Fluoride-free waterproof agent as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of waterproof agents, and particularly relates to a fluoride-free waterproof agent and a preparation method and application thereof. The fluoride-free waterproof agent comprises the following components in percentage by mass: 15-30% of cationic silicone wax, 20-35% of cationic water-based resin, 1-5% of a cosolvent, 20-50% of water and 1-5% of a cross-linking agent, the cationic silicone wax comprises self-emulsifying type cationic silicone wax. According to the fluoride-free waterproof agent, the self-emulsifying cationic silicone wax is adopted, so that introduction of a small molecular emulsifier is avoided. The fluoride-free waterproof agent not only can endow fabrics with excellent waterproofness and soft hand feeling, but also can remarkably improve the hand scratch phenomenon and improve the durability of the finishing effect, and can be widely applied to the fields of textiles, coatings and leather.

Description

Technical Field

[0001] This invention belongs to the field of waterproofing agent technology, specifically relating to a fluorine-free waterproofing agent, its preparation method, and its application. Background Technology

[0002] The textile industry has seen an increasingly urgent demand for multifunctional and environmentally friendly textile auxiliaries in recent years, particularly in the field of waterproofing finishing. Traditional fluorinated waterproofing agents are limited in application due to potential environmental risks, making fluorinated-free waterproofing agents a growing focus of research and development. Currently, most mainstream fluorinated-free waterproofing agents are based on cationic acrylic polymer emulsions, which provide waterproofing by forming a film on the fiber surface. However, to maintain emulsion stability, a large amount of small-molecule emulsifiers are usually introduced into the formulation. These emulsifiers easily migrate to the film surface during finishing and drying, or form water-soluble channels on the fibers due to their hydrophilicity, significantly reducing the continuity and hydrophobic density of the waterproof film, leading to a decrease in final waterproofing performance and poor wash resistance. Furthermore, while conventional acrylic waterproofing agents can provide a certain degree of waterproofing, they often result in a stiff and rough feel to the fabric, sacrificing softness and wearing comfort, failing to meet the pursuit of a soft touch in high-end textiles.

[0003] To balance waterproofing and a smooth feel, the industry often employs a process of compounding silicone softeners with waterproofing agents. However, ordinary silicone materials have poor compatibility with acrylic emulsions, easily causing problems such as oil drift and demulsification, affecting application performance. While some modified silicone oils can improve compatibility, they still largely rely on added emulsifiers for dispersion, failing to fundamentally solve the negative impacts introduced by the emulsifiers themselves. Therefore, developing a novel auxiliary agent that is perfectly compatible with cationic systems, avoids the performance losses caused by additional emulsifiers, and significantly enhances the softness of fabrics has become a crucial technological breakthrough. Summary of the Invention

[0004] Against this backdrop, the present invention aims to provide a fluorine-free waterproofing agent, its preparation method, and its application. This fluorine-free waterproofing agent is formulated by adding cationic silicone wax, a crosslinking agent, and a cationic resin. The cationic silicone wax used possesses unique self-emulsifying capabilities, allowing it to disperse stably in water without the need for external emulsifiers. This fundamentally eliminates the problem of deterioration in waterproofing performance caused by the addition of emulsifiers. It not only effectively maintains or even enhances waterproof durability but also significantly improves the softness and smoothness of fabrics. After the cationic silicone wax and cationic aqueous resin synergistically form a film, a softer, smoother hydrophobic film can be formed on the fiber surface, significantly improving the feel and style of the fabric and giving textiles a higher level of comfort and fullness.

[0005] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a fluorine-free waterproofing agent, comprising, by weight percentage, 15-30% cationic silicone wax, 20-35% cationic waterborne resin, 1-5% cosolvent, 20-50% water, and 1-5% crosslinking agent; the self-emulsifying cationic silicone wax is represented by the following average composition formula (I): R 1 a R 2 b R 3 c SiO （4-a-b-c） / 2 (I); Among them, R 1 It is represented by the following general formula (II): (II); Among them, R 4 It is selected from one of substituted or unsubstituted alkyl, aryl, and polyether groups, and the alkyl group is optionally interrupted by one or more oxygen atoms; Each R 5 They may be the same or different, selected from straight-chain or branched alkyl groups, and have at least one R. 5 Selected from C8~C45 alkyl groups, R 2 It is represented by the following general formula (Ⅲ): (Ⅲ); where R 8 Selected from substituted or unsubstituted hydrocarbon groups; R 3 It is an organic group; a is 0.01~0.5, b is 0.05~0.5, and c is 1.4~2.5.

[0006] Preferably, the cationic silicone wax is prepared by the following method: S1. Hydrogen-containing polysiloxane and unsaturated group-containing epoxy compound are reacted with a first catalyst to obtain epoxy-modified polysiloxane; S2. The epoxy-modified polysiloxane, long-chain alkyl fatty acid, and second catalyst are reacted to obtain epoxy silicone wax; S3. The obtained epoxy silicone wax, long alkyl chain tertiary amine and organic acid are reacted to obtain cationic silicone wax.

[0007] More specifically, in step S1, the specific steps include: in a nitrogen atmosphere, first blending hydrogen-containing polysiloxane, unsaturated epoxy compound and first catalyst, and holding at 60~140 ℃ for 1~30 h to obtain epoxy-modified polysiloxane.

[0008] Preferably, in step S1, the molar ratio between the hydrogen-containing polysiloxane and the allyl epoxy derivative is 1:(2.1~45), and the amount of catalyst used is 1~30 ppm; Preferably, in step S2, the molar ratio between the epoxy silicone oil intermediate and the long-chain alkyl fatty acid is 1:(1.1~30), and the amount of catalyst used is 30~500 ppm; Preferably, in step S3, the molar ratio between the epoxy silicone wax, the long alkyl chain tertiary amine, and the organic acid is 1:(1.1~30):(1.1~32).

[0009] Preferably, in step S1, the unsaturated epoxy compound includes one or more of allyl glycidyl ether, allyl functionalized bisphenol A epoxy resin, allyl phenyl glycidyl ether, eugenol glycidyl ether, trimethylolpropane diallyl ether glycidyl ether, allyl cyclohexyl glycidyl ester, glycidyl methacrylate, and allyl furfuryl glycidyl ether.

[0010] More preferably, in step S1, the unsaturated epoxy compound includes one or more of allyl glycidyl ether, allyl phenyl glycidyl ether, eugenol glycidyl ether, trimethylolpropane diallyl ether glycidyl ether, allyl cyclohexyl glycidyl ester, glycidyl methacrylate, and allyl furfuryl glycidyl ether.

[0011] Preferably, in step S1, the first catalyst is one or a combination of two or more of the following: Karstedt catalyst, Speier catalyst, and modified catalyst.

[0012] Preferably, in step S1, the molecular weight of the hydrogen-containing polysiloxane is 500~18000 g / mol, and the hydrogen content is 0.05~2.0%.

[0013] More preferably, in step S1, the molecular weight of the hydrogen-containing polysiloxane is 500 to 16000. g / mol, with a hydrogen content of 0.1-1.5%; for example, it can be 500 (0.6% hydrogen content), 600 (0.55% hydrogen content), 980 (0.45% hydrogen content), 1350 (0.53% hydrogen content), 1450 (0.65% hydrogen content), 1500 (0.68% hydrogen content), 2000 (0.75% hydrogen content), 3500 (0.36% hydrogen content), 4000 (0.49% hydrogen content), 6000 (0.36% hydrogen content), 6000 (0.75% hydrogen content), 9000 (1.28% hydrogen content), 10000 (1.05% hydrogen content), 13000 (0.45% hydrogen content), 15000 (0.75% hydrogen content), etc.

[0014] Preferably, in step S1, the molecular weight of the hydrogen-containing polysiloxane is 500~18000 g / mol, and the hydrogen content is 0.05~2.0%.

[0015] More preferably, in step S1, the molecular weight of the hydrogen-containing polysiloxane is 500 to 16000. g / mol, with a hydrogen content of 0.1-1.5%; for example, it can be 500 (0.6% hydrogen content), 600 (0.55% hydrogen content), 980 (0.45% hydrogen content), 1350 (0.53% hydrogen content), 1450 (0.65% hydrogen content), 1500 (0.68% hydrogen content), 2000 (0.75% hydrogen content), 3500 (0.36% hydrogen content), 4000 (0.49% hydrogen content), 6000 (0.36% hydrogen content), 6000 (0.75% hydrogen content), 9000 (1.28% hydrogen content), 10000 (1.05% hydrogen content), 13000 (0.45% hydrogen content), 15000 (0.75% hydrogen content), etc.

[0016] Preferably, step S2 includes the following steps: mixing the obtained epoxy-modified polysiloxane, long-chain fatty acid and catalyst, heating to 70~150 ℃ and reacting for 5~24 h to obtain epoxy silicone wax.

[0017] Preferably, in step S2, the long alkyl chain fatty acid includes one or more of the following: lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, erucic acid, palmitoleic acid, ricinoleic acid, α-linolenic acid, γ-linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid.

[0018] More preferably, in step S2, the long alkyl chain fatty acid is one or a combination of two or more of palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, erucic acid, palmitoleic acid, ricinoleic acid, α-linolenic acid, γ-linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid.

[0019] Preferably, step S3 specifically includes: reacting the epoxy silicone wax obtained in step S2 with a long alkyl chain tertiary amine and an organic acid at 40~100 °C for 1~16 h to obtain cationic silicone wax.

[0020] Preferably, in step S3, the long alkyl chain tertiary amine includes one or more of the following: trioctylamine, tridecylamine, tri(dodecyl)amine, di(dodecyl)methylamine, di(tetradecyl)methylamine, di(hexadecyl)methylamine, di(octadecyl)methylamine, decyl dimethylamine, dodecyl dimethylamine, and tetradecyl dimethylamine. More preferably, in step S3, the long alkyl chain tertiary amine includes one or more of the following: tridecylamine, tri(dodecyl)amine, di(dodecyl)methylamine, di(tetradecyl)methylamine, di(hexadecyl)methylamine, di(octadecyl)methylamine, decyl dimethylamine, dodecyl dimethylamine, and tetradecyl dimethylamine.

[0021] Preferably, the cationic aqueous resin includes one or more of cationic acrylate emulsion, cationic polyurethane aqueous resin, cationic epoxy aqueous resin, and cationic silicone resin.

[0022] Preferably, the cationic aqueous resin includes one or more of the following: cationic pure acrylate emulsion, cationic organosilicon modified acrylate emulsion, cationic organic / inorganic hybrid acrylate emulsion, and cationic styrene-acrylic emulsion.

[0023] Preferably, the co-solvent includes one or more of the following: ethanol, acetone, isopropanol, propylene glycol, PEG-200, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, methyl ethyl ketone, dipropylene glycol ethyl ether, tripropylene glycol ethyl ether, ethylene glycol, ethylene glycol ether, butanone, and cyclohexanone.

[0024] Preferably, the crosslinking agent comprises an organic polyacid.

[0025] Preferably, the crosslinking agent includes one or more of butanetetracarboxylic acid, citric acid, butanetetracarboxylic acid, tannic acid, and malic acid.

[0026] Secondly, the present invention provides a method for preparing the above-mentioned fluorine-free waterproofing agent, the method comprising the following steps: S1. After mixing cationic silicone wax with a co-solvent, heat and stir until completely dissolved. Then, add the first portion of water while stirring and continue stirring to obtain a cationic silicone wax emulsion. S2. The cationic silicone wax emulsion obtained in step S1 is mixed evenly with cationic aqueous resin, crosslinking agent and remaining water to obtain fluorine-free waterproofing agent.

[0027] Preferably, in step S1, the heating temperature is 70-90℃, and the stirring time is 20-60 minutes.

[0028] Preferably, the particle size of the cationic silicone wax emulsion is 200~900nm.

[0029] Thirdly, the present invention provides the application of a fluorine-free waterproofing agent as described in the first aspect or a fluorine-free waterproofing agent prepared according to the preparation method described in the second aspect in textiles, leather, and coatings.

[0030] Preferably, the textile includes any one of cotton, polyester, wool, acrylic, or blends thereof.

[0031] Fourthly, the present invention provides a fabric finishing agent comprising 1-10% waterproofing agent and 90-99% water, wherein the waterproofing agent comprises a fluorine-free waterproofing agent as described in the first aspect or a fluorine-free waterproofing agent prepared according to the preparation method described in the second aspect.

[0032] Compared with the prior art, the present invention has at least the following beneficial effects: (1) This invention introduces a cationic silicone wax with self-emulsifying properties. This cationic silicone wax can spontaneously disperse in the aqueous phase to form a stable emulsion without relying on external emulsifiers, thanks to the long alkyl chain cationic functional groups introduced in its molecular structure. This fundamentally avoids the many drawbacks of traditional non-self-emulsifying silicone waxes or silicone oils that require surfactants for emulsification. In traditional processes, the addition of small molecule emulsifiers not only easily migrates to the membrane surface, affecting continuous film formation, but also forms water-soluble channels on the fiber surface due to their hydrophilicity, severely degrading the waterproof performance. However, this invention, by introducing this cationic silicone wax, achieves the integration of emulsification and waterproofing functions, significantly improving the hydrophobic density and membrane integrity of the waterproofing agent, thereby suppressing the problem of decreased waterproof performance caused by the introduction of emulsifiers at the source.

[0033] (2) The fluorine-free waterproofing agent provided by this invention is obtained by compounding cationic silicone wax with cationic resin, crosslinking agent, etc. This self-emulsifying cationic silicone wax not only endows the system with excellent self-emulsifying ability, but also further enhances the comprehensive performance of the waterproofing agent. On the one hand, cationic silicone wax itself has good fiber affinity and soft and smooth properties. After it forms a film with cationic waterborne resin, especially acrylate copolymer, it can form a softer and smoother hydrophobic film on the fiber surface, which significantly improves the hand feel and style of the fabric and gives the textile a higher level of comfort and fullness. On the other hand, the cationic silicone wax forms a more stable bond with the resin molecular chain and fiber substrate through chemical or physical anchoring, which greatly improves the durability of waterproofing finishing. After multiple washes, it can still maintain excellent hydrophobic effect and hand feel stability, thereby effectively extending the functional life of textiles and meeting the dual needs of the high-end market for lasting softness and waterproof performance. Attached Figure Description

[0034] Figure 1 The infrared spectrum of the soft, hydrophobic, self-emulsifying cationic silicone wax (ZG1) obtained in Example 1 of this invention is shown.

[0035] Figure 2 Image 'a' shows a blank fabric sample undergoing a waterproof test.

[0036] Figure 2b is a photograph of a fabric sample treated with cationic acrylic emulsion undergoing a waterproof test.

[0037] Figure 2 c is a photograph of the fabric sample treated according to Application Example 1 of the present invention, which was washed 10 times and then subjected to a waterproof test. Detailed Implementation

[0038] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way. Example 1

[0039] 1-1 Preparation of Soft Hydrophobic Self-Emulsifying Cationic Silicone Wax This synthetic example provides a method for preparing a soft, hydrophobic, self-emulsifying cationic silicone wax, which includes the following steps: The raw materials for preparing soft, hydrophobic, self-emulsifying cationic silicone wax include: 0.5 mol of hydrogen-containing silicone oil (Sloco Polymer, Mn=1500 g / mol, hydrogen content 0.6%), 2 mol of allyl glycidyl ether, 5 ppm of chloroplatinic acid catalyst, 1 mol of stearic acid, 0.05 mol of tetrabutylammonium bromide, 1 mol of docosyldimethyl tertiary amine and 1.1 mol of glacial acetic acid.

[0040] The preparation method of the above-mentioned soft, hydrophobic, self-emulsifying cationic silicone wax includes the following steps, and its synthesis route is as follows: Figure 1 As shown: After mixing the hydrogen-containing silicone oil and chloroplatinic acid catalyst evenly, the mixture was stirred and heated until it reached 75 °C. Allyl glycidyl ether was then slowly added dropwise over 2 hours. The mixture was kept at this temperature for another 3 hours and then allowed to cool naturally to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, a measured amount of stearic acid and tetrabutylammonium bromide were added to the obtained epoxy intermediate. The mixture was then slowly heated to 85 °C and kept at this temperature for 4 hours. After cooling to 60 °C, a measured amount of docosyldimethyl tertiary amine and glacial acetic acid were added. The mixture was stirred and reacted for 6 hours and then allowed to cool naturally to room temperature to obtain a soft, hydrophobic, self-emulsifying cationic silicone wax (ZG1).

[0041] 1-2 Preparation of fluorine-free waterproofing agent The raw materials for preparing fluorine-free waterproofing agents include: 20g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG1), 30g of cationic acrylate emulsion (Dolphin1911R), 1g of dipropylene glycol methyl ether, 2g of butanetetracarboxylic acid, and 47g of deionized water.

[0042] The preparation method of the above-mentioned fluorine-free waterproofing agent includes the following steps: 20 g of the soft, hydrophobic, self-emulsifying cationic silicone wax (ZG1) was heated to 80 °C until completely dissolved. A co-solvent was added, and 30 g of deionized water at 80 °C was slowly added dropwise under high-speed stirring for 30 min to obtain a stable emulsion with a particle size of 200-600 nm. Finally, 30 g of cationic acrylate emulsion (Dolphin 1911R), 2 g of butanetetracarboxylic acid, and 17 g of deionized water were added and mixed evenly to obtain the fluorine-free waterproofing agent (ZF1). Example 2

[0043] 2-1 Preparation of Soft Hydrophobic Self-Emulsifying Cationic Silicone Wax This synthetic example provides a method for preparing a soft, hydrophobic, self-emulsifying cationic silicone wax, which includes the following steps: The raw materials for preparing soft, hydrophobic, self-emulsifying cationic silicone wax include: 0.5 mol of hydrogen-containing silicone oil (Sloco Polymer, Mn=2000 g / mol, hydrogen content 0.75%), 7.8 mol of allyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 3 mol of behenic acid, 0.2 mol of tetrabutylammonium bromide, 4 mol of docosyl dimethyl tertiary amine and 4.2 mol of glacial acetic acid.

[0044] The preparation method of the above-mentioned soft, hydrophobic, self-emulsifying cationic silicone wax includes the following steps: After uniformly mixing hydrogen-containing silicone oil and chloroplatinic acid catalyst, the mixture was heated while stirring. Once the system reached 110 °C, allyl glycidyl ether was slowly added dropwise over 2 hours. The reaction was continued at this temperature for 5 hours, and then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, a measured amount of behenic acid and tetrabutylammonium bromide were added to the obtained epoxy intermediate, and the temperature was slowly raised to 95 °C. After the reaction was continued at this temperature for 5 hours, the temperature was lowered to 60 °C, and a measured amount of docosyldimethyl tertiary amine and glacial acetic acid were added. The reaction was stirred for 6 hours, and then naturally cooled to room temperature to obtain a soft, hydrophobic, self-emulsifying cationic silicone wax (ZG2).

[0045] 2-2 Preparation of Fluorine-Free Waterproofing Agent The raw materials for preparing fluorine-free waterproofing agents include: 20g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG2), 30g of cationic acrylate emulsion (Dolphin1911R), 1g of dipropylene glycol methyl ether, 2g of butanetetracarboxylic acid, and 47g of deionized water.

[0046] The preparation method of the above-mentioned fluorine-free waterproofing agent includes the following steps: 20 g of the soft, hydrophobic, self-emulsifying cationic silicone wax (ZG2) was heated to 80 °C until completely dissolved. A co-solvent was added, and 35 g of deionized water at 80 °C was slowly added dropwise under high-speed stirring for 30 min to obtain a stable emulsion with a particle size of 200-600 nm. Finally, 30 g of cationic acrylate emulsion (Dolphin 1911R), 2 g of butanetetracarboxylic acid, and 12 g of deionized water were added and mixed evenly to obtain the fluorine-free waterproofing agent (ZF2). Example 3

[0047] 3-1 Preparation of Soft Hydrophobic Self-Emulsifying Cationic Silicone Wax This synthetic example provides a method for preparing a soft, hydrophobic, self-emulsifying cationic silicone wax, which includes the following steps: The raw materials for preparing soft, hydrophobic, self-emulsifying cationic silicone wax include: 0.5 mol of hydrogen-containing silicone oil (Sloco Polymer, Mn=2000 g / mol, hydrogen content 0.75%), 7.8 mol of allyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 5 mol of behenic acid, 0.2 mol of tetrabutylammonium bromide, 3 mol of docosyl dimethyl tertiary amine and 3.2 mol of glacial acetic acid.

[0048] The preparation method of the above-mentioned soft, hydrophobic, self-emulsifying cationic silicone wax includes the following steps: After thoroughly mixing the hydrogen-containing silicone oil and chloroplatinic acid catalyst, the mixture was heated while stirring. Once the system reached 110 °C, allyl glycidyl ether was slowly added dropwise over 2 hours. The reaction was then maintained at this temperature for another 5 hours, followed by natural cooling to room temperature. An epoxy polysiloxane intermediate was obtained; then, a measured amount of behenic acid and tetrabutylammonium bromide were added to the obtained epoxy intermediate, the temperature was slowly raised to 95 °C, and the reaction was maintained at this temperature for 5 h. After that, the temperature was lowered to 60 °C, and a measured amount of docosyldimethyl tertiary amine and glacial acetic acid were added. After stirring and reacting for 6 h, the mixture was naturally cooled to room temperature to obtain a soft, hydrophobic, self-emulsifying cationic silicone wax (ZG3).

[0049] 3-2 Preparation of Fluorine-Free Waterproofing Agent The raw materials for preparing fluorine-free waterproofing agents include: 20g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG3), 30g of cationic acrylate emulsion (Dolphin1911R), 1g of dipropylene glycol methyl ether, 2g of butanetetracarboxylic acid, and 47g of deionized water.

[0050] The preparation method of the above-mentioned fluorine-free waterproofing agent includes the following steps: 20 g of the soft, hydrophobic, self-emulsifying cationic silicone wax (ZG3) was heated to 80 °C until completely dissolved. A co-solvent was added, and 37 g of deionized water at 80 °C was slowly added dropwise under high-speed stirring for 30 min to obtain a stable emulsion with a particle size of 200-600 nm. Finally, 30 g of cationic acrylate emulsion (Dolphin 1911R), 2 g of butanetetracarboxylic acid, and 10 g of deionized water were added and mixed evenly to obtain the fluorine-free waterproofing agent (ZF3). Example 4

[0051] 4-1 Preparation of Soft, Hydrophobic, Self-Emulsifying Cationic Silicone Wax This synthetic example provides a method for preparing a soft, hydrophobic, self-emulsifying cationic silicone wax, which includes the following steps: The raw materials for preparing soft, hydrophobic, self-emulsifying cationic silicone wax include: 0.5 mol of hydrogen-containing silicone oil (Sloco Polymer, Mn=6000 g / mol, hydrogen content 0.36%), 11 mol of allyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 6 mol of behenic acid, 0.2 mol of tetrabutylammonium bromide, 5.5 mol of docosyldimethyl tertiary amine and 6 mol of glacial acetic acid.

[0052] The preparation method of the above-mentioned soft, hydrophobic, self-emulsifying cationic silicone wax includes the following steps: After uniformly mixing hydrogen-containing silicone oil and chloroplatinic acid catalyst, the mixture was heated while stirring. Once the system reached 120 °C, allyl glycidyl ether was slowly added dropwise over 2 hours. The reaction was continued at this temperature for 6 hours, and then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, a measured amount of behenic acid and tetrabutylammonium bromide were added to the obtained epoxy intermediate, and the temperature was slowly raised to 110 °C. After reacting at this temperature for 4 hours, the temperature was lowered to 60 °C, and a measured amount of docosyldimethyl tertiary amine and glacial acetic acid were added. The mixture was stirred and reacted for 6 hours, and then naturally cooled to room temperature to obtain a soft, hydrophobic, self-emulsifying cationic silicone wax (ZG4).

[0053] 4-2 Preparation of Fluorine-Free Waterproofing Agent The raw materials for preparing fluorine-free waterproofing agents include: 20g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG4), 30g of cationic acrylate emulsion (Dolphin1911R), 1g of dipropylene glycol methyl ether, 2g of citric acid, and 47g of deionized water.

[0054] The preparation method of the above-mentioned fluorine-free waterproofing agent includes the following steps: 20 g of the soft, hydrophobic, self-emulsifying cationic silicone wax (ZG4) was heated to 80 °C until completely dissolved. A co-solvent was added, and 44 g of deionized water at 80 °C was slowly added dropwise under high-speed stirring for 30 min to obtain a stable emulsion with a particle size of 200-600 nm. Finally, 30 g of cationic acrylate emulsion (Dolphin 1911R), 2 g of citric acid, and 3 g of deionized water were added and mixed evenly to obtain the fluorine-free waterproofing agent (ZF4). Example 5

[0055] 5-1 Preparation of Soft, Hydrophobic, Self-Emulsifying Cationic Silicone Wax This synthetic example provides a method for preparing a soft, hydrophobic, self-emulsifying cationic silicone wax, which includes the following steps: The raw materials for preparing soft, hydrophobic, self-emulsifying cationic silicone wax include: 0.5 mol of hydrogen-containing silicone oil (Sloco Polymer, Mn=6000 g / mol, hydrogen content 0.36%), 11 mol of allyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 8 mol of behenic acid, 0.2 mol of tetrabutylammonium bromide, 4 mol of docosyl dimethyl tertiary amine and 4.4 mol of glacial acetic acid.

[0056] The preparation method of the above-mentioned soft, hydrophobic, self-emulsifying cationic silicone wax includes the following steps: After uniformly mixing the hydrogen-containing silicone oil and chloroplatinic acid catalyst, the mixture was heated while stirring. Once the system reached 120 °C, allyl glycidyl ether was slowly added dropwise over 2 hours. The reaction was continued at this temperature for 6 hours, and then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, a measured amount of behenic acid and tetrabutylammonium bromide were added to the obtained epoxy intermediate, and the temperature was slowly raised to 105 °C. After reacting at this temperature for 4 hours, the temperature was lowered to 60 °C, and a measured amount of docosyldimethyl tertiary amine and glacial acetic acid were added. The mixture was stirred and reacted for 6 hours, and then naturally cooled to room temperature to obtain a soft, hydrophobic, self-emulsifying cationic silicone wax (ZG5).

[0057] 5-2 Preparation of Fluorine-Free Waterproofing Agent The raw materials for preparing fluorine-free waterproofing agents include: 20g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG5), 30g of cationic acrylate emulsion (Dolphin1911R), 1g of dipropylene glycol methyl ether, 2g of citric acid, and 47g of deionized water.

[0058] The preparation method of the above-mentioned fluorine-free waterproofing agent includes the following steps: 20 g of the soft, hydrophobic, self-emulsifying cationic silicone wax (ZG5) was heated to 80 °C until completely dissolved. A co-solvent was added, and 44 g of deionized water at 80 °C was slowly added dropwise under high-speed stirring for 30 min to obtain a stable emulsion with a particle size of 200-600 nm. Finally, 30 g of cationic acrylate emulsion (Dolphin 1911R), 2 g of citric acid, and 3 g of deionized water were added and mixed evenly to obtain the fluorine-free waterproofing agent (ZF5). Example 6

[0059] 6-1 Preparation of Soft, Hydrophobic, Self-Emulsifying Cationic Silicone Wax This synthetic example provides a method for preparing a soft, hydrophobic, self-emulsifying cationic silicone wax, which includes the following steps: The raw materials for preparing soft, hydrophobic, self-emulsifying cationic silicone wax include: 0.5 mol of hydrogen-containing silicone oil (Sloco Polymer, Mn=6000 g / mol, hydrogen content 0.36%), 11 mol of allyl phenyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 6 mol of behenic acid, 0.2 mol of tetrabutylammonium bromide, 5.5 mol of docosyl dimethyl tertiary amine and 6 mol of glacial acetic acid.

[0060] The preparation method of the above-mentioned soft hydrophobic self-emulsifying cationic silicone wax includes the following steps: After mixing the hydrogen-containing silicone oil and chloroplatinic acid catalyst evenly, the mixture is heated while stirring. When the system reaches 120 °C, allyl phenyl glycidyl ether is slowly added dropwise. The addition is completed in 2 hours. The reaction is continued at the same temperature for 4 hours. The mixture is then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, a measured amount of behenic acid and tetrabutylammonium bromide are added to the obtained epoxy intermediate. The temperature is slowly raised to 115 °C. The reaction is continued at the same temperature for 3 hours. The temperature is then lowered to 60 °C, and a measured amount of docosyl dimethyl tertiary amine and glacial acetic acid are added. The mixture is stirred and reacted for 6 hours. The mixture is then naturally cooled to room temperature to obtain a soft hydrophobic self-emulsifying cationic silicone wax (ZG6).

[0061] 6-2 Preparation of Fluorine-Free Waterproofing Agent The raw materials for preparing fluorine-free waterproofing agents include: 20g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG6), 30g of cationic acrylate emulsion (Dolphin1911R), 1g of dipropylene glycol methyl ether, 2g of citric acid, and 47g of deionized water.

[0062] The preparation method of the above-mentioned fluorine-free waterproofing agent includes the following steps: 20 g of the soft, hydrophobic, self-emulsifying cationic silicone wax (ZG6) was heated to 80 °C until completely dissolved. A co-solvent was added, and 46 g of deionized water at 80 °C was slowly added dropwise under high-speed stirring for 30 min to obtain a stable emulsion with a particle size of 200-600 nm. Finally, 30 g of cationic acrylate emulsion (Dolphin 1911R), 2 g of citric acid, and 1 g of deionized water were added and mixed evenly to obtain the fluorine-free waterproofing agent (ZF6). Example 7

[0063] 7-1 Preparation of Soft, Hydrophobic, Self-Emulsifying Cationic Silicone Wax This synthetic example provides a method for preparing a soft, hydrophobic, self-emulsifying cationic silicone wax, which includes the following steps: The raw materials for preparing soft, hydrophobic, self-emulsifying cationic silicone wax include: 0.5 mol of hydrogen-containing silicone oil (Sloco Polymer, Mn=6000 g / mol, hydrogen content 0.45%), 14 mol of allyl phenyl glycidyl ether, 10 ppm of chloroplatinic acid catalyst, 7 mol of behenic acid, 0.3 mol of tetrabutylammonium bromide, 7 mol of docosyl dimethyl tertiary amine and 7.5 mol of glacial acetic acid.

[0064] The preparation method of the above-mentioned soft, hydrophobic, self-emulsifying cationic silicone wax includes the following steps: After uniformly mixing the hydrogen-containing silicone oil and chloroplatinic acid catalyst, the mixture was heated while stirring. Once the system reached 135 °C, allyl phenyl glycidyl ether was slowly added dropwise over 2 hours. The reaction was continued at this temperature for 5 hours, and then naturally cooled to room temperature to obtain an epoxy polysiloxane intermediate. Subsequently, the system was cooled to 115 °C, and measured amounts of behenic acid and tetrabutylammonium bromide were added sequentially. After the reaction was continued at this temperature for 5 hours, the temperature was lowered to 60 °C, and measured amounts of docosyl dimethyl tertiary amine and glacial acetic acid were added. The reaction was stirred for 8 hours, and then naturally cooled to room temperature to obtain a soft, hydrophobic, self-emulsifying cationic silicone wax (ZG7).

[0065] 7-2 Preparation of Fluorine-Free Waterproofing Agent The raw materials for preparing fluorine-free waterproofing agents include: 20g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG7), 30g of cationic acrylate emulsion (Dolphin1911R), 1g of dipropylene glycol methyl ether, 2g of citric acid, and 47g of deionized water.

[0066] The preparation method of the above-mentioned fluorine-free waterproofing agent includes the following steps: 20 g of the soft, hydrophobic, self-emulsifying cationic silicone wax (ZG7) was heated to 80 °C until completely dissolved. A small amount of co-solvent was added, and 46 g of deionized water at 80 °C was slowly added dropwise under high-speed stirring for 30 min to obtain a stable emulsion with a particle size of 200-600 nm. Finally, 30 g of cationic acrylate emulsion (Dolphin 1911R), 2 g of citric acid, and 1 g of deionized water were added and mixed evenly to obtain the fluorine-free waterproofing agent (ZF7). Example 8

[0067] This embodiment provides a fluorine-free waterproofing agent, which comprises the following components: 15g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG7), 33g of cationic acrylate emulsion (Dolphin1911R), 1g of dipropylene glycol methyl ether, 1g of citric acid, and 50g of deionized water.

[0068] The preparation method of the above-mentioned fluorine-free waterproofing agent includes the following steps: 15 g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG7) was heated to 90 °C until completely dissolved. A small amount of co-solvent was added, and 40 g of deionized water at 90 °C was slowly added dropwise under high-speed stirring for 20 min to obtain a stable emulsion with a particle size of 380 nm. Finally, 33 g of cationic acrylate emulsion (Dolphin 1911R), 1 g of citric acid, and 10 g of deionized water were added and mixed evenly to obtain a fluorine-free waterproofing agent (ZF8). Example 9

[0069] This embodiment provides a fluorine-free waterproofing agent, which comprises the following components: 30g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG2), 20g of cationic acrylate emulsion (Dolphin1911R), 5g of dipropylene glycol methyl ether, 5g of citric acid, and 40g of deionized water.

[0070] The preparation method of the above-mentioned fluorine-free waterproofing agent includes the following steps: 30g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG2) was heated to 85°C until completely dissolved. A small amount of co-solvent was added, and 38g of deionized water at 85°C was slowly added dropwise under high-speed stirring for 60 minutes to obtain a stable emulsion with a particle size of 450 nm. Finally, 20g of cationic acrylate emulsion (Dolphin 1911R), 5g of citric acid, and 2g of deionized water were added and mixed evenly to obtain a fluorine-free waterproofing agent (ZF9). Example 10

[0071] This embodiment provides a fluorine-free waterproofing agent, which comprises the following components: 25g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG3), 35g of cationic acrylate emulsion (Dolphin1911R), 3g of dipropylene glycol methyl ether, 3g of citric acid, and 34g of deionized water.

[0072] The preparation method of the above-mentioned fluorine-free waterproofing agent includes the following steps: 25g of soft, hydrophobic, self-emulsifying cationic silicone wax (ZG3) was heated to 70°C until completely dissolved. Then, 30g of deionized water at 70°C was slowly added dropwise while stirring at high speed for 40 minutes to obtain a stable emulsion with a particle size of 300 nm. Finally, 35g of cationic acrylate emulsion (Dolphin 1911R), 3g of citric acid, and 4g of deionized water were added and mixed evenly to obtain a fluorine-free waterproofing agent (ZF10).

[0073] Comparative Example 1 The difference between this comparative example and Example 1 is that this comparative example uses 2 moles of octadecene and 0.5 moles of hydrogen-containing silicone oil (Sloco Polymer, Mn=1500 g / mol, hydrogen content 0.6%) to synthesize an inert alkyl silicone wax ZG11, while the remaining steps for preparing the fluorine-free waterproofing agent remain unchanged. However, because the obtained ZG11 does not possess self-emulsifying properties, it cannot form a stable emulsion when used to prepare the fluorine-free waterproofing agent according to the process described in Example 1.

[0074] Comparative Example 2 The only difference between the comparative example and Example 1 is that the molar ratio of stearic acid to allyl glycidyl ether is changed to 1:1, and docosyl dimethyl tertiary amine is not added to obtain hydroxyl-containing silicone wax ZG12; then, following the preparation process of the fluorine-free waterproofing agent in Example 1, 5% fatty alcohol polyoxyethylene ether emulsifier is added, and the amount of deionized water is reduced by 5%, while the other components and steps remain unchanged to obtain fluorine-free waterproofing agent ZF12.

[0075] Comparative Example 3 The only difference between this comparative example and Example 1 is that the amount of self-emulsifying cationic silicone wax added is changed to 10g, and the amount of cationic acrylic emulsion added is changed to 38g (ZF13).

[0076] Comparative Example 4 The only difference between this comparative example and Example 1 is that the amount of self-emulsifying cationic silicone wax added is changed to 35g, and the amount of cationic acrylic emulsion added is changed to 13g (ZF14).

[0077] Application Examples 1-10 A fabric padding finishing solution contains 6 g of a fluorine-free waterproofing agent and 94 g of deionized water, wherein the fluorine-free waterproofing agent was prepared in Examples 1 to 10 respectively.

[0078] Compare and contrast examples 1-4 A padding finishing solution for a fabric comprises 6 g of a fluorine-free waterproofing agent obtained in Comparative Examples 1 to 4, and 94 g of deionized water.

[0079] Performance testing

[0080] The fluorine-free waterproofing finishing solutions obtained from Application Examples 1-10 and Comparative Application Examples 1-4 were used to treat cotton fabrics according to the following process: soaping → two dips and two nips (80% pick-up) → baking (170 ℃ × 2 min). The treated fabrics were then subjected to the following performance tests, using the following methods: (1) Waterproof performance test: After the treated fabric is washed 10 times, the finished fabric is tested in accordance with GB / T 4745-2012 "Test and evaluation of waterproof performance of textiles - water-wetting method". According to the water-wetting performance, the waterproof performance is divided into 1 to 5 levels, of which level 5 is the best, indicating that there are no water droplets or wetting on the sample surface; level 4 indicates that the sample surface is wetted at sporadic spray points; level 3 indicates that the sample surface is wetted at spray points; level 2 indicates that the sample surface is wetted beyond the spray points, and the wetted area is half of the sprayed area; level 1 indicates that the sample surface is completely wetted.

[0081] (2) Softness test: Cut the treated fabric into 10×10 cm pieces and measure the softness using a computer softness meter. The smaller the test force required, the better the softness of the fabric. Test the softness before washing and after 10 washes.

[0082] (3) Friction resistance test: The fabric to be tested was cut into upper samples of 30 mm × 28 mm and lower samples of 30 mm × 77 mm. The lower sample was fixed in the clamp device of the YG821L air quality tester platform, and the upper sample was placed on the surface of the lower sample with the same fabric orientation. The friction performance was tested under the standard test environment of 22 ± 2 ℃ and 68% ± 2% relative humidity. The coefficient of friction was tested before washing and after 10 washes.

[0083] The above washing procedure is carried out in accordance with the method in ISO 105-C04-2010.

[0084] Specific test results are shown in Table 1 and... Figure 2 As shown, a fabric sample that has not been treated with a fluorine-free waterproofing emulsion is used as a blank example for comparison.

[0085] Table 1

[0086] As shown in Table 1, the fluorine-free waterproofing agent provided in this embodiment of the invention, when applied to textile finishing processes, imparts excellent softness, smoothness, and durability to fabrics. Compared to untreated fabrics, fabrics treated with the self-emulsifying cationic fluorine-free waterproofing agent of this embodiment exhibit superior softness before washing. Specifically, the fabric treated with ZF5 exhibits the highest softness, being 2.27 times that of the blank fabric and 2.49 times that of the fabric treated with pure cationic acrylate emulsion (Dolphin 1911R). This phenomenon can be attributed to the high molecular weight of the silicone wax component in ZF5 and the high proportion of siloxane segments in its molecular structure, thus imparting a superior soft hand feel to the fabric; while the pure cationic acrylate emulsion, due to its rigid acrylate structure, forms a harder film on the fabric surface, resulting in lower softness than the blank fabric. After standard washing, the softness of fabrics treated with finishing solutions containing ZF1 to ZF9 only shows a slight decrease, and the reduction in waterproofing performance is limited. This is mainly due to the cross-linking of hydroxyl groups in the molecule with the fiber under the action of polycarboxylic acids, which enhances the adhesion strength; in addition, the electrostatic adsorption between cationic groups and fibers also improves the bonding strength. The synergistic effect of these two factors significantly enhances the durability of the waterproofing agent. In contrast, the waterproofing performance of fabrics treated with ZF12 is significantly reduced. This is because its molecules lack cationic groups, and the emulsifier introduced during the preparation process weakens the cross-linking density between silicone wax and fibers to some extent, resulting in a decrease in hand feel and waterproofing performance after washing. This result further indicates that the self-emulsifying cationic silicone wax prepared using this invention can effectively avoid the problems of decreased waterproofing and poor hand feel caused by added emulsifiers, and has high practical application value.

[0087] Furthermore, taking GF1-treated fabrics as an example, the waterproofing performance of the fluorine-free waterproofing agent of this invention is evaluated. From... Figure 2 As can be seen, after 10 standard washes, the blank fabric sample was completely soaked in the spray test, with a waterproof rating of Level 1. Fabrics treated with pure acrylic emulsion (1911R) achieved a waterproof rating of Level 2, while fabrics treated with GF1 achieved a waterproof rating of Level 4 or higher, and were also softer and scratch-free. This is mainly due to the soft, hydrophobic cationic silicone wax structure introduced into the waterproofing agent, and the enhanced bonding force between the waterproofing agent and fibers with the assistance of a crosslinking agent. Furthermore, the introduction of siloxane segments further improved the fabric's softness. These results demonstrate that the self-emulsifying cationic silicone wax-based fluorine-free waterproofing agent synthesized in this invention can effectively improve the waterproofness and wash resistance of fabrics.

[0088] As can be seen from Comparative Examples 3 and 4, when the amount of self-emulsifying cationic silicone wax added is outside the range specified in this invention, the water resistance decreases.

[0089] This fluorine-free waterproofing agent, prepared based on cationic silicone wax, has broad application prospects in the field of hydrophobic finishing of textiles. It is suitable for various fiber materials such as cotton, linen, silk, and chemical fibers, and can significantly improve the waterproof performance and wearing comfort of fabrics. It provides a new technical approach for the textile finishing industry and helps to promote the industry towards high performance and environmental protection.

[0090] The applicant declares that the present invention has provided a detailed description of a fluorine-free waterproofing agent, its preparation method, and its application through the above embodiments. However, it should be understood that the described embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. Any modifications, alterations, or equivalent substitutions made to the technical solution within the spirit and principles of the present invention, including but not limited to equivalent substitutions of raw material components, reasonable introduction of auxiliary components, and adjustments to specific process parameters, should be included within the protection scope of the present invention.

Claims

1. A fluorine-free water repellent agent, characterized by comprising: The fluorine-free waterproof agent comprises, by mass percentage, 15-30% of cationic silicone wax, 20-35% of cationic water-based resin, 1-5% of cosolvent, 20-50% of water, and 1-5% of crosslinking agent. The cationic silicone wax includes a self-emulsifying cationic silicone wax; the self-emulsifying cationic silicone wax is represented by the following average composition formula (I): R 1 a R 2 b R 3 c SiO （4-a-b-c） / 2 (I); wherein R 1 is represented by the following general formula (II): （Ⅱ）； wherein R 4 is selected from one of substituted or unsubstituted alkyl, aryl, polyether groups, and the alkyl is optionally interrupted by one or more oxygen atoms; each R 5 may be the same or different and are selected from linear or branched alkyl groups and at least one R 5 is selected from C8to C45alkyl groups, R 2 represented by the following general formula (III): (III); wherein R 8 selected from substituted or unsubstituted hydrocarbyl groups; R 3 R is an organic group; * represents a connection position; a is 0.01-0.5, b is 0.05-0.5, and c is 1.4-2.

5.

2. The fluorine-free water repellent agent according to claim 1, characterized by, The cationic water-based resin comprises one or two or more of cationic acrylate emulsion, cationic polyurethane water-based resin, cationic epoxy water-based resin, and cationic silicone resin.

3. The fluorine-free water repellent agent according to claim 1, characterized by, The cationic water-based resin comprises one or two or more of cationic pure acrylate emulsion, cationic silicone-modified acrylate emulsion, cationic organic / inorganic hybrid acrylate emulsion, and cationic styrene-acrylic emulsion.

4. The fluorine-free water repellent agent according to claim 1, characterized by, The cosolvent comprises one or two or more of ethanol, acetone, isopropyl alcohol, propylene glycol, PEG-200, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, methyl ethyl ketone, dipropylene glycol ethyl ether, tripropylene glycol ethyl ether, ethylene glycol, ethylene glycol ether, butanone, and cyclohexanone.

5. The fluorine-free water repellent agent according to claim 1, characterized by, The crosslinking agent comprises organic polybasic acid.

6. The fluorine-free water repellent agent according to claim 1, characterized by, The crosslinking agent comprises one or two or more of butane tetracarboxylic acid, citric acid, butane tetracarboxylic acid, tannic acid, and malic acid.

7. The method of producing a fluorine-free water repellent according to any one of claims 1 to 6, characterized by, The preparation method comprises the following steps: S1. After mixing the cationic silicone wax with the cosolvent and heating and stirring until complete dissolution, the first portion of water is added under stirring, and the stirring is continued to obtain a cationic silicone wax emulsion; S2. The cationic silicone wax emulsion obtained in step S1 is mixed with the cationic water-based resin, the crosslinking agent, and the remaining water to obtain the fluorine-free waterproof agent.

8. The preparation method according to claim 7, characterized in that, In step S1, the heating temperature is 70-90°C, and the time for the continued stirring is 20-60 min.

9. Use of the fluorine-free waterproof agent according to any one of claims 1-6 or prepared according to the preparation method of claim 7 or 8 in textiles, leather, and coatings.

10. A fabric aftertreatment agent characterized in that, The waterproof agent comprises 1-10% of the fluorine-free waterproof agent according to any one of claims 1-6 or prepared according to the preparation method of claim 7 or 8, and 90-99% of water.

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