Anti-siphon fluoride-free waterproof agent as well as preparation method and application thereof

Abstract

The invention discloses an anti-siphon fluoride-free waterproof agent and a preparation method and application thereof.According to the anti-siphon fluoride-free waterproof agent, a fluoride-free waterproof agent polymer grafted with cross-linking groups serves as a matrix and is matched with a waterborne polyurethane cross-linking agent to form a double-cross-linking system, and ion modification components with ion supply groups are used as auxiliary materials; and a multi-functional component consisting of a long-chain alkyl group, a polysiloxane chain segment and a closed polyurethane cross-linking agent is compounded. The adhesive force of the coating and the microfiber leather base material is remarkably improved through a double-crosslinking system, and the service life of the anti-siphon effect is prolonged; the ion modified component is adapted to various composite materials, so that local anti-siphon failure is avoided; the anti-siphon water-proofing agent has the advantages of balanced water proofing, antifouling, air permeability and flexibility, no fluorine in the whole process, conformity with environmental regulations, lower cost than fluorine-containing water-proofing agents, and suitableness for anti-siphon treatment of microfiber leather upper materials of sports shoes, outdoor shoes and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of fine chemical industry, and particularly relates to a siphon-proof fluorine-free waterproof agent and a preparation method and application thereof. BACKGROUND

[0002] The upper material of sports shoes mainly includes leather materials, mesh materials and textile materials, among which leather materials are the core components for ensuring the support and wear resistance of the shoe materials. Although natural leather has advantages in bending resistance, tensile strength and air permeability, it has defects of poor water resistance and high price, resulting in an application proportion of less than 10% in the field of sports shoes. As a substitute for natural leather, artificial leather has formed a technical upgrading path of "artificial leather-synthetic leather-microfiber leather", and microfiber leather has become the mainstream choice due to its performance advantages.

[0003] Microfiber leather is usually processed through spinning, webbing, impregnation and curing processes by using ultra-fine fibers, polyurethane, natural leather scraps and the like, and has the characteristics of environmental protection, light weight and superior physical properties, and has been widely applied to the upper of mid-to-high-end sports shoes. Although microfiber leather has excellent comprehensive performance, it still has obvious shortcomings in functional properties: insufficient siphon-proof performance and poor air permeability, which are key problems limiting its further application. The siphon-proof performance refers to the ability to prevent shoe materials (uppers, soles, laces, etc.) from absorbing water, stains or chemicals due to capillary phenomenon through material processing or structural design, and this performance directly determines the wearing experience of shoe materials in humid and dirty environments (such as keeping the inside of the shoe dry and prolonging the service life of the shoe materials). The existing microfiber leather has capillary channels formed between fibers, which easily causes water penetration in rainy days, sports sweating and other scenarios, and stains are easily attached and difficult to clean, especially in the field of outdoor shoes and professional sports shoes which have high requirements for weather resistance, the above problems are more prominent.

[0004] At present, the siphon-proof function of microfiber leather is mainly realized by coating a waterproof agent, which can be divided into fluorine-containing waterproof agent and fluorine-free waterproof agent according to the composition, and the industry usually evaluates the performance according to standards such as AATCC22 (water absorption test), AATCC197 (vertical wicking test), ASTM-D2099 (dynamic waterproof test of leather), etc. Both types of waterproof agents have their own advantages and disadvantages but have obvious limitations: Fluorine-containing waterproof agent: fluorocarbon compounds are the core, and the siphon-proof performance is excellent (initial contact angle > 110°, water droplets roll off quickly, and can resist heavy rain and oily stains), but fluorocarbon compounds have biological accumulation, which does not meet the requirements of environmental protection regulations, and the cost is 40%-60% higher than that of fluorine-free waterproof agent, which is difficult to popularize in the low-end shoe market.

[0005] Fluorine-free waterproof agent: acrylate polymers, polysiloxanes and the like are the main components, and it has the advantages of environmental protection and low cost, which is the development trend of the industry, but the existing products have three core technical defects, which seriously restrict their application: 1. Durability is poor: the coating has poor adhesion to the microfiber leather substrate, the waterproof performance decreases by more than 50% after 5000 times of Martin's friction test, and can only withstand 10-20 times of standard washing (fluorine-containing waterproof agent can withstand 30-50 times), and is prone to siphon failure due to bending, friction and washing.

[0006] 2. Low process adaptability: the upper of sports shoes is usually a composite material of "microfiber leather + mesh fabric / textile", and the adsorption of different materials to the coating is quite different. The existing fluorine-free waterproof agent cannot uniformly penetrate (such as knitted mesh fabric, the coverage rate is less than 60%), and local siphon failure is prone to occur.

[0007] 3. Multiple performances are difficult to balance: in order to improve the siphon effect, the coating often needs to be thickened or densified, which leads to a decrease in shoe material permeability and a decrease in wearing comfort; and only water-based stains can be prevented, oil-based stains cannot be prevented, and it is difficult to meet the needs of complex sports scenarios.

[0008] In summary, the existing fluorine-containing waterproof agent is limited due to environmental protection and cost problems, and the fluorine-free waterproof agent has technical bottlenecks in durability, process adaptability and multiple performance compatibility. Therefore, it is a key problem in the industry to develop a siphon-free fluorine-free waterproof agent that can simultaneously overcome the above-mentioned pain points. SUMMARY

[0009] The purpose of the present application is to provide a siphon-free fluorine-free waterproof agent and a preparation method thereof. Through innovative formula design and process optimization, the waterproof agent can be permanently attached and uniformly distributed on the surface of microfiber leather, while balancing the siphon, air permeability and flexibility, and meeting the dual needs of siphon performance and wearing experience of sports shoes, outdoor shoes and other shoes.

[0010] In order to achieve the above-mentioned application purposes, the following technical solutions are adopted in the present application: A siphon-free fluorine-free waterproof agent, comprising the following components by mass percentage: (1) Fluorine-free waterproof agent polymer: 30%-50%, the molecular chain of the fluorine-free waterproof agent polymer is grafted with a crosslinking group, and the crosslinking group is selected from at least one of an epoxy group, an amino group and a carboxyl group; (2) Water-based polyurethane crosslinking agent: 5%-15%, the water-based polyurethane crosslinking agent can react with the crosslinking group on the molecular chain of the fluorine-free waterproof agent polymer; (3) Ionic modification component: 8%-20%, the ionic modification component has an ionic supply group, and the ionic supply group is selected from at least one of a sulfonic acid group, a phosphoric acid group and a quaternary ammonium salt group; (4) Multi-functional component: 15%-35%, the multi-functional component is composed of a long-chain alkyl component, a polysiloxane chain segment component and a blocked polyurethane crosslinking agent in a weight ratio of (2-4):(1-3):(1-2). (5) Water: balance.

[0011] Further, the fluorine-free water repellent polymer is an acrylate copolymer, and the molar content of the crosslinking group in the fluorine-free water repellent polymer molecular chain is 5%-12%.

[0012] The acrylate copolymer is selected as the base body, the polymer itself has basic hydrophobic properties, and the grafted crosslinking group can form a chemical bond with the subsequent crosslinking agent to provide a reaction site for improving the durability of the coating, solving the problem of "weak adhesion" of traditional fluorine-free water repellents. The selection of acrylate copolymer takes into account environmental protection and cost, and has good compatibility with microfiber leather substrate.

[0013] Further, the ionic modification component is at least one of sodium p-styrenesulfonate, phosphoric acid ester bisphenol A acrylate, and dodecyl dimethyl benzyl ammonium chloride.

[0014] The ionic supply group can adapt to the surface properties of different materials (such as the polar polyurethane of microfiber leather and the cellulose hydroxyl of the mesh) in the microfiber leather composite upper surface through charge adsorption, improve the uniformity of the water repellent in heterogeneous materials, solve the problem of "local anti-syphon failure", and make the coverage rate of the coating in the area with uneven porosity such as knitted mesh reach more than 90%.

[0015] Further, the long-chain alkyl component is at least one of octadecyl acrylate and eicosyl methacrylate; and the polysiloxane segment component is at least one of polydimethylsiloxane acrylate and polymethylphenylsiloxane.

[0016] Further, the deblocking temperature of the blocked polyurethane crosslinking agent is 80-120°C, and the blocked polyurethane crosslinking agent is at least one of caprolactam blocked isocyanate and methyl ethyl ketoxime blocked isocyanate.

[0017] Further, the (4) multi-functional component specifically is: the long-chain alkyl component is octadecyl acrylate, the polysiloxane segment component is polydimethylsiloxane acrylate, and the blocked polyurethane crosslinking agent is caprolactam blocked isocyanate, and the weight ratio of the three is 3:2:1.5.

[0018] The long-chain alkyl component, the polysiloxane segment component, and the blocked polyurethane crosslinking agent are compounded in a specific ratio to achieve a balance of "waterproof-breathable-flexibility" and solve the defects of traditional fluorine-free water repellents "difficult to balance performance".

[0019] Further, the water-based polyurethane crosslinking agent is a water-based polyurethane containing hydroxyl groups, and the solid content is 30%-45%.

[0020] The water-based polyurethane containing hydroxyl groups can be cross-linked with the cross-linking groups of the fluorine-free water repellent polymer in the molecule to form a double cross-linking network: the internal cross-linking enhances the structural strength of the coating itself to resist micro-damage caused by friction; and the external cross-linking improves the bonding force between the coating and the microfiber leather substrate to avoid the coating from falling off during bending, and fundamentally improves the durability.

[0021] The application also discloses a preparation method of the anti-siphon fluorine-free water repellent. S1: the fluorine-free water repellent polymer and water are weighed according to the percentage by weight, the fluorine-free water repellent polymer is added into the water, and stirring is performed to form a uniform polymer dispersion liquid; S2: an ion modification component is added into the polymer dispersion liquid obtained in step S1, and stirring is performed to obtain a modified polymer dispersion liquid; S3: the water-based polyurethane cross-linking agent and the multi-functional component are sequentially added into the modified polymer dispersion liquid obtained in step S2, and stirring is performed for 120 min to 180 min to maintain the dispersion uniformity of the system; S4: after the stirring is completed, the system is allowed to stand for 24 h to 48 h, impurities with a particle size greater than 5 mu m are removed through filtration, and the anti-siphon fluorine-free water repellent is obtained.

[0022] Further, in step S3, the multi-functional component is added in the following sequence: the long-chain alkyl component is added first, the polysiloxane segment component is added after stirring for 30 min, and the blocked polyurethane cross-linking agent is added after stirring for 45 min.

[0023] Further, in step S4, the filtration is performed by using a microporous filter membrane with a pore size of 0.22 mu m to 0.45 mu m, and the filtration pressure is controlled to be 0.1 MPa to 0.2 MPa.

[0024] The application also discloses an application of the anti-siphon fluorine-free water repellent in a microfiber leather shoe material.

[0025] The water repellent is prepared by optimizing the preparation process parameters to ensure that the components fully function and improve the stability of the product.

[0026] Compared with the prior art, the technical scheme of the application has the following remarkable beneficial effects: 1. The durability is greatly improved The double cross-linking system composed of the "fluorine-free water repellent polymer cross-linking group + water-based polyurethane cross-linking agent" can not only enhance the structural strength of the coating itself, but also improve the adhesion between the coating and the microfiber leather substrate, effectively resist the bending and friction damage during the wearing of the shoe material, and reduce the damage of water washing, sweat and acid-base environment to the coating. Compared with the problems of easy falling off and rapid decay of the anti-siphon performance of the traditional fluorine-free water repellent, the microfiber leather treated by the water repellent of the application can maintain stable anti-siphon effect for a long time, and the service life is significantly prolonged.

[0027] 2. Significantly optimized process adaptability The introduction of ion-donating groups in the ion-modified components can adapt to the surface characteristics of different materials (such as microfiber leather, knitted mesh, and textiles) in microfiber leather composite uppers, enhancing the penetration and adsorption capacity of waterproofing agents in heterogeneous materials and avoiding the problem of insufficient local coating coverage due to material differences. Whether it's a mainstream athletic shoe composite structure such as "microfiber leather + mesh" or "microfiber leather + textiles," uniform coating can be achieved, significantly reducing the probability of localized anti-siphon failure. It is adaptable to current mainstream athletic shoe upper material combinations, with a coating coverage rate of ≥90% in areas with uneven porosity such as knitted mesh, and a localized anti-siphon failure rate reduced to <5% (compared to >40% for traditional fluorine-free waterproofing agents). It is suitable for anti-siphon treatment of mainstream athletic shoe composite materials.

[0028] 3. High-efficiency balance of multiple performance aspects The synergistic effect of multiple functional components achieves a balance of "anti-siphoning, breathability, and stain resistance": Anti-siphon and anti-fouling: The initial waterproof contact angle reaches 95-100°, and the 24-hour capillary water seepage is 0, which can resist both water-based stains and light oil stains. Breathability: After coating, the breathability of microfiber leather is ≥3000g / (m²・24h), with a decrease of only ≤30% (compared to 40-70% decrease with traditional fluorine-free waterproofing agents). 4. Outstanding advantages in environmental protection and cost. The waterproofing agent of this invention is free of fluorocarbons and poses no risk of bioaccumulation, meeting global regulations on the environmental friendliness of footwear materials. The raw materials are made from conventional environmentally friendly components, resulting in a significantly lower cost than fluorinated waterproofing agents. Furthermore, the preparation process requires no special equipment, is simple to operate, and is easy to mass-produce industrially, balancing environmental compliance with the economic viability of market penetration. Detailed Implementation

[0029] The present application will be further illustrated by the following embodiments, but the scope of protection of the present application is not limited to the embodiments.

[0030] Raw material preparation: The raw materials used in this embodiment and comparative example are all commercially available industrial-grade products, as detailed below: Fluorine-free waterproofing polymer: acrylate copolymer (grafted with epoxy and amino groups respectively, molar content 8%). Waterborne polyurethane crosslinking agent: Hydroxyl-containing waterborne polyurethane (40% solid content); Ion-modified components: Sodium p-styrene sulfonate (containing sulfonic acid groups), dodecyl dimethyl benzyl ammonium chloride (containing quaternary ammonium salt groups); Multi-functional components: Stearyl acrylate (long-chain alkyl component), dimethicone acrylate (polysiloxane segment component), caprolactam blocked isocyanate (blocked polyurethane crosslinking agent, deblocking temperature 100°C); Deionized water: self-made (conductivity <10 μS / cm); Comparative raw materials: conventional fluorine-free waterproofing agent (without crosslinking group, ionic modifier component, commercially available), fluorine-containing waterproofing agent (fluorocarbon compound type, commercially available).

[0031] Example 1: 1. Formulation composition: Acrylate copolymer (grafted epoxy group): 4000 g; Water-based polyurethane crosslinking agent: 1000 g; Ionic modifier component (sodium p-styrenesulfonate): 1500 g; Multi-functional components (stearyl acrylate: dimethicone acrylate: caprolactam blocked isocyanate = 3:2:1.5): 2000 g; Deionized water: 1500 g.

[0032] 2. Preparation steps: S1: Weigh the acrylate copolymer and deionized water, add them to the reaction kettle, stir at 30°C and 250 r / min for 40 min to form a uniform polymer dispersion; S2: Add sodium p-styrenesulfonate to the dispersion, heat to 45°C, and stir at 300 r / min for 75 min to obtain a modified polymer dispersion; S3: First, add stearyl acrylate to the modified dispersion and stir for 30 min; then add dimethicone acrylate and continue stirring for 45 min; finally, add caprolactam blocked isocyanate and water-based polyurethane crosslinking agent, control the temperature at 50°C and the stirring speed at 350 r / min for 150 min, and take samples every 30 min to ensure uniform dispersion of the system; S4: After stirring, cool the system to 28°C, and store it in a light-proof, sealed environment with a relative humidity of 50% for 36 h; then filter it using a 0.45 μm microporous filter under a pressure of 0.15 MPa to remove impurities and obtain a siphon-resistant fluorine-free waterproofing agent.

[0033] The waterproofing agent obtained in Example 1 above was used to treat the microfiber leather composite upper by "immersion method". Example 2:

[0034] 1. Formulation composition: Acrylate copolymer (grafted amino group): 3500 g; Aqueous polyurethane crosslinking agent: 1200 g; Ionic modification component (dodecyl dimethyl benzyl ammonium chloride): 1200 g; Multi-functional component (octadecyl acrylate: polydimethylsiloxane acrylate: caprolactam blocked isocyanate = 2.5:2.5:1.2): 1800 g; Deionized water: 2300 g.

[0035] 2. Preparation steps: S1: The acrylate copolymer and deionized water were weighed and stirred at 28°C and a rotation speed of 220 r / min for 45 min to form a polymer dispersion; S2: Dodecyl dimethyl benzyl ammonium chloride was added, the temperature was raised to 42°C, and stirring was performed at a rotation speed of 280 r / min for 80 min to obtain a modified dispersion; S3: Octadecyl acrylate (stirring for 30 min), polydimethylsiloxane acrylate (stirring for 45 min), and caprolactam blocked isocyanate were sequentially added, and an aqueous polyurethane crosslinking agent was synchronously added, and stirring was performed at 48°C and a rotation speed of 320 r / min for 160 min; S4: The temperature was lowered to 26°C, and the mixture was sealed in the dark (relative humidity 45%) and aged for 40 h, and then filtered through a 0.22 μm microporous filter membrane (0.12 MPa pressure) to obtain the target anti-siphon fluorine-free waterproof agent.

[0036] The waterproof agent obtained in Example 2 was used to treat the microfiber leather composite upper by the “dipping method”. Example 3:

[0037] 1. Formula composition: Acrylate copolymer (grafted epoxy group): 4500 g; Aqueous polyurethane crosslinking agent: 800 g; Ionic modification component (sodium p-styrenesulfonate: dodecyl dimethyl benzyl ammonium chloride = 1:1): 1000 g; Multi-functional component (octadecyl acrylate: polydimethylsiloxane acrylate: caprolactam blocked isocyanate = 3.5:1.5:1.8): 2200 g; Deionized water: 1500 g.

[0038] 2. Preparation steps: S1: The acrylate copolymer (grafted epoxy group) and deionized water were stirred at 32°C and a rotation speed of 280 r / min for 35 min to form a dispersion; S2: The mixed ionic modification component was added, the temperature was raised to 48°C, and stirring was performed at a rotation speed of 320 r / min for 70 min; S3: Add octadecyl acrylate (stir for 30 min), polydimethylsiloxane acrylate (stir for 45 min), caprolactam blocked isocyanate, and water-based polyurethane crosslinking agent in sequence, and stir at 52°C and 380 r / min for 140 min; S4: Cool down to 30°C, seal in dark (relative humidity 55%) and mature for 30 h, filter through a 0.45 μm microporous filter membrane (0.18 MPa pressure) to obtain the target anti-siphon fluorine-free waterproof agent.

[0039] The waterproof agent obtained in Example 3 above is used to treat the microfiber leather composite upper by the "dipping method".

[0040] Comparative Example 1: (traditional fluorine-free waterproof agent) Formulation composition: traditional acrylate fluorine-free waterproof agent (without crosslinking group) 40%, water 60%; Preparation steps: directly mix the traditional fluorine-free waterproof agent with water, stir at 30°C and 250 r / min for 30 min, without ion modification, crosslinking agent compounding and maturation steps.

[0041] Comparative Example 2: (fluorine-free waterproof agent without crosslinking system) Formulation composition: fluorine-free waterproof agent polymer in Example 1 40%, ion modification component 15%, multi-functional component 20%, water 25% (remove water-based polyurethane crosslinking agent); Preparation steps: same as Example 1, but no water-based polyurethane crosslinking agent is added in S3 step.

[0042] Comparative Example 3: (fluorine-containing waterproof agent) Commercial fluorocarbon compound waterproof agent is directly diluted according to the instruction manual and used for testing (as a performance reference).

[0043] The waterproof agents in Examples 1-3 and Comparative Examples 1-3 above are used to treat the same specification of microfiber leather composite uppers (microfiber leather + knitted mesh cloth) by the "dipping method" (waterproof agent is diluted to 15 wt%, microfiber leather shoe material is soaked for 40 min, and cured at 110°C for 30 min), and the performance is tested according to the following industry standards: Test item Test standard Core evaluation index Anti-siphon performance AATCC 197-2016 "Vertical wicking test" Initial contact angle, 24h capillary water penetration Durability Martindale abrasion test, washing resistance test Waterproof retention rate after 13,000 rubs, washing resistance times Process adaptability Visual + weighing method Knitted mesh area coating coverage Air permeability GB / T 10655-2003 "Fabric moisture permeability determination" Air permeability change rate The test results are shown in the following table: Test item Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3 Initial contact angle 98° 96° 100° 90° 95° 115° 24h capillary water penetration 0 0 0 5g 0 0 Waterproof retention rate after 13,000 rubs ≥82% ≥80% ≥85% ＜40% ＜50% ≥90% Washing resistance times 28 times 26 times 30 times 12 times 18 times 45 times Knitted mesh coating coverage 92% 91% 93% 58% 90% 95% Air permeability change rate -28% -25% -30% -65% -27% -20% Result analysis: 1. Anti-siphon performance: the initial contact angle of Examples 1-3 is 96°-100°, and the 24 h capillary water penetration amount is 0, which is better than that of Comparative Example 1 (traditional fluorine-free waterproof agent, initial contact angle 90°, 24 h capillary water penetration amount 5 g), although it is slightly lower than that of Comparative Example 3 (fluorine-containing waterproof agent, initial contact angle 115°), but it already meets the daily anti-splashing and anti-siphon requirements in light rain environment of sports shoes.

[0044] 2. Durability: The waterproof performance retention rates of Examples 1-3 are all ≥80% after 13,000 times of Martin Dale friction test, and the water washing resistance times are 26-30 times, which are significantly better than those of Comparative Example 1 (waterproof retention rate <40% after friction, water washing resistance 12 times) and Comparative Example 2 (no crosslinking system, waterproof retention rate <50% after friction, water washing resistance 18 times). This shows that the double crosslinking system composed of "fluorine-free waterproof agent polymer crosslinking group + waterborne polyurethane crosslinking agent" in the application can effectively enhance the adhesion of the coating to the microfiber leather substrate and the structural strength of the coating itself, and solve the core problems of easy peeling and poor weather resistance of traditional fluorine-free waterproof agents.

[0045] 3. Process adaptability: The coating coverage of Examples 1-3 on the knitted mesh area in the microfiber leather composite upper is 91%-93%, which is much higher than that of Comparative Example 1 (58%), close to that of Comparative Example 2 (90%) and Comparative Example 3 (95%), which verifies that the ion-modified component can adapt to the surface characteristics of different materials through charge adsorption, improve the uniformity of waterproof agent penetration in composite materials, and avoid local siphon failure.

[0046] 4. Air permeability: The air permeability of Examples 1-3 only decreases by 25%-30%, compared with the decrease of 65% of Comparative Example 1, realizing the synergistic improvement of "anti-siphon - air permeability - flexibility - stain resistance".

[0047] In summary, the application solves the three major pain points of poor durability, low process adaptability, and difficult to balance multiple performances of existing fluorine-free waterproof agents for microfiber leather shoe materials through the technical scheme of "double crosslinking enhancement + ion modification adaptation + multi-component synergy", and balances environmental regulation and practical value, which can be widely applied to anti-siphon treatment of microfiber leather shoe materials such as sports shoes and outdoor shoes.

[0048] The above examples are only used to illustrate the technical solutions of the application, and not to limit them. Although the application has been described in detail with reference to the above examples, those skilled in the art should understand that they can still modify the technical solutions described in the above examples, or make equivalent substitutions for part or all of the technical features; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the above examples.

Claims

1. A siphon-preventing fluorine-free water repellent agent, characterized by comprising: By mass percentage, the following components are included: (1) Fluorine-free waterproof agent polymer: 30%-50%, the molecular chain of the fluorine-free waterproof agent polymer is grafted with crosslinking groups selected from at least one of epoxy group, amino group, and carboxyl group; (2) Water-based polyurethane crosslinking agent: 5%-15%, the water-based polyurethane crosslinking agent can have a crosslinking reaction with the crosslinking groups on the molecular chain of the fluorine-free waterproof agent polymer; (3) Ionic modification component: 8%-20%, the ionic modification component has an ionic supply group selected from at least one of sulfonic acid group, phosphoric acid group, and quaternary ammonium salt group; (4) Multi-functional component: 15%-35%, the multi-functional component is composed of long-chain alkyl component, polysiloxane chain segment component, and blocked polyurethane crosslinking agent in a weight ratio of (2-4):(1-3):(1-2); (5) Water: the balance.

2. The anti-siphon, fluorochemical-free repellent agent of claim 1, wherein, The fluorine-free waterproof agent polymer is an acrylate copolymer, and the molar content of the crosslinking groups in the molecular chain of the fluorine-free waterproof agent polymer is 5%-12%.

3. The anti-siphon, fluorochemical-free repellent agent of claim 1, wherein, The ionic modification component is at least one of sodium p-styrenesulfonate, phosphate ester bisphenol A acrylate, and dodecyl dimethyl benzyl ammonium chloride.

4. The anti-siphon, fluorochemical-free, water repellent agent of claim 1, wherein, The long-chain alkyl component is at least one of octadecyl acrylate and eicosyl methacrylate; the polysiloxane chain segment component is at least one of polydimethylsiloxane acrylate and polymethylphenylsiloxane.

5. The anti-siphon, fluorochemical-free, water repellent agent of claim 1, wherein, The deblocking temperature of the blocked polyurethane crosslinking agent is 80°C-120°C, and the blocked polyurethane crosslinking agent is at least one of caprolactam blocked isocyanate and methyl ethyl ketone oxime blocked isocyanate.

6. The anti-siphon, fluorochemical-free, water repellent agent of claim 1, wherein, The multi-functional component (4) is specifically: the long-chain alkyl component is octadecyl acrylate, the polysiloxane chain segment component is polydimethylsiloxane acrylate, and the blocked polyurethane crosslinking agent is caprolactam blocked isocyanate, and the weight ratio of the three is 3:2:1.

5.

7. The anti-siphon, fluorochemical-free, water repellent agent of claim 1, wherein, The water-based polyurethane crosslinking agent is a water-based polyurethane containing a hydroxyl group, and the solid content is 30%-45%.

8. A method of preparing an anti-siphon, fluorine-free water repellent according to any one of claims 1 to 7, characterized in that, The following steps are included: S1: fluorine-free waterproof agent polymer and water are weighed by mass percentage, the fluorine-free waterproof agent polymer is added to water, and stirring is performed to form a uniform polymer dispersion liquid; S2: the ionic modification component is added to the polymer dispersion liquid obtained in step S1, and stirring is performed to obtain a modified polymer dispersion liquid; S3: the water-based polyurethane crosslinking agent and the multi-functional component are sequentially added to the modified polymer dispersion liquid obtained in step S2, and stirring is performed for 120min-180min to maintain the dispersion uniformity of the system; S4: after the stirring is completed, the system is left to stand for 24h-48h, filtration is performed using a microporous filter membrane with a pore size of 0.22μm-0.45μm, impurities with a particle size greater than 5μm are removed by filtration, the filtration pressure is controlled at 0.1MPa-0.2MPa, and an anti-siphon fluorine-free waterproof agent is obtained.

9. The production method according to claim 8, characterized by, In step S3, the multi-functional component is added in the following order: the long-chain alkyl component is added first, stirring is performed for 30min, then the polysiloxane chain segment component is added, and stirring is continued for 45min, and then the blocked polyurethane crosslinking agent is added.

10. Use of a hydrophobic agent according to any one of claims 1 to 7, which is free from fluorine, for the production of a superfabric leather shoe material which is free from siphoning.