Preparation method of functional super-hydrophobic emulsion based on polyacrylate pressure-sensitive adhesive viscosity

Abstract

The invention relates to a preparation method of a functional super-hydrophobic emulsion based on polyacrylate pressure-sensitive adhesive viscosity. According to the method, a seed emulsion polymerization one-pot method is adopted, a polyacrylate type pressure-sensitive adhesive is used for replacing currently used polydopamine and polymeric monomers to carry out free radical copolymerization or stepwise polymerization to obtain functional rigid polymer microspheres, the rigid polymer microspheres are used as seeds to grow the polyacrylate type pressure-sensitive adhesive, and the polyacrylate type pressure-sensitive adhesive is prepared. Through physical viscosity and chemical crosslinking, the adhesive force of the microspheres on the fiber surface is enhanced. According to the invention, the production process is simplified, the chromatic aberration is eliminated, the production process is effectively simplified, and meanwhile, the requirements of modern industry on economic and green production are met.

Description

Technical Field

[0001] The technical solution of the present invention relates to the field of fluorine-free superhydrophobic functional textiles, and in particular to a preparation method of a functional superhydrophobic emulsion based on the adhesiveness of polyacrylate pressure-sensitive adhesive. Background Art

[0002] With the continuous improvement of people's living standards and the progress of technology, the development of traditional textiles towards functional textiles has become an inevitable trend. Consumers' demands for functional textiles are becoming increasingly diversified, no longer limited to basic functions such as warmth retention and body covering, and the demands for textiles with special functions such as waterproof, breathable, heat storage, photochromic, thermochromic, flame retardant, ultraviolet protection, antibacterial, and radiative cooling are continuously increasing. Especially in the fields of outdoor, sports, medical, and workwear, the demand for functional textiles is particularly prominent. For functional fabrics, once wetted by water, problems such as temperature control failure, bacterial growth, color bleeding, fading, fiber structure deformation, reduced breathability, and decreased comfort will directly lead to a significant reduction or even complete failure of the fabric's functionality. Therefore, ensuring that the fabric has durable high waterproof performance is an important basis for maintaining its functionality.

[0003] In recent years, the superhydrophobic effect has become the ultimate pursuit in the field of waterproofing. By analyzing the micro-nano structure and low surface energy characteristics of the lotus leaf surface, the core principle of achieving superhydrophobicity through "structure-chemistry" synergy has been revealed. The developed bionic superhydrophobic coating technologies mainly include two approaches: one is to use low surface energy substances such as fluorocarbons, long-chain alkanes, and siloxanes to reduce the surface free energy; the other is to construct a multi-level micro-nano structure by introducing nanoparticles (such as silica and titanium dioxide). The synergistic effect of the two can endow the material with excellent superhydrophobic properties.

[0004] In the development process of superhydrophobic coatings, per- and polyfluoroalkyl substances (PFAS) have been widely used in the textile industry due to their extremely low surface energy, such as waterproof treatment, fireproof coatings, etc. However, the persistence, long-range migration, bioaccumulation, and biotoxicity of PFAS have caused long-term adverse effects on human health and the environment, and are known as "forever chemicals" (Boland M R, Davidson L M, Canelón S P, et al. Harnessing electronic health records to study emerging environmental disasters: a proof of concept with perfluoroalkyl substances (PFAS) [J]. NPJ Digital Medicine, 2021, 4(1): 122.). In recent years, many countries and international organizations around the world have increasingly strict control over PFAS. The textile industry needs to actively respond to this trend and is undergoing an iterative upgrade from a fluorinated system to a fluorine-free system (Wei Lihua, Wang Didi, Liu Qi, et al. Product standards and detection status of perfluoro- and polyfluoro compounds in Chinese textiles [J]. China Fiber Inspection, 2024(5).).

[0005] Common methods reported in current literature for constructing fluorine-free superhydrophobic functional fabrics include spraying, dip coating, etching, electrospinning, self-assembly, etc. These methods often involve complex processes, high costs, safety risks, and can cause changes in fabric flexibility, strength, color, etc. For example, Tan Yaxi and Zhang Chunming (Tan Yaxi, Zhang Chunming. Preparation and properties of chitosan / TiO2 / Ag superhydrophobic antibacterial cotton fabrics [J]. Cotton Textile Technology, 2025, 53(02): 1-6.) used hydrothermal method and photochemical reduction deposition method with ethanol and isopropanol as solvents to prepare a composite material of chitosan (CS) loaded with titanium dioxide (TiO2) and silver nanoparticles (Ag NPs), and combined with silane coupling agent and polydimethylsiloxane (PDMS) for impregnation modification of pure cotton fabrics. The modified cotton fabrics have good hydrophobic and self-cleaning properties, and the antibacterial rates against Staphylococcus aureus and Escherichia coli reach 99.99% and 99.97% respectively. However, this method not only has difficulty in getting rid of the use of solvents, but also affects the air permeability, flexibility, mechanical properties, etc. of the fibers.

[0006] In addition, Patent CN118127830A discloses a preparation method of a fluorine-free superhydrophobic temperature-adjustable textile. This method prepares an adhesive phase change microsphere emulsion through emulsion polymerization combined with oxidative self-polymerization, and obtains the fluorine-free superhydrophobic temperature-adjustable textile through a finishing treatment process of two dipping-rolling-baking processes in combination with a fluorine-free water repellent. However, the alkaline environment during the oxidative self-polymerization of dopamine in the phase change microsphere emulsion will affect the emulsion stability, and the color of the phase change microsphere emulsion wrapped with polydopamine is usually dark brown or black, resulting in color change of the fabric before and after treatment, and the preparation process is complex, with a polymerization time as long as 24 hours.

[0007] Based on the disadvantages of poor adhesion, insufficient durability, and single functionality of the traditional functional superhydrophobic coatings, the preparation of fluorine-free, breathable, long-lasting, soft, and colorless superhydrophobic functional textiles is an inevitable trend in the development of current functional textiles. Summary of the Invention

[0008] The purpose of the present invention is to provide a preparation method of a functional superhydrophobic emulsion based on the adhesion of polyacrylate pressure-sensitive adhesive in view of the deficiencies of the prior art. This method adopts the seed emulsion polymerization one-pot method, replaces the currently used polydopamine with polyacrylate-based pressure-sensitive adhesive, and obtains functional rigid polymer microspheres through free radical copolymerization or step polymerization of polymerization monomers. Using these rigid microspheres as seeds, polyacrylate-based pressure-sensitive adhesives are grown, and the adhesion of the microspheres on the fiber surface is enhanced through physical adhesion and chemical cross-linking. The present invention not only simplifies the production process (combining two steps into one), but also eliminates color difference, effectively simplifies the production process, and at the same time meets the requirements of modern industry for economical and green production.

[0009] The technical solution adopted by the present invention is as follows:

[0010] A preparation method of a functional superhydrophobic emulsion based on the adhesion of polyacrylate pressure-sensitive adhesive, comprising the following steps:

[0011] Mix emulsion A and emulsion B to obtain a core-shell fluorine-free superhydrophobic emulsion based on the adhesion of polyacrylate pressure-sensitive adhesive;

[0012] Among them, the mass ratio of emulsion A to emulsion B is 1:0.1 - 100;

[0013] The preparation method of the said emulsion A:

[0014] (1) The preparation of the rigid polymer core emulsion is one of the following two methods:

[0015] Method 1: Prepare a monolayer core-shell structure functional polymer microsphere emulsion based on free radical polymerization, comprising the following steps:

[0016] In a four-necked flask, the emulsifier was uniformly dispersed in deionized water as the aqueous phase; the unsaturated monomer, functional raw material, and initiator were mixed as the oil phase; the oil phase was added dropwise to the aqueous phase under high-speed dispersion and pre-emulsified for 2 to 60 minutes, then heated to 50 to 85 °C, and polymerized for 6 to 12 hours under stirring to obtain a monolayer core-shell structure functional polymer microsphere emulsion;

[0017] Among them, the addition amount of the emulsifier was 0.05 to 20% of the mass of deionized water; the mass ratio of the unsaturated monomer to the functional raw material was 10:1 to 20; the mass of the initiator was 0.02 to 10% of the mass of the unsaturated monomer; the mass ratio of the oil phase to the aqueous phase was 0.1 to 1:1;

[0018] The rotation speed of high-speed dispersion was 2000 to 10000 rpm; the rotation speed of stirring was 200 to 600 rpm;

[0019] The emulsifier was one or more of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecylbenzenesulfonate, sodium dodecyl diphenyl ether disulfonate, sodium oleate, secondary alkyl sulfonate, dodecyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, cetyl benzyl trimethyl ammonium chloride, hyperbranched gemini quaternary ammonium salt, etc., and one or more of fatty alcohol polyoxyethylene ether, octadecylamine polyoxyethylene ether, etc.;

[0020] The unsaturated monomer was one or more of methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxypropyl ester, acrylonitrile, styrene, ethyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, n-octyl methacrylate, divinylbenzene, butadiene, vinyl chloride, vinylidene chloride, vinyl pyrrolidone, etc.;

[0021] The functional raw material was one or more of spiropyran, thiazine, oxazine, phenazine, arylmethane dye, tetrazolium salt dye, crystal violet lactone, fluoran dye, stearic acid, bisphenol A, lactic acid, hydroxybenzoic acid, gallic acid, hydroxybenzoate, alkyl gallate, salicylic acid, 2,4-dihydroxybenzoic acid, aromatic sulfone, hydroxycoumarin, paraffin, dodecane, tetradecane, hexadecane, octadecane, dodecanol, tetradecanol, hexadecanol, octadecanol, dodecanoic acid, tetradecanoic acid, dodecyl ester, myristyl myristate, etc.;

[0022] The initiator included one or more of benzoyl peroxide, azobisisobutyronitrile (AIBN), azobisisoheptonitrile, potassium persulfate, ammonium persulfate, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, cumene hydroperoxide, azobisisobutylamidine dihydrochloride, etc.;

[0023] Alternatively, Method 2 involves gradually polymerizing to prepare a monolayer core-shell structured functional polymer microsphere emulsion, including the following steps:

[0024] Pre-polymerize a mixture of isocyanate-based reaction monomers and polyol-based reaction monomers at 60 - 80°C for 2 - 6 h to form a prepolymer, add a small molecule chain extender for chain extension reaction for 2 - 6 h, add a capping agent and react for 2 - 6 h, cool down to 30 - 50°C, add a neutralizing agent to adjust the pH value to 3 - 12 (forming a hydrophilic macromolecule as an emulsifier), add a functional raw material, mix evenly, then add deionized water and emulsify for 0.2 - 1 h until the emulsion color is light blue or milky white, heat up to 50 - 85°C, and react for 6 - 12 h to obtain a monolayer core-shell structured functional polymer microsphere emulsion;

[0025] Among them, the molar ratio of isocyanate group monomers to polyol-based monomers is 20 - 0.5:1; the molar ratio of the small molecule chain extender to isocyanate group monomers is 0.2 - 20:1; the molar ratio of the capping agent to isocyanate group monomers is 0.2 - 20:1; the mass ratio of the functional raw material to the prepolymer is 1:0.1 - 5;

[0026] The mass of deionized water is 0.5 - 10 times the total mass of the prepolymer and the functional raw material;

[0027] The isocyanate-based reaction monomers are one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate;

[0028] The polyol-based reaction monomers are polyether polyol, polyester polyol, tetramethylene ether glycol, polyethylene glycol, polypropylene glycol, polyester amide, acrylic polyol, castor oil-based polyol, polydimethylsiloxane or polycarbonate diol;

[0029] The small molecule chain extender is one or more of 1,4-butanediol, ethylene glycol, dimethylolpropionic acid, sodium 2-(2-aminoethylamino)ethanesulfonate, diethylenetriamine, N-methyldiethanolamine;

[0030] The capping agent is one or more of phenol, nonylphenol, methyl ethyl ketoxime, caprolactam, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 1,3-diazole, 1,2-diazole;

[0031] The neutralizing agent is one or more of triethylamine, ammonia water, sodium hydroxide, hydrochloric acid, acetic acid, epichlorohydrin;

[0032] (2) Using the single-layer core-shell structured functional polymer microsphere emulsion as seeds, a mixture of soft monomers and functional monomers is added drop by drop, and an aqueous solution of an initiator with a mass fraction of 0.1 - 5% is added dropwise. React for 6 - 12 h to obtain Emulsion A with a polyacrylate as the viscous shell layer and a rigid core-shell structured functional polymer as the support structure;

[0033] Among them, the mass ratio of the soft monomer to the functional monomer is 1:0.1 - 0.5; the mass of the initiator is 0.02 - 10% of the sum of the masses of the soft monomer and the functional monomer; the mass ratio of the single-layer core-shell structured functional polymer microsphere emulsion to the monomer mixture is 100:1 - 20;

[0034] The dropping time of the aqueous solution of the initiator is 0.1 - 2 h; the dropping time of the mixture is 0.5 - 3 h;

[0035] The soft monomer is one or more of ethyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, n-octyl methacrylate;

[0036] The functional monomer is one or more of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, acrylamide, N-methylolacrylamide, diacetone acrylamide, ethyl acetoacetate methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, γ-methacryloxypropyltrimethoxysilane;

[0037] The particle size of the polymer microspheres is 30 - 1000 nm; the mass fraction of the polymer microspheres is 5 - 40%;

[0038] The preparation method of the said Emulsion B:

[0039] Mix the fluorine-free waterproofing agent and the blocked isocyanate crosslinking agent evenly, and then dilute it with deionized water into a low-concentration fluorine-free waterproofing agent emulsion;

[0040] In the said Emulsion B, the mass ratio of the fluorine-free waterproofing agent to the blocked isocyanate crosslinking agent is 1:0.01 - 1;

[0041] In the said Emulsion B, the fluorine-free waterproofing agent is one or more of silicone waterproofing agents, polyurethane waterproofing agents, polyacrylate waterproofing agents;

[0042] The said blocked isocyanate crosslinking agent is specifically one of phenol-type isocyanate crosslinking agents, ethanol-type isocyanate crosslinking agents, caprolactam-type isocyanate crosslinking agents, methyl ethyl ketoxime-type isocyanate crosslinking agents, sodium bisulfite-type isocyanate crosslinking agents;

[0043] The mass fraction of the waterproofing agent of the polymer in the emulsion B is 10-80%;

[0044] The mass fraction of the polymer in the low-concentration fluorine-free waterproofing agent emulsion in the emulsion B is 0.2-5%;

[0045] The application of the functional superhydrophobic emulsion based on the tackiness of polyacrylate pressure-sensitive adhesive prepared by the method includes the following steps:

[0046] Immerse the fabric in the functional superhydrophobic emulsion based on the tackiness of polyacrylate pressure-sensitive adhesive for 1-100 s, then roll it with a rolling machine under a pressure of 0.1-10 MPa and a vehicle speed of 1-80 m / min, and perform high-temperature setting at 120-180 °C for 30-600 s to obtain a fluorine-free superhydrophobic textile;

[0047] The fabric described above can be one or a blended fabric of cotton, acrylic, polyester, aramid, spandex, nylon, vinylon, polypropylene, non-woven fabric.

[0048] The substantial features of the present invention are:

[0049] In the preparation of the currently disclosed functional polymer microsphere emulsion, the silanol-based compound formed by the hydrolysis of the silane coupling agent is mainly used to interact with the surface of the fiber substrate to enhance the adhesion of the microspheres on the fiber surface. However, there are few adhesion sites, resulting in insufficient adhesion;

[0050] The present invention is based on the principle of free radical polymerization. The polyacrylate soft monomer and the functional monomer are copolymerized on the surface layer of the rigid functional polymer microspheres with different crosslinking degrees to coat the polyacrylate adhesive with pressure-sensitive adhesive tackiness and hydroxyl reaction activity, and obtain a pressure-sensitive adhesive type "rigid core @ flexible shell" functional polymer microsphere emulsion with a double-shell structure.

[0051] The beneficial effects of the present invention are:

[0052] The core layer of the polymer microspheres in the emulsion A in the present invention is a rigid polymer microsphere, which forms a micro-nano rough structure on the fiber surface; the shell layer is a polyacrylate-type pressure-sensitive adhesive with hydroxyl reaction activity, which serves as a binding layer with the fiber. Under the action of the pressure of the rolling machine and the isocyanate crosslinking agent, the polymer composite microspheres are fixed to the fabric fiber surface through physical tackiness and chemical crosslinking to adhere firmly and uniformly. For example, the superhydrophobic polyester taffeta textile prepared in Example 1 can withstand 35 laundering cycles, which is 20% higher than that of the patent CN118127830A of this research group.

[0053] The pressure-sensitive adhesive core-shell structure polymer microspheres with a "rigid core@flexible shell" composite structure in the emulsion A of the present invention have super strong bonding properties on cotton, acrylic, polyester, aramid, spandex, nylon, vinylon, polypropylene, non-woven fabrics or blended fabrics, and can effectively solve the problem that existing waterproofing agents only have a waterproof effect on a single fabric and have poor versatility.

[0054] The emulsion A and the emulsion B in the present invention are both fluorine-free water-based emulsions and are environmentally friendly.

[0055] The emulsion A and emulsion B in the present invention can be adjusted to different proportions and concentrations according to different application scenarios, and have strong adaptability and controllable costs.

[0056] The combined use of emulsion A and emulsion B in the present invention can provide excellent super-hydrophobic performance and strong wash resistance while ensuring the softness, breathability and comfort of the fabric, and can effectively solve the problems of hand scratches, hard hand feel, and no shade drying effect caused by existing waterproofing agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is a scanning electron microscope photograph of the polyester textile treated in Example 1.

[0058] Figure 2 This is a graph showing the relationship between the color of the functional polymer microspheres prepared in Example 1 and temperature. DETAILED DESCRIPTION

[0059] In order to enable technicians in the relevant technical field to accurately understand and implement the technical solution of the present invention, a detailed explanation is given in combination with specific implementation methods and drawings. It should be particularly noted that the embodiments listed herein are only exemplary implementation methods for explaining the technical principles and in no way constitute a limitation on the scope of protection of the present invention. Based on the technical features defined in the claims of the present invention, derivative implementation methods such as equivalent replacement, process parameter adjustment and material improvement made by technicians in the relevant field through conventional experimental means without departing from the core concept of the present invention should all be covered within the scope of protection of the present invention.

[0060] Embodiment 1:

[0061] (1) Emulsion A: At a rotation speed of 300 rpm, 0.05 g of sodium dodecyl sulfate was uniformly dispersed in 70 mL of deionized water to obtain an aqueous dispersion of the emulsifier; under magnetic stirring at 45 °C, 0.05 g of fluorane dye as the core material, 0.45 g of bisphenol A, 10 g of n-tetradecanol, and 7.5 g of styrene, 2.5 g of divinylbenzene, and 0.1 g of AIBN as the shell material were mixed evenly to form an oil phase. The oil phase was added dropwise to the aqueous phase under high-speed dispersion at 5000 rpm. After the addition was completed, pre-emulsification was carried out for 5 min, and the pre-emulsion was reacted at 75 °C for 6 h to obtain a monolayer core-shell structured functional polymer microsphere emulsion; then, a mixed solution of 2.5 g of n-butyl acrylate and 0.5 g of γ-methacryloxypropyltrimethoxysilane was added dropwise, and 10.1 g of an aqueous solution of 1.0% KPS was added dropwise over 0.5 h. After the reaction for 6 h, the reaction was terminated to obtain a pressure-sensitive adhesive functional polymer microsphere emulsion A with a mass fraction of 27.5%;

[0062] (2) Emulsion B: After mixing 3 g of an organosilicon waterproofing agent with a mass fraction of 30% and 0.5 g of a methyl ethyl ketoxime type blocked isocyanate crosslinking agent with a mass fraction of 30%, 46.5 mL of deionized water was added for dilution to obtain a fluorine-free waterproofing agent emulsion with a mass fraction of 2.1%;

[0063] (3) After uniformly mixing 1 g of Emulsion A and 50 g of Emulsion B, a polyester fabric (25×25 cm) was first immersed in the mixed solution for 10 s, then the nip roller pressure was 0.4 MPa, the vehicle speed was 6.5 m / min, and it was dried at 150 °C for 60 s to obtain a functional superhydrophobic polyester textile based on polyacrylate pressure-sensitive adhesiveness.

[0064] Figure 1 Figure 1 is a scanning electron microscope photograph of the polyester textile after being treated by Example 1. For the treated polyester fabric, the polymer microspheres are evenly and densely distributed on the fiber surface, having an obvious rough structure.

[0065] Figure 2 Figure 2 is a graph showing the relationship between the color of the pressure-sensitive adhesive functional polymer microspheres prepared by Example 1 and the temperature. When the temperature is 35.4 °C, the color is darker, showing black. As the temperature increases, the color gradually becomes lighter; when the temperature is 37.7 °C, it is light gray; when the temperature continues to rise to 40.2 °C, it is white.

[0066] Table 1 shows the test data of the hydrophobicity, wash resistance in the hanging dry and tumble dry states, hand feel, and hand scratch of the polyester fabric treated by this Example 1. Different from the traditional direct use of nanoparticles, this method uses nano-microspheres coated with polyurethane-based pressure-sensitive adhesives, and the soft segments and hard segments of which are intertwined with each other, which can not only provide a rough structure (enhancing the superhydrophobic performance) while ensuring strong adhesion (excellent wash resistance), and does not affect the hand feel and hand scratch of the fabric.

[0067] Details of the test results of the polyester fabric treated in Example 1

[0068]

[0069] Example 2:

[0070] A functional superhydrophobic polyamide textile based on the adhesiveness of polyacrylate pressure-sensitive adhesive, the preparation method is the same as that of Example 1, the only difference is that: polyamide textile is used instead of polyester textile.

[0071] Example 3:

[0072] A functional superhydrophobic aramid textile based on the adhesiveness of polyacrylate pressure-sensitive adhesive, the preparation method is the same as that of Example 1, the only difference is that: aramid textile is used instead of polyester textile.

[0073] Example 4:

[0074] A functional superhydrophobic spandex textile based on the adhesiveness of polyacrylate pressure-sensitive adhesive, the preparation method is the same as that of Example 1, the only difference is that: spandex textile is used instead of polyester textile.

[0075] Example 5:

[0076] (1) Emulsion A: At a rotation speed of 300 rpm, 0.05 g of sodium dodecyl sulfate was uniformly dispersed in 50 mL of deionized water to obtain an aqueous dispersion of the emulsifier; under magnetic stirring at 45 °C, 0.05 g of crystal violet lactone as the core material, 0.45 g of bisphenol A, 10 g of n-tetradecanol, and 7.5 g of styrene, 2.5 g of divinylbenzene and 0.1 g of AIBN as the shell materials were mixed evenly to form an oil phase. The oil phase was added dropwise to the water phase under high-speed dispersion at 5000 rpm. After the addition was completed, pre-emulsification was carried out for 5 min, and the pre-emulsion was reacted at 75 °C for 6 h; then a mixed solution of 2.5 g of n-butyl acrylate and 7.5 g of lauryl acrylate was added dropwise, and 0.5 h was required to add dropwise 0.5 h of an aqueous solution of 10.1 mass fraction of 1.0% KPS, and the reaction was carried out for 6 h; a pressure-sensitive adhesive type functional polymer microsphere emulsion A with a mass fraction of 27.5% was prepared;

[0077] (2) Emulsion B: After mixing 3 g of an organosilicon waterproofing agent with a mass fraction of 30% and 0.5 g of a methyl ethyl ketoxime type blocked isocyanate crosslinking agent with a mass fraction of 30%, 46.5 mL of deionized water was added for dilution to obtain a fluorine-free waterproofing agent emulsion with a mass fraction of 2.1%;

[0078] (3) After uniformly mixing 1 g of Emulsion A with 50 g of Emulsion B, first immerse a polyester fabric (25×25 cm) in the mixed solution for 10 s, with a nip pressure of 0.4 MPa and a vehicle speed of 6.5 m / min, and then dry it at 150 °C for 60 s to obtain a functional superhydrophobic polyester textile based on the tackiness of polyacrylate pressure-sensitive adhesive.

[0079] Example 6:

[0080] A functional superhydrophobic polyamide textile based on the tackiness of polyacrylate pressure-sensitive adhesive, the preparation method is the same as that of Example 5, the only difference is that: a polyamide textile is used instead of a polyester textile.

[0081] Example 7:

[0082] A functional superhydrophobic aramid textile based on the tackiness of polyacrylate pressure-sensitive adhesive, the preparation method is the same as that of Example 5, the only difference is that: an aramid textile is used instead of a polyester textile.

[0083] Example 8:

[0084] A functional superhydrophobic spandex textile based on the tackiness of polyacrylate pressure-sensitive adhesive, the preparation method is the same as that of Example 5, the only difference is that: a spandex textile is used instead of a polyester textile.

[0085] Example 9:

[0086] (1) Emulsion A: Pre-polymerize 4.45 g (i.e., 20.00 mmol) of IPDI with 10 g of polypropylene glycol (molecular weight of 1000 g / mol, i.e., 10.00 mmol) at 60 °C for 3 h, then add 0.9 g of dimethylolpropionic acid (i.e., 6.71 mmol) for chain extension for 4 h to obtain a prepolymer. Add 0.91 g of hydroxyethyl methacrylate (7.00 mmol) as a capping agent and react for 3 h (removing the remaining isocyanate groups and introducing carbon-carbon double bonds). After cooling to 45 °C, neutralize it with 0.3 g of 28% ammonia water to pH = 9, then add 0.05 g of crystal violet lactone as the core material, 0.45 g of bisphenol A, and 10 g of n-tetradecanol and mix evenly. Then add 80 g of deionized water and emulsify it to milky white at a speed of 2000 rpm, heat it to 75 °C, and react for 6 h. Then add 7.5 g of ethyl acrylate and 2.5 g of 2-hydroxyethyl acrylate, and dropwise add 10 g of an aqueous solution of 1.0% initiator and react for 8 h to obtain Emulsion A with a mass fraction of 29.2% having a polyacrylate as the tacky shell layer and a rigid core-shell structure functional polymer as the supporting structure.

[0087] (2) Emulsion B: After mixing 3 g of a 30% organosilicon waterproofing agent and 0.5 g of a 30% methyl ethyl ketoxime - type blocked isocyanate cross - linker, 46.5 mL of deionized water was added for dilution to obtain a fluorine - free waterproofing agent emulsion with a mass fraction of 2.1%.

[0088] (3) After uniformly mixing 1 g of Emulsion A and 50 g of Emulsion B, a polyester fabric (25×25 cm) was first immersed in the mixed solution for 10 s, with a nip pressure of 0.4 MPa and a vehicle speed of 6.5 m / min, and then dried at 150 °C for 60 s to obtain a functional super - hydrophobic polyester textile based on the adhesion of polyacrylate pressure - sensitive adhesive.

[0089] It can be seen from the above examples that the present invention aims to solve the problems existing in the preparation process of traditional functional super - hydrophobic textiles, such as complex process, high cost, and insufficient durability, and provides a simple preparation method. Functional rigid - core microspheres are prepared based on the principles of free - radical or step - growth polymerization; polyacrylate pressure - sensitive adhesives are grown on the surface of the functional rigid - core microspheres, and through physical adhesion and chemical cross - linking, the adhesion of the microspheres on the fiber surface is enhanced; at the same time, it is compounded with a waterproofing agent emulsion to jointly form a low - surface - energy polymer film on the fiber surface. In the present invention, the environmental protection characteristics of the fluorine - free system conform to the development trend of green chemistry; at the application level, the functional core - shell structure design not only ensures functionality but also maintains strong adhesion to the substrate, and at the same time has strong process compatibility and can be applied to the large - scale production of various textile substrates.

[0090] Matters not covered in the present invention are well - known technologies.

Claims

1. A preparation method of a functional superhydrophobic emulsion based on the adhesiveness of polyacrylate pressure-sensitive adhesive, characterized in that, It includes the following steps: Mix emulsion A and emulsion B to obtain a core-shell fluorine-free superhydrophobic emulsion based on the viscosity of polyacrylate pressure-sensitive adhesive; Among them, the mass ratio of emulsion A to emulsion B is 1:0.1 - 100; The preparation method of the described emulsion A: (1) The preparation of the rigid polymer core emulsion is one of the following two methods: Method 1: Prepare a monolayer core-shell structured functional polymer microsphere emulsion based on free radical polymerization, including the following steps: In a four-necked flask, disperse the emulsifier evenly in deionized water as the aqueous phase; mix the unsaturated monomer, functional raw material, and initiator as the oil phase; dropwise add the oil phase into the aqueous phase under high-speed dispersion for pre-emulsification for 2 - 60 min, heat up to 50 - 85 °C, and carry out a polymerization reaction for 6 - 12 h under stirring to obtain a monolayer core-shell structured functional polymer microsphere emulsion; Among them, the addition amount of the emulsifier is 0.05 - 20% of the mass of deionized water; the mass ratio of the unsaturated monomer to the functional raw material is 10:1 - 20; the mass of the initiator is 0.02 - 10% of the mass of the unsaturated monomer; the mass ratio of the oil phase to the aqueous phase is 0.1 - 1:1; The described emulsifier is one or several of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl diphenyl ether disulfonate, sodium oleate, secondary alkyl sulfonate, dodecyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl benzyl trimethyl ammonium chloride, hyperbranched gemini quaternary ammonium salt, etc., and one or several of fatty alcohol polyoxyethylene ether, octadecylamine polyoxyethylene ether; The described unsaturated monomer is one or several of methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxypropyl ester, acrylonitrile, styrene, ethyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, n-octyl methacrylate, divinylbenzene, butadiene, vinyl chloride, vinylidene chloride, vinyl pyrrolidone; The described functional raw material is one or several of spiropyran, thiazine, oxazine, phenazine, arylmethane dye, tetrazolium salt dye, crystal violet lactone, fluoran dye, stearic acid, bisphenol A, lactic acid, hydroxybenzoic acid, gallic acid, hydroxybenzoate, alkyl gallate, salicylic acid, 2,4-dihydroxybenzoic acid, aromatic sulfone, hydroxycoumarin, paraffin, dodecane, tetradecane, hexadecane, octadecane, dodecanol, tetradecanol, hexadecanol, octadecanol, dodecanoic acid, tetradecanoic acid, dodecyl ester, myristyl myristate; The described initiator includes one or several of benzoyl peroxide, azobisisobutyronitrile (AIBN), azodiisooctanenitrile, potassium persulfate, ammonium persulfate, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, cumene hydroperoxide, azodiisobutylamidine dihydrochloride; Or, Method 2: Prepare a monolayer core-shell structured functional polymer microsphere emulsion by stepwise polymerization, including the following steps: A mixture of isocyanate-based reactive monomers and polyol-based reactive monomers is pre-polymerized at 60 - 80 °C for 2 - 6 h to form a prepolymer, a small molecule chain extender is added for chain extension reaction for 2 - 6 h, a capping agent is added for reaction for 2 - 6 h, the temperature is lowered to 30 - 50 °C, a neutralizing agent is added to adjust the pH value to 3 - 12, a functional raw material is added and mixed evenly, and then deionized water is added for emulsification for 0.2 - 1 h until the emulsion color is light blue or milky white. The temperature is raised to 50 - 85 °C and reacted for 6 - 12 h to obtain a monolayer core-shell structured functional polymer microsphere emulsion; Among them, the molar ratio of the isocyanate group monomer to the polyol-based monomer is 20 - 0.5:1; the molar ratio of the small molecule chain extender to the isocyanate group monomer is 0.2 - 20:1; the molar ratio of the capping agent to the isocyanate group monomer is 0.2 - 20:1; the mass ratio of the functional raw material to the prepolymer is 1:0.1 - 5; The mass of deionized water is 0.5 - 10 times the total mass of the prepolymer and the functional raw material; The isocyanate-based reactive monomers are one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate; The polyol-based reactive monomers are polyether polyol, polyester polyol, tetramethylene ether glycol, polyethylene glycol, polypropylene glycol, polyester amide, acrylic polyol, castor oil-based polyol, polydimethylsiloxane or polycarbonate diol; The small molecule chain extenders are one or more of 1,4-butanediol, ethylene glycol, dimethylolpropionic acid, sodium 2-(2-aminoethylamino)ethanesulfonate, diethylenetriamine, N-methyldiethanolamine; The capping agents are one or more of phenol, nonylphenol, methyl ethyl ketone oxime, caprolactam, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 1,3-diazole, 1,2-diazole; The neutralizing agents are one or more of triethylamine, ammonia water, sodium hydroxide, hydrochloric acid, acetic acid, epichlorohydrin; (2) Using the monolayer core-shell structured functional polymer microsphere emulsion as a seed, a mixture of soft monomers and functional monomers is added dropwise, and an aqueous solution of an initiator with a mass fraction of 0.1 - 5% is added dropwise, and reacted for 6 - 12 h to obtain Emulsion A with a polyacrylate as the viscous shell layer and a rigid core-shell structured functional polymer as the support structure; Among them, the mass ratio of the soft monomer to the functional monomer is 1:0.1 - 0.5; the mass of the initiator is 0.02 - 10% of the sum of the masses of the soft monomer and the functional monomer; the mass ratio of the monolayer core-shell structured functional polymer microsphere emulsion to the monomer mixture is 100:1 - 20; The soft monomers are one or more of ethyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, n-octyl methacrylate; The functional monomer is one or more of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, acrylamide, N-methylolacrylamide, diacetone acrylamide, ethyl acetoacetate methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, γ-methacryloxypropyltrimethoxysilane; The preparation method of the emulsion B: Mix the fluorine-free water repellent and the blocked isocyanate crosslinking agent evenly, and then dilute them with deionized water into a low-concentration fluorine-free water repellent emulsion; In the emulsion B, the mass ratio of the fluorine-free water repellent to the blocked isocyanate crosslinking agent is 1:0.01-1; The fluorine-free water repellent in the emulsion B is one or more of silicone water repellents, polyurethane water repellents, and polyacrylate water repellents; The specific blocked isocyanate crosslinking agent is one of phenol-type isocyanate crosslinking agent, ethanol-type isocyanate crosslinking agent, caprolactam-type isocyanate crosslinking agent, methyl ethyl ketone oxime-type isocyanate crosslinking agent, and sodium bisulfite-type isocyanate crosslinking agent.

2. The preparation method of the functional superhydrophobic emulsion based on the adhesiveness of the polyacrylate pressure-sensitive adhesive as described in claim 1, characterized in that, In Method 1, the rotation speed of high-speed dispersion is 2000-10000 rpm; the rotation speed of stirring is 200-600 rpm.

3. The preparation method of the functional superhydrophobic emulsion based on the adhesiveness of polyacrylate pressure-sensitive adhesive as claimed in claim 1, characterized in that, In step (2), the dropping time of the aqueous solution of the initiator is 0.1-2 h; the dropping time of the mixed solution is 0.5-3 h.

4. The preparation method of the functional superhydrophobic emulsion based on the adhesiveness of polyacrylate pressure-sensitive adhesive according to claim 1, characterized in that, The particle size of the polymer microspheres is 30-1000 nm; the mass fraction of the polymer microspheres is 5-40%.

5. The preparation method of the functional superhydrophobic emulsion based on the adhesiveness of polyacrylate pressure-sensitive adhesive, characterized in that, In the emulsion B, the mass fraction of the polymer water repellent is 10-80%; In the low-concentration fluorine-free water repellent emulsion in the emulsion B, the mass fraction of the polymer is 0.2-5%.

6. The application of the functional superhydrophobic emulsion based on the tackiness of polyacrylate pressure-sensitive adhesive prepared by the method according to claim 1, including the following steps: Immerse the fabric in the functional superhydrophobic emulsion based on the tackiness of polyacrylate pressure-sensitive adhesive for 1-100 s, then roll it with a rolling press under a pressure of 0.1-10 MPa and a vehicle speed of 1-80 m / min, and perform high-temperature setting at 120-180 °C for 30-600 s to obtain a fluorine-free superhydrophobic textile; The fabric can be one or a blended fabric of cotton, acrylic, polyester, aramid, spandex, nylon, vinylon, polypropylene, and non-woven fabric.

Images