heating, heating to 60-70 ℃, adding the residual 1/4 of dibenzoyl peroxide, reacting for 1 hour, then respectively dropwise adding the residual pre-emulsion and dibenzoyl peroxide, continuing to react for 4-5 hours after 4 hours of dropwise addition is completed, and cooling to obtain a mixed liquid material;

(4) and (3) adding the product obtained in the step (1) into the mixed liquid material obtained in the step (3), and performing dispersion treatment by using ultrasonic waves, wherein the ultrasonic treatment frequency is 60-80 KHz, the treatment time is 3-5 min, and the pH value is adjusted to 2.5-4.0, so as to obtain a high polymer liquid, namely the high-concentration fluorine-containing water-repellent oil-repellent agent.

In any of the above embodiments, preferably, the fluoroacrylate is prepared by:

(1) adding 100 parts by weight of nonafluoro-4-iodobutane, 15-20 parts by weight of diisopropanolamine and 0.5-1 part by weight of azobisisobutyronitrile into a reactor, heating to 62-65 ℃, introducing ethylene at 0.6-0.8 MPa, controlling the reaction temperature at 60-65 ℃, stopping the reaction until the pressure is not reduced any more, and obtaining a first product;

(2) adding the first product into another reactor, stirring and heating to 125-130 ℃, controlling the pressure to be 0.5-1 MPa, adding 1-methyl-2-pyrrolidone with the weight 1.5-2 times of that of the first product, continuously reacting for 30-35 hours, and neutralizing and separating to obtain a second product;

(3) and adding a catalyst accounting for 1-1.5% of the weight of the second product and methacrylic acid accounting for 20-25% of the weight of the second product, fully stirring and heating to 100-110 ℃, reacting for 3-4 hours, and separating and purifying to obtain the fluorine-containing acrylate.

In any of the above embodiments, preferably, the acetylacetonatoacrylamide is prepared by:

(1) mixing dimethyl ketone and cyanoethylene and concentrated sulfuric acid according to a molar ratio of 3: 2: 4, stirring, and reacting at 45-50 ℃ for 1-1.5 hours to obtain a first product;

(2) adding methyl acetate into the first product for crystallization, wherein the volume ratio of the methyl acetate to the first product is 3:1, and then carrying out solid-liquid separation and water washing to obtain a solid product;

(3) and (3) dissolving the solid product into water to obtain an aqueous solution, wherein the mass ratio of the solid product to the water is 1:10, and then treating the aqueous solution by a dialysis device to obtain the final acetylacetone acrylamide.

The product of the invention is milk white semitransparent emulsion, is weak cationic and is easy to dilute and disperse in water.

The invention is obtained according to years of practical application practice and experience, adopts the best technical means and measures to carry out combined optimization, obtains the optimal technical effect, is not simple superposition and splicing of technical characteristics, and has obvious significance.

The invention has the beneficial effects that:

1. compared with the prior art, the high-concentration fluorine-containing water and water repellent agent for textiles has the characteristics of strong adhesion capability, no volatile organic solvent, excellent oil and water repellent performance and the like, and has good application prospect.

2. The product of the invention does not contain the potential risk of generating PFOA, is an environment-friendly product and accords with the national industrial policy; the manufacturing method is simple and convenient for industrial production; high reaction conversion rate and high purity of intermediate products, is beneficial to the subsequent reaction, and is beneficial to improving the yield and reducing the cost.

3. The method simplifies the treatment process, reduces the generation of side reactions and byproducts, successfully avoids the problems of quick temperature rise, low yield, environmental pollution of waste water and waste residues and the like caused by neutralization treatment, greatly shortens the post-treatment time, improves the production efficiency, has safer and more environment-friendly process, and saves resources.

4. The invention has excellent and durable water and oil repellent performance, and is suitable for the waterproof finishing of filaments, staple fibers and various special fabrics; the product is a high-concentration finishing agent, can be diluted for use and has good low-temperature baking performance; the stability is good and the noise is small due to residues, dyes and blending aids of the previous working procedure. And the product does not belong to (flammable and explosive) dangerous goods, is convenient to take and use, does not contain alkylphenol ethoxylates (APEO), and does not contain PFOA and PFOS which are suspected to influence the environment (lower than the detection limit).

Detailed Description

The invention is further described with reference to specific examples, but the scope of the claims is not limited thereto.