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

Abstract

The invention relates to a preparation method of a functional super-hydrophobic emulsion based on the viscosity of a polyurethane pressure-sensitive adhesive. According to the method, a polyurethane pressure-sensitive adhesive is adopted, a polyurethane prepolymer containing a hydrophilic group is obtained through step-by-step polymerization of a reaction monomer, a hydrophilic polyurethane macromolecular chain serves as an emulsifier, a free radical polymerization monomer and a functional raw material are emulsified, polymerization is initiated under the action of an initiator, and the hydrophilic pressure-sensitive adhesive is obtained. The core-shell structure composite microsphere is characterized by a rigid core (functional polymer microsphere) and a flexible shell (polyurethane). According to the invention, the production process is simplified, the chromatic aberration is eliminated, the problem of performance weakness of a single material is solved through a structural-chemical synergistic effect, and the super-hydrophobic performance is realized.

Description

Technical Field

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

[0002] With the improvement of living quality and the development of technology, traditional textiles are accelerating their transformation towards multifunctionality. The current market demand has broken through the basic functions of warmth retention and body covering, and has shifted towards composite functions such as waterproofing, breathability, intelligent temperature regulation (photo / thermochromism), flame retardancy, and antibacterial properties, especially in the fields of outdoor equipment, medical protection, and work clothing. However, once a fabric gets waterlogged, it will cause structural deformation, bacterial growth, and a decrease in breathability, which will directly lead to the simultaneous loss of functions. Therefore, constructing a durable waterproof barrier is the core prerequisite for maintaining the multifunctionality of textiles. 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 the "structure-chemistry" synergy has been revealed. The bionic superhydrophobic coating technologies developed based on this 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.

[0003] 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 in waterproof treatment and fireproof coatings. However, the persistence, long-range migration, bioaccumulation, and biotoxicity of PFAS have caused long-term adverse effects on human health and the environment, and they are known as "forever chemicals" (Boland M R,Davidson L M,Canelón S P,et al.Harnessing electronic healthrecords to study emerging environmental disasters:a proof of concept withperfluoroalkyl substances(PFAS)[J].NPJ Digital Medicine,2021,4(1):122.). In recent years, many countries and international organizations around the world have been increasingly strict in the control of 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 polyfluoroalkyl compounds in Chinese textiles[J].China Fiber Inspection,2024(5).).

[0004] Common methods for constructing fluorine-free superhydrophobic functional fabrics reported in current literature include spraying, dip coating, etching, electrospinning, self-assembly, etc. These methods are often complex in process, high in cost, have safety risks, and can cause changes in the flexibility, strength, color, etc. of the fabric. For example, Zhang Chunming et al. (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.

[0005] In addition, Patent CN118127830A discloses a preparation method of a fluorine-free superhydrophobic and temperature-adjustable textile. This method prepares an adhesive phase change microsphere emulsion through emulsion polymerization combined with oxidative self-polymerization, and obtains a fluorine-free superhydrophobic and temperature-adjustable textile through a two-step pad-dry-cure process of finishing treatment 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, and the polymerization time is as long as 24 hours.

[0006] Based on the disadvantages of poor adhesion, poor durability, and single functionality of traditional functional superhydrophobic coatings, preparing fluorine-free, breathable, long-lasting, soft, and colorless-changing superhydrophobic functional textiles is an inevitable trend in the development of current functional textiles. Summary of the Invention

[0007] The purpose of the present invention is to provide a preparation method of a functional superhydrophobic emulsion based on the adhesiveness of polyurethane pressure-sensitive adhesive in view of the deficiencies of the prior art. This method uses polyurethane-based pressure-sensitive adhesive to replace the currently used polydopamine, and obtains a polyurethane prepolymer containing hydrophilic groups through stepwise polymerization of reaction monomers. Using this polyurethane prepolymer as an emulsifier, emulsifying free radical polymerization monomers and functional raw materials, and initiating polymerization under the action of an initiator to form core-shell structure composite microspheres characterized by "rigid core (functional polymer microspheres) @ flexible shell (polyurethane)". The present invention not only simplifies the production process (combining two steps into one), but also eliminates color difference, and solves the performance short board of single materials through the "structure-chemistry" synergistic effect to achieve superhydrophobic performance.

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

[0009] A preparation method of a functional superhydrophobic emulsion based on the adhesiveness of polyurethane pressure-sensitive adhesive, comprising the following steps:

[0010] Mix emulsion A and emulsion B to obtain a core-shell fluorine-free superhydrophobic emulsion based on the adhesiveness of polyurethane pressure-sensitive adhesive;

[0011] Wherein, the mass ratio of emulsion A to emulsion B is 1:0.1 to 100;

[0012] The preparation method of the said emulsion A:

[0013] Mix the isocyanate group monomer and the oligomeric alcohol monomer, and pre-polymerize at 60-120 °C for 2-6 h, then add a hydrophilic chain extender for chain extension reaction for 2-7 h to obtain a prepolymer; then cool down to 30-80 °C, add a neutralizer to adjust the pH value to 3-12, and emulsify with deionized water under stirring for 0.2-1 h until the emulsion color is light blue or milky white. Then add a free radical polymerization monomer, a functional raw material, and an initiator to initiate the polymerization of the monomer for 3-24 h, and finally form emulsion A with a polyurethane sticky shell layer and a rigid core-shell structure functional polymer as the supporting structure;

[0014] Wherein, the molar ratio of the isocyanate group monomer to the oligomeric alcohol monomer is 20-0.5:1; the molar ratio of the hydrophilic chain extender to the isocyanate group monomer is 0.2-20:1; the mass ratio of the free radical polymerization monomer to the prepolymer is 10-0.1:20; the addition amount of the initiator is 0.02-10% of the mass of the free radical polymerization monomer; the mass ratio of the functional raw material to the free radical polymerization monomer is 0.1-5:1;

[0015] The stirring speed is 300-5000 rpm; the mass of deionized water is 0.5-10 times the sum of the masses of the prepolymer, the free radical polymerization monomer, and the functional raw material;

[0016] The said isocyanate monomer is one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate;

[0017] The said oligomeric alcohol monomer is one or more of polyether polyol, polyester polyol, tetramethylene ether glycol, polyethylene glycol, polypropylene glycol, polyester amide, acrylic polyol, castor oil-based polyol, polydimethylsiloxane, polycarbonate diol;

[0018] The said hydrophilic chain extender is one or more of 1,4-butanediol, ethylene glycol, dimethylolpropionic acid, sodium 2-aminoethanesulfonate, diethylenetriamine, N-methyldiethanolamine;

[0019] The said neutralizer is one or more of triethylamine, ammonia water, sodium hydroxide, hydrochloric acid, acetic acid, epichlorohydrin;

[0020] The free radical polymerization monomer is one or more of ethyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, n-octyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, acrylamide, styrene, divinylbenzene, N-hydroxymethylacrylamide, diacetone acrylamide, ethyl acetoacetate methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, γ-methacryloxypropyltrimethoxysilane;

[0021] The functional raw material is one or more of spiropyran, thiazine, oxazine, phenazine, arylmethane dye, tetrazolium salt dye, crystal violet lactone, fluorane 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;

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

[0023] The molecular weight of the polyurethane macromolecular emulsifier is 300 - 20000;

[0024] The particle size of the polymer microspheres is 30 - 1000 nm; the mass fraction of the polymer microspheres is 5 - 40%;

[0025] The preparation method of the emulsion B:

[0026] Mix the fluorine-free waterproofing agent and the blocked isocyanate crosslinking agent, and dilute them with deionized water into a low-concentration fluorine-free waterproofing agent emulsion, namely emulsion B;

[0027] Among them, the mass ratio of the fluorine-free waterproofing agent to the blocked isocyanate crosslinking agent is 1:0.01 - 1;

[0028] The fluorine-free waterproofing agent is one or more of silicone waterproofing agent, polyurethane waterproofing agent, polyurethane waterproofing agent;

[0029] 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 ketoxime-type isocyanate crosslinking agent, sodium bisulfite-type isocyanate crosslinking agent;

[0030] The mass fraction of the polymer in the water repellent in Emulsion B is 10-80%;

[0031] The mass fraction of the polymer in the low-concentration fluorine-free water repellent emulsion in Emulsion B is 0.2-5%;

[0032] The application of the functional superhydrophobic emulsion based on the adhesiveness of polyurethane pressure-sensitive adhesive prepared by the method includes the following steps:

[0033] Immerse the fabric in the functional superhydrophobic emulsion based on the adhesiveness of polyurethane pressure-sensitive adhesive for 1-100 s, then roll it through a rolling machine with 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;

[0034] The fabric described above can be one or a blended fabric of cotton, acrylic, polyester, aramid, spandex, nylon, vinylon, polypropylene, non-woven fabric.

[0035] The substantial features of the present invention are:

[0036] 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;

[0037] In the present invention, a polyurethane prepolymer containing hydrophilic groups is obtained by stepwise polymerization of the reaction monomers, and this polyurethane prepolymer is used as an emulsifier to emulsify free radical polymerization monomers and functional raw materials, and polymerization is initiated under the action of an initiator to form a core-shell structure composite microsphere characterized by "rigid core (functional polymer microsphere) @ flexible shell (polyurethane)".

[0038] The beneficial effects of the present invention are:

[0039] The core layer of the polymer microspheres in Emulsion A in the present invention is rigid functional polymer microspheres, which form a micro-nano rough structure on the fiber surface; the shell layer is a polyurethane-based 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 cross-linking agent, the polymer composite microspheres are fixed to the fabric fiber surface through physical adhesion and chemical cross-linking to adhere firmly and evenly. For example, the superhydrophobic taffeta textile prepared in Example 1 can withstand 35 laundering cycles, which is 20% higher than that in Patent CN118127830A.

[0040] 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.

[0041] The emulsion A and the emulsion B in the present invention are both fluorine-free water-based emulsions and are environmentally friendly.

[0042] 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.

[0043] 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

[0044] Figure 1 This is a scanning electron microscope photograph of the functional polymer microspheres in Example 1.

[0045] 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

[0046] 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.

[0047] Embodiment 1:

[0048] (1) Emulsion A: 4.45 g of isophorone diisocyanate (i.e., 20.00 mmol) and 10 g of polypropylene glycol (molecular weight 1000 g / mol, i.e., 10.00 mmol) were pre-polymerized at 60 °C for 3 h, then 0.9 g of dimethylolpropionic acid (i.e., 6.67 mmol) was added for chain extension for 4 h to obtain a prepolymer. After neutralizing to pH = 9 with 0.3 g of 28% ammonia water by mass, 80 g of deionized water was added at a rotation speed of 2000 rpm and emulsified to milky white. A polyurethane molecular chain containing hydrophilic groups was used as a macromolecular emulsifier. Then, 0.05 g of fluorane dye, 0.45 g of bisphenol A, 10 g of n-tetradecanol, 7.5 g of styrene, 2.5 g of divinylbenzene and 0.2 g of AIBN were added to initiate monomer polymerization for 8 h (due to its hydrophobic property, it enters the interior of polyurethane latex particles), and Emulsion A with a mass fraction of 31.0% and having a rigid core-shell support structure, a pressure-sensitive adhesive shell and the synergistic effect of functional nanoparticles was obtained;

[0049] (2) Emulsion B: After mixing 3 g of a 30% organosilicon waterproofing agent (commercial product) by mass and 0.5 g of a 30% methyl ethyl ketoxime-type blocked isocyanate crosslinking agent by mass, 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%;

[0050] (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 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 the adhesiveness of polyurethane pressure-sensitive adhesive.

[0051] Figure 1 Figure 10 is a scanning electron microscope photograph of the functional nanoparticles prepared in Example 1.

[0052] Figure 2 Figure 14 is a graph showing the relationship between the color of the pressure-sensitive adhesive functional polymer microspheres prepared in Example 1 and temperature. When the temperature is 32.1 °C, the color is black. As the temperature increases, the color gradually fades. When it reaches 37.6 °C, it is light gray. As the temperature further increases, when it reaches 40.1 °C, it is white.

[0053] 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 in Example 1. Different from the traditional direct use of nanoparticles, this method uses nano-microspheres coated with polyurethane-based pressure-sensitive adhesives. The soft segments and hard segments 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.

[0054] Details of the test results of the polyester fabric treated in Example 1

[0055]

[0056] Example 2:

[0057] A functional superhydrophobic polyamide textile based on the adhesiveness of polyurethane 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.

[0058] Example 3:

[0059] A functional superhydrophobic aramid textile based on the adhesiveness of polyurethane 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.

[0060] Example 4:

[0061] A functional superhydrophobic spandex textile based on the adhesiveness of polyurethane 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.

[0062] Example 5:

[0063] (1) 4.45 g of isophorone diisocyanate (i.e., 20.00 mmol) and 10 g of polytetrahydrofuran ether glycol (molecular weight of 1000 g / mol, i.e., 10.00 mmol) were pre-polymerized at 85 °C for 3 h, then 0.9 g of dimethylolpropionic acid (6.67 mmol) was added for chain extension for 4 h to obtain a prepolymer. After neutralizing to pH = 9 with 0.3 g of ammonia water with a mass fraction of 28%, 80 g of deionized water was added at a rotation speed of 2000 rpm to emulsify until milky white, obtaining a polyurethane molecular chain containing hydrophilic groups as a macromolecular emulsifier. Then 0.05 g of crystal violet lactone, 0.45 g of bisphenol A, 10 g of n-tetradecanol, 7.5 g of styrene, 2.5 g of divinylbenzene and 0.2 g of AIBN were added to initiate monomer polymerization for 8 h, and finally an emulsion A with a mass fraction of 31.0% was formed, with a polyurethane as the sticky shell layer and a rigid core-shell structure functional polymer as the support structure;

[0064] (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%;

[0065] (3) After uniformly mixing 1 g of emulsion A and 50 g of emulsion B, first immerse a polyester fabric (25×25 cm) in the mixed solution for 10 s, with a calender pressure of 0.4 MPa, a vehicle speed of 6.5 m / min, and dry it at 150 °C to obtain a functional superhydrophobic polyester textile based on the adhesiveness of polyurethane pressure-sensitive adhesive.

[0066] Example 6:

[0067] A functional superhydrophobic polyamide textile based on the adhesiveness of polyurethane 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.

[0068] Example 7:

[0069] A functional superhydrophobic aramid textile based on the adhesiveness of polyurethane 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.

[0070] Example 8:

[0071] A functional superhydrophobic spandex textile based on the adhesiveness of polyurethane 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.

[0072] As can be seen from the above examples, the present invention aims to solve the problems existing in the preparation process of traditional functional superhydrophobic textiles, such as complex process, high cost and insufficient durability, and provides a simple preparation method. The present invention gradually polymerizes reaction monomers to obtain a polyurethane prepolymer containing hydrophilic groups, uses this polyurethane prepolymer as an emulsifier to emulsify free radical polymerization monomers and functional raw materials, and initiates polymerization under the action of an initiator to form core-shell structure composite microspheres characterized by "rigid core (functional polymer microspheres) @ flexible shell (polyurethane)"; 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. 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.

[0073] 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 polyurethane 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 adhesiveness of polyurethane pressure-sensitive adhesive; Among them, the mass ratio of emulsion A to emulsion B is 1:0.1 - 100; The preparation method of the said emulsion A: Mix the isocyanate group monomer and the oligomeric alcohol monomer, and pre-polymerize at 60 - 120 °C for 2 - 6 h, then add a hydrophilic chain extender for chain extension reaction for 2 - 7 h to obtain a prepolymer; then cool down to 30 - 80 °C, add a neutralizing agent to adjust the pH value to 3 - 12, and emulsify with deionized water under stirring for 0.2 - 1 h until the emulsion color is light blue or milky white, then add a free radical polymerization monomer, a functional raw material, and an initiator to initiate the polymerization of the monomer for 3 - 24 h, and finally form emulsion A with a polyurethane sticky shell layer and a rigid core-shell structure functional polymer as the supporting structure; Among them, the molar ratio of the isocyanate group monomer to the oligomeric alcohol monomer is 20 - 0.5:1; the molar ratio of the hydrophilic chain extender to the isocyanate group monomer is 0.2 - 20:1; the mass ratio of the free radical polymerization monomer to the prepolymer is 10 - 0.1:20; the addition amount of the initiator is 0.02 - 10% of the mass of the free radical polymerization monomer; the mass ratio of the functional raw material to the free radical polymerization monomer is 0.1 - 5:1; The mass of deionized water is 0.5 - 10 times the sum of the masses of the prepolymer, the free radical polymerization monomer, and the functional raw material; The said isocyanate monomer is one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate; The said oligomeric alcohol monomer is one or more of polyether polyol, polyester polyol, tetramethylene ether glycol, polyethylene glycol, polypropylene glycol, polyester amide, acrylic polyol, castor oil-based polyol, polydimethylsiloxane, polycarbonate diol; The said hydrophilic chain extender is one or more of 1,4-butanediol, ethylene glycol, dimethylolpropionic acid, sodium 2-aminoethanesulfonate, diethylenetriamine, N-methyldiethanolamine; The said neutralizing agent is one or more of triethylamine, ammonia water, sodium hydroxide, hydrochloric acid, acetic acid, epichlorohydrin; The said free radical polymerization monomer is one or more of ethyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, n-octyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, acrylamide, styrene, divinylbenzene, N-hydroxymethylacrylamide, diacetone acrylamide, ethyl acetoacetate methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, γ-methacryloxypropyltrimethoxysilane; The functional raw materials are 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; The initiators are one or more of benzoyl peroxide, azobisisobutyronitrile (AIBN), azodiisooctanenitrile, potassium persulfate, ammonium persulfate, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, cumene hydroperoxide; The preparation method of the emulsion B: Mix the fluorine-free waterproofing agent with the blocked isocyanate crosslinking agent, and dilute it with deionized water into a low-concentration fluorine-free waterproofing agent emulsion, namely emulsion B; Among them, the mass ratio of the fluorine-free waterproofing agent to the blocked isocyanate crosslinking agent is 1:0.01-1; The fluorine-free waterproofing agent is one or more of silicone waterproofing agents, polyurethane waterproofing agents; 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, sodium bisulfite-type isocyanate crosslinking agent.

2. The preparation method of the functional superhydrophobic emulsion based on the adhesion of polyurethane pressure-sensitive adhesive, characterized in that, In the preparation of emulsion A, the stirring speed is 300-5000 rpm.

3. The preparation method of the functional superhydrophobic emulsion based on the adhesiveness of polyurethane pressure-sensitive adhesive, characterized in that, The molecular weight of the polyurethane macromolecular emulsifier is 300-20000.

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

6. The preparation method of the functional superhydrophobic emulsion based on the adhesiveness of polyurethane pressure-sensitive adhesive, characterized in that, The application of the functional superhydrophobic emulsion based on the adhesiveness of polyurethane pressure-sensitive adhesive prepared by the method includes the following steps: Immerse the fabric in the functional superhydrophobic emulsion based on the adhesiveness of polyurethane pressure-sensitive adhesive for 1-100 s, then roll it through a roller press with a pressure of 0.1-10 MPa and a vehicle speed of 1-80 m / min, and carry out 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, non-woven fabric.

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