Preparation method of universal strong washable super-hydrophobic fluoride-free waterproof agent

Abstract

The invention relates to a preparation method of a universal super-hydrophobic fluoride-free waterproof agent with strong washability. According to the method, a polymeric monomer and a polymerizable silane coupling agent are subjected to free radical copolymerization or polycondensation to obtain an emulsion A, and a silanol-based compound formed by hydrolysis of the silane coupling agent interacts with the surface of a fiber base material to enhance the adhesive force of microspheres on the fiber surface; meanwhile, organic silicon in the emulsion B is cured on the surfaces of the polymer microspheres and the fibers to form a film, so that the firmness of the fabric is further enhanced, and the washability of the fabric is remarkably improved while an excellent hydrophobic effect is ensured. According to the invention, simplification and batch production of the production process are effectively realized, and meanwhile, the requirements of modern industry on economic and green production are met.

Description

Technical Field

[0001] The technical scheme of the present invention relates to the field of technical processing of fluorine-free waterproofing agents for textiles, and in particular to a method for preparing a universal, highly washable, super-hydrophobic fluorine-free waterproofing agent for textiles. Background Art

[0002] The super-hydrophobic structure of lotus leaves is a special and creative bionic structure. Due to its natural waterproof properties, it has attracted much attention in scientific research and industry. In the past few decades, bionic super-hydrophobic surfaces based on lotus leaf structures have been widely used in self-cleaning, oil-water separation, anti-corrosion, anti-icing and drag reduction coatings. With the rise of smart textiles, lotus leaf-like super-hydrophobic textiles have gradually become an important development direction for future clothing and functional materials.

[0003] There are two main methods for preparing textiles with superhydrophobic properties. The first is to increase the micro-nanoscale roughness of the fabric fiber surface, and use the air barrier formed by air trapped in the irregular structure of the solid-liquid interface to reduce the contact area between water and the fabric surface, thereby achieving a superhydrophobic effect. The second method is to reduce the surface energy of the fabric, making it difficult for high surface energy liquids such as water to adhere, forming a higher contact angle (Jian Y, Tang W, Xu T, et al. Imparting durable superhydrophobic / oleophobic properties to wood surfaces by means of PFDMS@MTCS vapordeposition[J]. Progress in Organic Coatings, 2023, 185: 107926.).

[0004] However, the traditional method of constructing super-hydrophobic textiles, such as sol-gel method, chemical vapor deposition method, electrostatic spinning method and plasma technology, is usually complex, environmentally friendly, harsh reaction conditions and high cost. In addition, although the textiles treated with long-chain fluorinated chemicals have excellent super-hydrophobicity, due to the bioaccumulation and difficult-to-decompose characteristics of fluorides (Scheringer M.Innovate beyond PFAS[J].Science, 2023, 381(6655): 251-251.), it has been banned in many countries. Therefore, it is imperative to develop a fluorine-free super-hydrophobic modification method. In addition, the preparation method of super-hydrophobic textiles in the future should also meet industrial needs, have cleanliness, simplicity, low cost and universality, and meet daily needs, such as washable, breathable, soft, no color difference and other characteristics.

[0005] For example, CN116731329A discloses a fluorinated block copolymer and a preparation method thereof for super-hydrophobic cotton fabric finishing, which is obtained by reacting hydroxyl-terminated polystyrene with perfluoropolyether carboxylic acid to obtain a fluorinated block copolymer, and then spraying the cotton fabric with a ball finish, and the water contact angle of the treated cotton fabric reaches 152.7 ± 1.9 °, achieving a super-hydrophobic effect. However, the method not only relies on fluorinated compounds, but also uses a large amount of organic solvents, and has poor washability. Feng et al. (Feng X, Guo X, Chen K, et al. Breathable, self-healable, durable superhydrophobic and UV-blocking cotton fabrics [J]. Chemical Engineering Journal, 2024, 492: 152420.) By covalently grafting TiO2 on the surface of cotton fabric, MAPOSS / PDMS composite coating is deposited on the surface of cotton fabric, which enhances its super-hydrophobicity and washability. However, the method has problems such as unstable TiO2 dispersion, large amount of organic solvent, poor fabric color difference and versatility. Therefore, the present invention aims to develop a method for preparing a super-hydrophobic textile waterproofing agent which is green, environmentally friendly, easy to mass-produce, and has versatility, super-hydrophobicity, shade-drying effect, and strong washability.

[0006] In addition, patent CN118127822A discloses a method for preparing fluorine-free environmentally friendly super-hydrophobic textiles; the method is to deposit a layer of polydopamine shell on the surface of polymer microspheres by surface oxidation self-polymerization, and use the super strong adhesion of polydopamine to achieve strong adhesion of microspheres on the fiber surface. However, since polydopamine is a melanin analog, its polymer emulsion color is usually dark brown or black, which causes color difference problems before and after treatment of fabrics, and the polymer microspheres with core-shell structure are prepared by a two-step method, the reaction time is more than 36 hours, and the preparation process is cumbersome and complicated. Summary of the invention

[0007] The object of the present invention is to provide a method for preparing a general-purpose strong washable super-hydrophobic fluorine-free waterproofing agent for textiles in view of the deficiencies in the prior art. The method obtains emulsion A by free radical copolymerization or polycondensation of polymerized monomers, and interacts with the surface of the fiber substrate using a silanol-based compound formed by hydrolysis of a polymerizable silane coupling agent to enhance the adhesion of microspheres on the fiber surface; At the same time, the organic silicon in emulsion B is used to solidify the polymer microspheres and the fiber surface into a film, and its firmness is further enhanced, thereby significantly improving the washability of the fabric while ensuring an excellent hydrophobic effect. The present invention effectively realizes the simplification and batching of the production process, and also meets the needs of modern industry for economic and green production.

[0008] The technical solution adopted by the present invention is as follows:

[0009] A method for preparing a universal strong washable super hydrophobic fluorine-free waterproofing agent comprises the preparation of two emulsions, a polymer microsphere emulsion (waterproofing agent emulsion A) and an organosilicon emulsion (waterproofing agent emulsion B), and the steps are as follows:

[0010] First, the preparation of waterproofing agent emulsion A:

[0011] The first emulsifier is added to deionized water and mixed, and then the mixed solution is dropped and pre-emulsified for 20 to 40 minutes; then the temperature is raised to 60 to 80° C.; the reaction is continued for 6 to 10 hours under stirring to obtain a waterproofing agent emulsion A;

[0012] Wherein, the mixed liquid is composed of polymerizable monomers and silane coupling agents;

[0013] The percentage content of each substance in the waterproofing agent emulsion A is 0.02-0.2% of the first emulsifier, 10-35% of the polymerized monomer, and 0.1-10% of the silane coupling agent;

[0014] Among them, the first emulsifier is one or more of anionic surfactants, cationic surfactants and nonionic surfactants; the anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl diphenyl ether disulfonate, sodium oleate, and secondary alkyl sodium sulfonate; the cationic surfactant is one or more of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, hexadecyl benzyl trimethyl ammonium chloride, and hyperbranched gemini quaternary ammonium salt; the nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether (AEO, peregal) series, octadecylamine polyoxyethylene ether, Tween series, Span series, OP series, and Tx series;

[0015] The polymerizable monomer is one or more of free radical copolymerizable monomers or condensation copolymerizable monomers;

[0016] The comonomer is prepared by using one or more of styrene, acrylic acid, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, lauryl methacrylate, octadecyl acrylate, and divinylbenzene as monomers, and adding an initiator;

[0017] The initiator includes one or more of dibenzoyl oxide, azobisisobutyronitrile (AIBN), azobisisoheptanenitrile, potassium persulfate, ammonium persulfate, tert-butyl perbenzoate, tert-butyl hydroperoxide, and isopropylbenzene hydroperoxide, and the added amount is 0.02-1% of the monomer mass;

[0018] The polycondensation monomer is one or more of isophorone diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, castor oil polyol, tetramethylene ether glycol, polyether polyol, polyester polyol, polytetramethylene ether, ethylenediamine, 1,4-butanediamine, 1,5-pentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, and epichlorohydrin;

[0019] The silane coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxy silane, 3-methacryloxypropyl tris (trimethylsiloxy) silane, 3-aminopropyl triethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl methyl diethoxy silane, N-(2-aminoethyl-3-aminopropyl) trimethoxy silane, diethylene triamino propyl trimethoxy silane, and 3-urea propyl trimethoxy silane;

[0020] Second, the preparation of waterproofing agent emulsion B:

[0021] The silicon source is used as the oil phase, and the aqueous solution of the second emulsifier is used as the water phase; then the oil phase is added dropwise to the water phase under high-speed dispersion, and after the addition is completed, the high-speed dispersion is continued for 5 to 60 minutes to obtain an organosilicon emulsion (waterproofing agent emulsion B);

[0022] Wherein, the silicon source is one or more of silicone oil, silicone resin, and silicone rubber;

[0023] The second emulsifier is one or more of anionic surfactants, cationic surfactants and nonionic surfactants; wherein the anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl diphenyl ether disulfonate, sodium oleate, and sodium secondary alkyl sulfonate; the cationic surfactant is one or more of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, hexadecyl benzyl trimethyl ammonium chloride, and hyperbranched gemini quaternary ammonium salt; the nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether (AEO, peregal) series, octadecylamine polyoxyethylene ether, Tween series, Span series, OP series, and Tx series;

[0024] The concentration of the aqueous solution of the second emulsifier is 0.2 to 20%;

[0025] The volume ratio of water phase to oil phase is 1:0.1-0.8;

[0026] The high-speed dispersion speed is 2000-10000 rpm;

[0027] The silicone oil is one or more of methyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, methyl phenyl vinyl silicone oil, hydroxy silicone oil, vinyl silicone oil, carboxyl modified silicone oil, amino modified silicone oil, polyether modified silicone oil, epoxy modified silicone oil;

[0028] The silicone resin is one or more of methyl silicone resin, phenyl silicone resin, methylphenyl silicone resin, epoxy silicone resin, hydroxy silicone resin, vinyl silicone resin, acrylic silicone resin, and phenolic silicone resin;

[0029] The silicone rubber is prepared by using one or more of methyl vinyl silicone oil, methyl phenyl vinyl silicone oil, hydroxy silicone oil, alkoxy silicone oil, alkyl hydrogen silicone oil, and epoxy modified silicone oil as monomers, and adding a catalyst and an inhibitor;

[0030] The catalyst is one or more of an organic amine compound, a hydroxylamine derivative, a carboxylic acid metal salt, an alkali metal hydroxide, a platinum catalyst, an organic tin catalyst, and an organic zinc bismuth catalyst, specifically triethylenediamine, N-hydroxyphthalimide, zinc isooctanoate, dibutyltin dilaurate, bismuth isooctanoate, lithium isooctanoate, platinum (0)-1,3-diethylene-1,1,3,3-tetramethyldisiloxane, and the amount added is 0.1-10% of the silicon source; the inhibitor is one or two of 1-ethynylcyclohexanol and 3,7,11-trimethyldodecyne-3-ol, and the amount added is 0.1-10% of the silicon source;

[0031] The waterproofing agent emulsion A in step (1) is characterized in that: the polymer microspheres are prepared by free radical copolymerization or polycondensation reaction between a polymer monomer and a silane coupling agent, and the silanol-based compounds hydrolyzed by the silane coupling agent interact with the surface of the fiber substrate to enhance the adhesion of the microspheres to the fiber surface; at the same time, the silicon source in the waterproofing agent emulsion B in step (2) can be cured to form a film on the polymer microspheres and the fiber surface, thereby significantly improving the washability of the fabric while ensuring an excellent hydrophobic effect.

[0032] The polymer microspheres in the waterproofing agent emulsion A of step (1) are either cross-linked or non-cross-linked with a particle size of 30 to 1000 nm. The cross-linked microspheres are attached to the surface of the fiber fabric to provide a rough structure, and the non-cross-linked microspheres are phase-separated from the silicone to form a hydrophobic nanostructure.

[0033] The application of the universal strong washable super hydrophobic fluorine-free waterproofing agent prepared by the method comprises the following steps:

[0034] The water-repellent emulsion A and the water-repellent emulsion B are diluted with deionized water respectively, and then the fabric is subjected to a low surface energy modification process therein to obtain a highly washable super-hydrophobic fluorine-free textile;

[0035] There are two ways to modify the surface energy:

[0036] Method 1: The fabric is immersed in the diluted waterproofing agent emulsion A for 1s to 10min, and then pressed by a roller with a pressure of 0.1 to 10MPa; after drying at 80 to 120℃, the fabric is immersed in the diluted emulsion B for 1s to 10min, and then pressed by a roller with a pressure of 0.1 to 10MPa; and high-temperature setting is performed at 120 to 180℃ for 1s to 10min;

[0037] Or, method 2:

[0038] The fabric is immersed in the diluted mixed emulsion for 1s to 10min, and then pressed by a roller with a pressure of 0.1 to 10MPa, and then shaped at a high temperature of 120 to 180℃;

[0039] The mixed emulsion is obtained by mixing the waterproofing agent emulsion A and the waterproofing agent emulsion B in a volume ratio of 1:0.1-10;

[0040] Waterproofing agent emulsion A is diluted to 0.1-10% with deionized water;

[0041] Waterproofing agent emulsion B is diluted to 0.1-10% with deionized water;

[0042] The mixed solution is diluted with deionized water to 0.1-10%.

[0043] The fabric substrate is one of polyester, spandex, nylon, acrylic, aramid, cotton fabric, non-woven fabric, melt-blown fabric or a blended fabric.

[0044] The essential features of the present invention are:

[0045] In the currently disclosed preparation of polymer microsphere emulsion, a polymer with a core-shell structure is formed by a two-step process of free radical polymerization and surface oxidation self-polymerization, that is, firstly, a single monomer is used for homopolymerization to obtain a polymer microsphere emulsion, and then surface oxidation self-polymerization is performed to obtain a core-shell structure polymer, and the strong adhesion of the polymer microspheres on the fiber surface is achieved through the strong adhesion effect of dopamine;

[0046] The present invention introduces a polymerizable silane coupling agent, combines the two-step reaction into one, prepares polymer microspheres with silane coupling agents through free radical copolymerization or polycondensation, and utilizes the silanol-based compounds formed by the hydrolysis of the silane coupling agent to interact with the surface of the fiber substrate to enhance the adhesion of the microspheres to the fiber surface, thereby simplifying the polymerization process and eliminating the color difference problem caused by polydopamine.

[0047] The beneficial effects of the present invention are:

[0048] The waterproofing agent emulsion A and the waterproofing agent emulsion B in the present invention are both water-based, do not contain volatile organic solvents and fluorine-containing reagents, and are harmless to the environment and human body; and low concentrations of the waterproofing agent emulsion A and the waterproofing agent emulsion B can achieve a super-hydrophobic effect, greatly reducing the use cost.

[0049] The present invention also solves the problem of the adverse effects of the fluorine-free waterproofing agents currently used for textiles on the color difference and feel of the fabrics, as well as the problem of poor shade drying effect, and effectively solves the problems of hand scratches, hardened feel, poor shade drying effect, etc. caused by the existing waterproofing agents. While having super wash-resistant and super hydrophobic properties, the softness, comfort and excellent shade drying hydrophobic effect of the fabric are ensured.

[0050] The invention greatly optimizes the preparation process, shortens the preparation time, simplifies the preparation process, shortens the preparation time from the original 36 hours to 8 hours, eliminates the color difference problem caused by polydopamine, and the obtained super-hydrophobic fabric has excellent wash resistance, which is increased from 15 washing cycles to 25 times. The process is simple, green and environmentally friendly, easy to mass produce, and has broad application prospects.

[0051] The highly washable super-hydrophobic fluorine-free waterproofing agent of the present invention has a super-hydrophobic effect on one or a blended fabric of polyester, spandex, nylon, acrylic fiber, aramid, cotton fabric, non-woven fabric, melt-blown fabric, and the waterproofing agent emulsion has universality in waterproofing treatment of different fabrics, solving the problem that the existing waterproofing agent has only a waterproofing effect on a single fabric and has poor universality. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 This is a scanning electron microscope photograph of the cross-linked styrene-vinyltriethoxysilane copolymer microspheres prepared in Example 1 of the present invention.

[0053] Figure 2 The following are scanning electron microscope photos of the polyester taffeta (polyester) textile before and after treatment in Example 1 of the present invention.

[0054] Figure 3 This is a static water contact angle photograph of the superhydrophobic polyester taffeta (polyester) textile treated in Example 1 of the present invention.

[0055] Figure 4 This is a graph showing the change in static contact angle of the superhydrophobic polyester taffeta (polyester) textile prepared in Example 1 of the present invention during washing cycles.

[0056] Figure 5 This is a scanning electron microscope photograph of the polyester taffeta (polyester) textile after being treated in Example 5 of the present invention.

[0057] Figure 6 This is the static water contact angle of the super hydrophobic polyester taffeta (polyester) textile treated in Example 5 of the present invention. DETAILED DESCRIPTION

[0058] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is now described in detail and clearly in conjunction with the embodiments and drawings. The specific embodiments provided herein are only used to illustrate the present invention and do not constitute any form of limitation. The described embodiments are only partial examples of the present invention, not all embodiments. Based on the embodiments of the present invention, other embodiments obtained by ordinary technicians in the field without creative work all belong to the protection scope of the present invention.

[0059] Embodiment 1:

[0060] (1) Preparation of waterproofing agent emulsion A: 0.05 g of sodium dodecyl sulfate and 180 mL of deionized water were added to a four-necked flask and mixed evenly, and a mixture of 21.5 g of styrene, 2 g of vinyl triethoxysilane, and 1.5 g of divinylbenzene monomer was added dropwise. After the addition was completed, the mixture was pre-emulsified for 30 min, the temperature was raised to 70° C., and a mixture of 0.2 g of potassium persulfate and 15 mL of deionized water was added dropwise. The reaction was continued for 8 h to obtain a cross-linked polymer microsphere waterproofing agent emulsion A with a mass percentage of 11%;

[0061] (2) Preparation of waterproofing agent emulsion B: 15 g of methyl hydrogen silicone oil and 15 g of vinyl silicone oil were mixed uniformly at 500 rpm as an oil phase, 0.04 g of sodium dodecyl sulfate, 3 g of peregal O-5 and 66.96 g of deionized water were mixed uniformly at 500 rpm as an aqueous phase, and the oil phase was added dropwise to the aqueous phase at a high-speed dispersion of 3000 rpm to obtain a high-concentration silicone waterproofing agent emulsion B with a mass percentage of 30%;

[0062] (3) After diluting the 11% water repellent emulsion A to 1.0% and the 30% water repellent emulsion B to 3.0% with deionized water, a polyester taffeta fabric (25 cm×25 cm) was first immersed and rolled in the diluted water repellent emulsion A, i.e. immersed for 10 seconds, with a rolling pressure of 0.4 MPa, a speed of 6.5 m / min, and dried at 80°C; then immersed and rolled in the diluted water repellent emulsion B, i.e. immersed for 10 seconds, with a rolling pressure of 0.4 MPa, and then high-temperature fixed at 160°C for 1 minute to obtain a highly washable super hydrophobic polyester taffeta fabric.

[0063] Figure 1 This is a scanning electron microscope photograph of the styrene-vinyl triethoxysilane copolymer prepared in Example 1. The microspheres are cross-linked, with a particle size of 150 to 1000 nm, and are polydisperse.

[0064] Figure 2The following are scanning electron microscope photos of polyester taffeta textiles before and after treatment by this method. The surface of the untreated polyester taffeta fabric is very smooth, while the treated polyester taffeta fabric has copolymer microspheres evenly and densely distributed on the fiber surface, with an obvious rough structure.

[0065] Figure 3 The static water contact angle of the super hydrophobic polyester taffeta (polyester) textile treated by Example 1 is 158.7°, indicating that the fluorine-free and environmentally friendly super hydrophobic polyester taffeta (polyester) fabric prepared by Example 1 of the present invention has good super hydrophobic properties.

[0066] The super hydrophobic polyester taffeta (polyester) textile prepared in Example 1 was subjected to a soap washing resistance test:

[0067] The super hydrophobic polyester taffeta (polyester) textile prepared in Example 1 was placed in a washing machine containing 0.13 wt% phosphorus-free WOB standard detergent, washed at 40°C for 15 min, dehydrated for 3 min, rinsed for 2 min, dehydrated for 3 min, rinsed again for 2 min, dehydrated for 3 min, and dried at 60°C for 30 min. This was one washing cycle, and the static contact angle of the fabric was tested every 5 cycles.

[0068] Figure 4 This is a picture of the static contact angle change of the super hydrophobic polyester taffeta (polyester) textile prepared in Example 1 during washing cycles. As can be seen from the figure, after 25 washing cycles, the contact angle dropped from 158.7° to 148.6°, and it has good soap resistance.

[0069] Embodiment 2:

[0070] A highly washable and super-hydrophobic nylon (polyamide) textile, the preparation method of which is the same as that of Example 1, except that the nylon (polyamide) textile is used instead of polyester taffeta (polyester) textile.

[0071] Embodiment 3:

[0072] A highly washable super-hydrophobic pongee (polyester) textile, the preparation method of which is the same as that of Example 1, except that the pongee (polyester) textile is used instead of the polyester taffeta (polyester) textile.

[0073] Embodiment 4:

[0074] A highly washable super-hydrophobic polyester taffeta (polyester) textile, the preparation method is the same as that of Example 1, except that step (3) is as follows: water-repellent emulsion A and water-repellent emulsion B are blended at a ratio of 4:1, and then diluted with deionized water to 2.0% (based on the sum of the mass of polymer microspheres and silicon source), and a polyester taffeta (polyester) fiber fabric (25 cm×25 cm) is dipped once in the diluted emulsion, i.e., high-temperature setting at 160°C for 30 seconds to obtain a super-hydrophobic polyester taffeta (polyester) textile.

[0075] Polyester taffeta, polyester pongee and nylon are three very representative textiles on the market that need to be waterproofed. Especially for polyester taffeta and nylon which are difficult to be waterproofed, the present invention can achieve excellent waterproof effects, indicating that the present invention has universality in improving the waterproof performance of textiles.

[0076] Embodiment 5:

[0077] (1) Add 0.05 g of sodium dodecyl sulfate and 180 mL of deionized water to a four-necked flask and mix well, then add dropwise a mixture of 19 g of lauryl methacrylate, 4 g of n-butyl acrylate, and 2 g of vinyl triethoxysilane for pre-emulsification for 30 min, heat to 75° C., then add dropwise a mixture of 0.2 g of potassium persulfate and 15 mL of deionized water, and continue the reaction for 8 h to obtain a uniform and stable waterproofing agent emulsion A containing linear polymer microspheres;

[0078] (2) Preparation of waterproofing agent emulsion B: 15 g of methyl hydrogen silicone oil and 15 g of vinyl silicone oil were mixed uniformly at 500 rpm as an oil phase, 0.04 g of sodium dodecyl sulfate, 3 g of peregal O-5 and 66.96 g of deionized water were mixed uniformly at 500 rpm as an aqueous phase, and the oil phase was added dropwise to the aqueous phase at a high-speed dispersion of 3000 rpm to obtain a 30% high-concentration silicone waterproofing agent emulsion B;

[0079] (3) Waterproofing agent emulsion A is diluted with deionized water to 1.0%, and waterproofing agent emulsion B is diluted with deionized water to 3.0%. A polyester taffeta (polyester) fabric (25 cm×25 cm) is first dipped and rolled in the diluted waterproofing agent emulsion A, i.e., immersed for 10 seconds, with a rolling pressure of 0.4 MPa, and dried at 80°C; then dipped and rolled in the diluted waterproofing agent emulsion B, i.e., immersed for 10 seconds, with a rolling pressure of 0.4 MPa, and then high-temperature fixed at 160°C for 1 minute to obtain a highly washable super-hydrophobic polyester taffeta (polyester) textile.

[0080] Figure 5 This is a scanning electron microscope photo of polyester taffeta textile treated by Example 5. From the figure, it can be seen that the linear copolymer microspheres and the organosilicon undergo phase separation to form a hydrophobic nanostructure.

[0081] Figure 6The static water contact angle of the super-hydrophobic polyester taffeta (polyester) textile treated in Example 5 was measured using an optical contact angle meter (DSA 30), and the angle was 156.4°. This indicates that the fluorine-free and environmentally friendly super-hydrophobic polyester taffeta (polyester) fabric prepared in Example 5 of the present invention has good super-hydrophobic properties.

[0082] Embodiment 6:

[0083] A highly washable and super-hydrophobic nylon taffeta (nylon) textile, the preparation method of which is the same as that of Example 5, except that the nylon taffeta (nylon) textile is used instead of the polyester taffeta (polyester) textile.

[0084] Embodiment 7:

[0085] A highly washable super-hydrophobic pongee (polyester) textile, the preparation method of which is the same as that of Example 5, except that the pongee (polyester) textile is used instead of the polyester taffeta (polyester) textile.

[0086] Embodiment 8:

[0087] A universal, highly washable, super-hydrophobic polyester taffeta (polyester) textile is prepared by the same method as in Example 5, except that step (3) comprises: mixing a water-repellent emulsion A with a water-repellent emulsion B at a ratio of 4:1, diluting the mixture to 2.0% with deionized water, and dipping and rolling a polyester taffeta (polyester) fiber fabric (25 cm×25 cm) in the diluted emulsion, i.e., dipping for 10 seconds, rolling at a pressure of 0.4 MPa, and high-temperature setting at 160°C for 30 seconds to obtain a super-hydrophobic polyester taffeta (polyester) textile.

[0088] It can be seen from the above examples that the present invention prepares a universal strong washable super hydrophobic fluorine-free waterproofing agent for textiles by emulsion polymerization and mechanical emulsification, and successfully prepares a variety of strong washable super hydrophobic fabrics by a simple one-immersion-one-rolling or two-immersion-two-rolling process. This method not only ensures excellent super hydrophobicity and washability, but also has the characteristics of being green, environmentally friendly, easy to mass-produce and widely applicable.

[0089] Matters not covered by the present invention are known technologies.

Claims

1. A method for preparing a universal strong washable super hydrophobic fluorine-free waterproofing agent, characterized in that it comprises the preparation of two emulsions, a polymer microsphere emulsion (waterproofing agent emulsion A) and an organosilicon emulsion (waterproofing agent emulsion B), and the steps are as follows: First, the waterproofing agent emulsion A can be prepared by free radical copolymerization or polycondensation, comprising the following steps: The first emulsifier is added to deionized water and mixed, and then the mixed solution is dropped and pre-emulsified for 10 to 40 minutes; then the temperature is raised to 60 to 80° C.; the reaction is continued for 6 to 10 hours under stirring to obtain a waterproofing agent emulsion A; in, The mixed liquid is composed of a polymerizable monomer and a polymerizable silane coupling agent; The percentage content of each substance in the waterproofing agent emulsion A is 0.02-0.2% of the first emulsifier, 10-35% of the polymerized monomer, and 0.1-10% of the silane coupling agent; Among them, the first emulsifier is one or more of anionic surfactants, cationic surfactants and nonionic surfactants; the anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl diphenyl ether disulfonate, sodium oleate, and secondary alkyl sodium sulfonate; the cationic surfactant is one or more of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, hexadecyl benzyl trimethyl ammonium chloride, and hyperbranched gemini quaternary ammonium salt; the nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether (AEO, peregal) series, octadecylamine polyoxyethylene ether, Tween series, Span series, OP series, and Tx series; The polymerizable monomer is one or more of free radical copolymerizable monomers or condensation copolymerizable monomers; The free radical copolymer monomer is prepared by using one or more of styrene, acrylic acid, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, lauryl methacrylate, octadecyl acrylate, and divinylbenzene as monomers, and simultaneously adding an initiator; The initiator includes one or more of dibenzoyl oxide, azobisisobutyronitrile (AIBN), azobisisoheptanenitrile, potassium persulfate, ammonium persulfate, tert-butyl perbenzoate, tert-butyl hydroperoxide, and isopropylbenzene hydroperoxide, and the added amount is 0.02-1% of the monomer mass; The polycondensation monomer is one or more of isophorone diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, castor oil polyol, tetramethylene ether glycol, polyether polyol, polyester polyol, polytetramethylene ether, ethylenediamine, 1,4-butanediamine, 1,5-pentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, and epichlorohydrin; The polymerizable silane coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxy silane, 3-methacryloxypropyl tris (trimethylsiloxy) silane, 3-aminopropyl triethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl methyl diethoxy silane, N-(2-aminoethyl-3-aminopropyl) trimethoxy silane, diethylene triamino propyl trimethoxy silane, and 3-urea propyl trimethoxy silane; The second method is to prepare a waterproofing agent emulsion B, comprising the following steps: The silicon source is used as the oil phase, and the aqueous solution of the second emulsifier is used as the water phase; then the oil phase is added dropwise to the water phase under high-speed dispersion, and after the addition is completed, the high-speed dispersion is continued for 5 to 60 minutes to obtain an organosilicon emulsion (waterproofing agent emulsion B); Wherein, the silicon source is one or more of silicone oil, silicone resin, and silicone rubber; The second emulsifier is one or more of anionic surfactants, cationic surfactants and nonionic surfactants; wherein the anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl diphenyl ether disulfonate, sodium oleate, and sodium secondary alkyl sulfonate; the cationic surfactant is one or more of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, hexadecyl benzyl trimethyl ammonium chloride, and hyperbranched gemini quaternary ammonium salt; the nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether (AEO, peregal) series, octadecylamine polyoxyethylene ether, Tween series, Span series, OP series, and Tx series; The concentration of the aqueous solution of the second emulsifier is 0.2-20%; the volume ratio of the water phase to the oil phase is 1:0.1-0.

8.

2. The preparation method of the universal strong washable super hydrophobic fluorine-free waterproofing agent as claimed in claim 1, characterized in that The rotation speed of the high-speed dispersion is 2000-10000 rpm.

3. The preparation method of the universal strong washable super hydrophobic fluorine-free waterproofing agent as claimed in claim 1, characterized in that The silicone oil is one or more of methyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, methyl phenyl vinyl silicone oil, hydroxy silicone oil, vinyl silicone oil, carboxyl modified silicone oil, amino modified silicone oil, polyether modified silicone oil, epoxy modified silicone oil; The silicone resin is one or more of methyl silicone resin, phenyl silicone resin, methylphenyl silicone resin, epoxy silicone resin, hydroxy silicone resin, vinyl silicone resin, acrylic silicone resin, and phenolic silicone resin; The silicone rubber uses one or more of methyl vinyl silicone oil, methyl phenyl vinyl silicone oil, hydroxy silicone oil, alkoxy silicone oil, alkyl hydrogen silicone oil and epoxy modified silicone oil as monomers.

4. The method for preparing the universal strong washable super hydrophobic fluorine-free waterproofing agent as claimed in claim 3, characterized in that: When the silicon source is silicone rubber, a catalyst and an inhibitor need to be added; The catalyst is one or more of an organic amine compound, a hydroxylamine derivative, a carboxylic acid metal salt, an alkali metal hydroxide, a platinum catalyst, an organic tin catalyst, and an organic zinc bismuth catalyst, and the added amount is 0.1 to 10% of the silicon source; The inhibitor is one or two of 1-ethynyl cyclohexanol and 3,7,11-trimethyldodecyn-3-ol, and the added amount is 0.1-10% of the silicon source.

5. The method for preparing a universal strong washable super hydrophobic fluorine-free waterproofing agent as claimed in claim 3, characterized in that the catalyst is triethylenediamine, N-hydroxyphthalimide, zinc isooctanoate, dibutyltin dilaurate, bismuth isooctanoate, lithium isooctanoate, platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane.

6. The use of a universal strong washable super hydrophobic fluorine-free waterproofing agent prepared by the method according to claim 1, characterized in that it comprises the following steps: The water-repellent emulsion A and the water-repellent emulsion B are diluted with deionized water respectively, and then the fabric is subjected to a low surface energy modification process therein to obtain a highly washable super-hydrophobic fluorine-free textile; There are two ways to modify the surface energy: Method 1: The fabric is immersed in the diluted waterproofing agent emulsion A for 1s to 10min, and then pressed by a roller with a pressure of 0.1 to 10MPa; after drying at 80 to 120℃, the fabric is immersed in the diluted emulsion B for 1s to 10min, and then pressed by a roller with a pressure of 0.1 to 10MPa; and high-temperature setting is performed at 120 to 180℃ for 1s to 10min; Or, method 2: The fabric is immersed in the diluted mixed emulsion for 1s to 10min, and then pressed by a roller with a pressure of 0.1 to 10MPa, and then shaped at a high temperature of 120 to 180℃; The mixed emulsion is obtained by mixing the waterproofing agent emulsion A and the waterproofing agent emulsion B in a volume ratio of 1:0.1-10; The waterproofing agent emulsion A is diluted with deionized water to 0.1-10%; the waterproofing agent emulsion B is diluted with deionized water to 0.1-10%; and the mixed solution is diluted with deionized water to 0.1-10%.

7. The use according to claim 6, characterized in that The fabric substrate is one of polyester, spandex, nylon, acrylic, aramid, cotton fabric, non-woven fabric, melt-blown fabric or a blended fabric.

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