Silicone resin modified waterproof material, preparation method and application thereof

Abstract

The application discloses a silicone resin modified waterproof material, a preparation method and application thereof. The material is introduced with a methacryloxypropyl group, an N-cyclohexyl-gamma-aminopropyl group, a phenyl group and a long carbon chain alkyl group. The material is prepared in two steps. First, a first product is prepared through reaction of multiple siloxanes, and then the first product is reacted with a side hydrogen-containing silicone oil and an alpha-olefin to obtain the target material. A fluorine-free waterproof finishing agent is prepared through emulsification of the target material. The product is environmentally friendly and compliant, has high waterproof and oil-proof performance, fabric softness and skin friendliness, is washable and durable, has simple process, is easy to obtain raw materials, is low in cost, is less in waste, is suitable for cotton shuttles and polyester fabrics, and can replace traditional fluorine-containing waterproof agents.

Description

Technical Field

[0001] This application relates to the field of fabric finishing agents, specifically to a silicone resin modified waterproof material, its preparation method, and its application. Background Technology

[0002] Textile waterproofing agents are important auxiliaries in the textile processing industry. With the increasing global awareness of environmental protection and the continuous tightening of environmental regulations, fluorine-free waterproofing agents are gradually becoming the core development direction of the textile waterproofing agent market. At present, the global waterproofing agent market is huge. Traditional fluorinated waterproofing agents once occupied an important position in the market due to their excellent waterproof and oil-repellent effects. However, their core raw materials, perfluorinated and polyfluoroalkyl substances (PFAS), have extremely strong environmental persistence. The CF bond is difficult to degrade naturally, has a long half-life, and is easy to accumulate in organisms and be amplified through the food chain, which can easily induce human diseases. To this end, my country has included PFOS, PFOA, and PFHxS substances in the "List of Key Controlled New Pollutants (2023 Edition)," prohibiting their use in textile production and processing except for special purposes; the EU's EN 17681-1:2025 testing standard will come into effect on October 31, 2025, significantly improving the detection accuracy of PFAS; France will also completely ban the production, import, export, and sale of textiles, footwear, and waterproofing agents containing PFAS from January 1, 2026, severely restricting the application of fluorinated waterproofing agents. Developing high-performance fluorine-free waterproofing agents to replace fluorinated waterproofing agents has become an inevitable and urgent need for the industry.

[0003] Although the research and application of fluorine-free waterproofing agents have made some progress, current fluorine-free waterproofing agents on the market still have many technical defects, making it difficult to completely replace fluorine-containing waterproofing agents. From a performance perspective, existing fluorine-free waterproofing agents can only meet basic waterproofing needs, and there is a significant gap compared to fluorine-containing waterproofing agents in terms of high-level waterproofing and oil-repellent effects, making them unsuitable for textile applications requiring oil and high waterproofing. From a cost perspective, the production cost of existing fluorine-free waterproofing agents is relatively high, and their market price is much higher than that of traditional fluorine-containing waterproofing agents, significantly increasing the usage costs for textile companies and reducing market acceptance. At the same time, some fluorine-free waterproofing agents also have unreasonable formulation designs, which can lead to a deterioration in the hand feel of fabrics treated with them, further limiting their market promotion and application.

[0004] With the continuous improvement of residents' living standards, consumers have placed higher demands on the overall performance of textile products. They are no longer satisfied with just the basic functions of fabrics, but rather have dual requirements for functionality and comfort. They demand excellent and stable waterproof and oil-repellent properties to meet the needs of various daily use scenarios, while also maintaining good softness, hand feel, and wearing comfort to avoid a decline in the wearing experience due to functional finishing. However, existing fluorine-free waterproofing agents generally suffer from the problem of not being able to simultaneously achieve waterproof and oil-repellent performance and fabric softness and comfort. In current technologies, attempting to improve the waterproof and oil-repellent effect of fluorine-free waterproofing agents often leads to a decrease in the softness and a worse hand feel of the finished fabric. Conversely, prioritizing the softness and comfort of the fabric sacrifices waterproof and oil-repellent performance. Therefore, developing a low-cost, simple-process silicone-modified fluorine-free waterproofing agent that can simultaneously impart excellent waterproof and oil-repellent effects to fabrics while maintaining good softness and comfort has become an urgent technical problem to be solved in the field of textile waterproofing finishing agents. Summary of the Invention

[0005] The purpose of this application is to provide a fluorine-free waterproof finishing agent that is waterproof, oil-proof, soft, and skin-friendly.

[0006] To achieve the above objectives, the technical solution adopted in this application is as follows: A silicone resin modified waterproof material is provided, the general structural formula of which is: Where z, a, b, c, d, m, n, e are integers, and 1 ≤ z ≤ 2, 13 ≤ a ≤ 17, 1 ≤ b ≤ 2, 4 ≤ c ≤ 5, 156 ≤ d ≤ 235, 0 <m≤45,0<n≤45,1≤e≤2。

[0007] This application also provides a method for preparing a silicone resin modified waterproof material, comprising the following steps: S1: reacting octamethylcyclotetrasiloxane, N-cyclohexyl-r-aminopropyldimethoxysilane, methacryloxypropyldimethylmethoxysilane and methylphenyldimethoxysilane to obtain a first product; S2: reacting hydrogen-containing silicone oil, the first product and α-olefin in a catalyst and solvent to obtain the silicone resin modified waterproof material; The structural formula of the first product is: Where m, n, and e are integers, and 0 <m≤45,0<n≤45,1≤e≤2。

[0008] The structural formula of the silicone resin modified waterproof material is: Where z, a, b, c, d, m, n, e are integers, and 1 ≤ z ≤ 2, 13 ≤ a ≤ 17, 1 ≤ b ≤ 2, 4 ≤ c ≤ 5, 156 ≤ d ≤ 235, 0 <m≤45,0<n≤45,1≤e≤2。

[0009] As a preferred embodiment, the α-olefin has a carbon chain with a carbon number of not less than 16.

[0010] As another preferred embodiment, the α-olefin is any one or a combination of 1-hexadecene, 1-octadecene, and 1-eicosene.

[0011] As another preferred option, the side-containing hydrogen silicone oil has a number-average molecular weight of 12,000 to 18,000.

[0012] As another preferred option, the hydrogen content of the side-containing hydrogen silicone oil is 0.033%~0.075%.

[0013] As another preferred option, the solvent is any one or a combination of more than one of isopropanol, ethylene glycol monobutyl ether, isopentyl glycol, and diethylene glycol monobutyl ether.

[0014] As another preferred embodiment, the specific steps include: S1: 2270-3116 parts by mass of the octamethylcyclotetrasiloxane, 200-300 parts by mass of the N-cyclohexyl-r-aminopropyldimethoxysilane, 400-500 parts by mass of the methacryloyloxypropyldimethylmethoxysilane, and 154-308 parts by mass of the methylphenyldimethoxysilane are heated to 120-140 °C, and 2-3 parts by mass of an alkaline catalyst are added. After maintaining the temperature for 6-12 hours, 2-3 parts by mass of phosphoric acid are added to the system for neutralization, followed by cooling and filtration to obtain the first product; S2: 1200-1800 parts by mass of the side-containing hydrogen silicone oil, 300-800 parts by mass of the first product, 224-560 parts by mass of the α-olefin, 1724-3160 parts by mass of the solvent, and 2-4 parts by mass of a 2% platinum catalyst are heated to 70-80 °C under an inert gas environment. The silicone resin modified waterproof material is obtained by heating at ℃ for 6-8 hours.

[0015] This application also provides a waterproof finishing agent, the raw materials of which include: hexadecyltrimethylammonium chloride and fatty alcohol polyoxyethylene ether, as well as the above-mentioned silicone resin modified waterproof material or silicone resin modified waterproof material prepared by the above-mentioned preparation method.

[0016] The waterproof finishing agent is prepared by mixing 100-120 parts by weight of the silicone resin waterproof material, 10-20 parts by weight of the hexadecyltrimethylammonium chloride and 10-20 parts by weight of the fatty alcohol polyoxyethylene ether, adding 100-140 parts by weight of water and 0.2-0.3 parts by weight of Karstedt catalyst for emulsification, thereby obtaining the waterproof finishing agent.

[0017] Compared with the prior art, the beneficial effects of this application are as follows: (1) The silicone resin modified fluorine-free waterproof material prepared in this application, through the synergistic effect of multiple functional groups and secondary cross-linking reaction, not only endows cotton, polyester and other fabrics with high-level waterproof and oil-proof properties, but also significantly reduces the bending stiffness of the fabric, improves the softness and hand feel, effectively solves the technical pain point that the waterproof and oil-proof properties of traditional fluorine-free waterproof agents are difficult to balance with the comfort of the fabric, and at the same time greatly improves the washability and durability of the waterproof and oil-proof effect of the fabric. (2) The silicone resin modified fluorine-free waterproof material prepared in this application significantly reduces the surface energy of the material through the synergistic structure and function of methacryloyloxypropyl, N-cyclohexyl-r-aminopropyl, phenyl and long carbon chain alkyl. Combined with the secondary crosslinking reaction, it forms a dense and continuous three-dimensional network protective film, which not only gives cotton, polyester and other fabrics high-level waterproof and oil-proof performance, but also significantly reduces the bending stiffness of the fabric and improves its softness and hand feel. It completely solves the core technical pain point that traditional fluorine-free waterproof agents cannot achieve both waterproof and oil-proof performance and fabric comfort. At the same time, it greatly improves the washability and durability of the waterproof and oil-proof effect of the fabric. (3) The preparation process of this technology is simple and controllable. Each step is a conventional unit operation in the fields of chemical and textile auxiliaries, without harsh reaction conditions such as high temperature and high pressure. The raw materials used are all readily available industrial products in the industry, without expensive customized raw materials. Moreover, the reaction has no obvious by-products and low material loss, which greatly reduces the production and application costs. At the same time, the production process has low emissions of waste, which meets the requirements of environmentally friendly industrial production. Detailed Implementation

[0018] The present application will be further described below with reference to specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments.

[0019] The terms “comprising” and “having”, and any variations thereof, in the specification and claims of this application are intended to cover non-exclusive inclusion, for example, a process, method, system, product, or device that includes a series of steps or units is not necessarily limited to those steps or units that are explicitly listed, but may include other steps or units that are not explicitly listed or that are inherent to such process, method, product, or device.

[0020] This application provides a silicone resin modified waterproof material, the general structural formula of which is: Where z, a, b, c, d, m, n, e are integers, and 1 ≤ z ≤ 2, 13 ≤ a ≤ 17, 1 ≤ b ≤ 2, 4 ≤ c ≤ 5, 156 ≤ d ≤ 235, 0 <m≤45,0<n≤45,1≤e≤2。

[0021] The silicone resin modified waterproof material of this application introduces a methacryloxypropyl structure into the product structure, which can undergo self-polymerization or cross-linking reaction with the fabric surface, so that the silicone resin modified waterproof material and the fabric fibers form stable chemical bonds, which greatly improves the adhesion of the waterproof finishing agent to the fabric surface, effectively avoids the peeling off of the waterproof coating during washing and friction, significantly improves the wash resistance and durability of the waterproof effect of the fabric, and solves the problem of easy decay of the waterproof effect of existing fluorine-free waterproof agents.

[0022] The organic segment of the methacryloxypropyl group introduces suitable organic functional groups into the polysiloxane backbone. The steric hindrance and polarity of its ester and propyl linkages can regulate the arrangement of polysiloxane molecules on the fabric surface. Combined with the cross-linking effect of carbon-carbon double bonds, this allows the silicone-modified waterproof material to form a continuous, dense, and flexible waterproof film on the fabric surface. The dense film effectively blocks water molecule penetration, enhancing the high-level waterproof effect; while the flexibility of the film synergizes with the flexibility of the polysiloxane backbone, preventing the waterproof coating from becoming too rigid and causing the fabric to feel stiff, thus achieving a balance between waterproof performance and fabric softness.

[0023] The silicone-modified waterproof material of this application also incorporates an N-cyclohexyl-r-aminopropyl structure, which synergistically forms with the phenyl group to reduce the surface energy of the polysiloxane material and enhance its repulsion against water and oil molecules. The alicyclic structure of the cyclohexyl group is more stable than the hydrophobic effect of straight-chain alkyl groups, making it suitable for the waterproof and oil-repellent requirements of different application scenarios and overcoming the shortcomings of traditional fluorine-free waterproofing agents in terms of poor oil-repellent performance.

[0024] Amino groups are inherently highly polar hydrophilic groups. Directly introducing aminopropyl groups into silicone waterproofing materials can easily lead to a significant decrease in the material's waterproofing effect due to the hydrophilicity of the amino group. This is a core technical bottleneck in traditional amino-modified silicone waterproofing materials. In this application, the amino group is linked to a cyclohexyl group. The large-volume alicyclic structure of the cyclohexyl group creates steric hindrance, effectively shielding the hydrophilic active sites of the amino group. This significantly suppresses the hydrophilic effect of the amino group, retaining only its polar binding properties, thus achieving the design goal of avoiding hydrophilic defects. The flexible alicyclic structure of the cyclohexyl group increases the flexibility of the polysiloxane molecule, synergizing with the smooth properties of the polysiloxane backbone, allowing the finished fabric to maintain good softness and hand feel.

[0025] The amino nitrogen atom in N-cyclohexyl-r-aminopropyl carries a lone pair of electrons, exhibiting strong polarity. It can form hydrogen bonds or polar electrostatic interactions with polar groups such as hydroxyl, carboxyl, and ester groups on the surface of cotton, polyester, and other fabric fibers. This results in a stable bond between the silicone-modified waterproofing material and the fabric fibers, exhibiting stronger adhesion compared to the simple physical adsorption of traditional fluorine-free waterproofing agents. This property effectively prevents the waterproof coating from peeling off during washing and friction, improving the wash resistance and durability of the fabric's waterproof and oil-repellent properties.

[0026] The polarity of amino groups allows waterproof material molecules to spread evenly on the surface of fabric fibers, avoiding uneven finishing effects caused by local aggregation and ensuring consistent waterproof and oil-repellent properties throughout the fabric. Simultaneously, the polarity of amino groups also enables waterproof material molecules to form a directional arrangement on the fabric fiber surface, reducing fiber adhesion and entanglement and lowering the fabric's bending stiffness.

[0027] The N-cyclohexyl-r-aminopropyl group forms a complementary synergy in structure and function with groups such as methacryloyloxypropyl, phenyl, and long-chain alkanes: methacryloyloxypropyl provides cross-linking reaction sites for the material, promoting the formation of a dense waterproof film on the fabric surface, while the polar binding effect of the N-cyclohexyl-r-aminopropyl group makes the cross-linking film formation process more uniform, avoiding film cracking and peeling; the phenyl group further enhances the material's oleophobicity and weather resistance, and combined with the low surface energy characteristics of the cyclohexyl group, achieves a dual improvement in waterproof and oil-repellent effects; the hydrophobic alkyl chain of the long-chain alkanes forms a hydrophobic synergy with the cyclohexyl group, enhancing the material's repellency against water and oil. Simultaneously, the introduction of this group does not disrupt the structural stability of the polysiloxane backbone, and during the hydrosilylation reaction, it can be grafted simultaneously with other groups and evenly distributed, ensuring the uniformity of the material structure and allowing the functions of each functional group to be fully utilized, ultimately achieving a comprehensive improvement in the material's waterproof and oil-repellent properties, softness and comfort, and stable adhesion.

[0028] The phenyl and cyclohexyl groups introduced into the product structure of this invention have extremely low surface tension. After grafting modification, the overall surface tension of the silicone resin modified waterproof material can be significantly reduced, far below the surface tension of water molecules and plant oil molecules. Liquids cannot spread and wet the material surface, thereby achieving the effect of water and oil repellency.

[0029] There is a synergistic effect between phenyl and cyclohexyl groups: the aromatic ring conjugated structure of phenyl makes its low surface energy properties more stable, and also improves the chemical stability and weather resistance of the material, preventing the surface tension from increasing due to environmental factors during use; the alicyclic structure of cyclohexyl groups has better flexibility and excellent compatibility with the polysiloxane backbone, ensuring the uniform distribution of low surface energy groups on the fiber surface and avoiding the problem of local failure of waterproof and oil-repellent performance caused by group aggregation. The composite introduction of these two types of cyclic groups, compared with the introduction of phenyl or cyclohexyl groups alone, can further reduce the surface tension of the material, resulting in a synergistic improvement in waterproof and oil-repellent effects, effectively making up for the technical deficiency of traditional fluorine-free waterproof materials that can only achieve basic waterproof and oil-repellent effects.

[0030] The silicone-modified waterproof material of this application retains unreacted olefin and silane groups in its molecular structure. These residual active groups provide reaction sites for secondary crosslinking during subsequent use. In the practical application stage of fabric finishing, after the waterproofing agent emulsion of this invention is attached to the surface of the fabric fibers through a padding process, the subsequent pre-baking process provides sufficient activation energy for the residual olefin and silane groups, triggering a secondary hydrosilylation crosslinking reaction between them.

[0031] This secondary cross-linking reaction is an intermolecular cross-linking polymerization that connects the originally linear or branched silicone resin molecules to form a three-dimensional network of silicone resin polymer film. Compared with linear molecules that have not undergone secondary cross-linking, the film-forming properties of the cross-linked molecular structure on the surface of fabric fibers are significantly improved: on the one hand, a dense, continuous, and pinhole-free uniform protective film can be formed on the fiber surface, avoiding the penetration channels of water and oil molecules caused by discontinuous film layers, thus strengthening the waterproof and oil-proof effect from a physical barrier level; on the other hand, the three-dimensional network film layer forms a multi-point anchoring bond with the fabric fibers, greatly improving the adhesion between the film layer and the fibers, making the protective film less likely to fall off during fabric use or washing, effectively enhancing the wash resistance and durability of the product's waterproof and oil-proof effects.

[0032] This application also provides a method for preparing a silicone resin-modified waterproof material, comprising the following steps: S1: Octamethylcyclotetrasiloxane, N-cyclohexyl-r-aminopropyldimethoxysilane, methacryloyloxypropyldimethylmethoxysilane and methylphenyldimethoxysilane are reacted to prepare the first product; S2: Hydrogen-containing silicone oil, the first product, and α-olefin are reacted in a catalyst and solvent to prepare the silicone resin modified waterproof material of this application.

[0033] In some embodiments, the structural formula of the first product is: Where m, n, e are integers, and 0 <m≤45,0<n≤45,1≤e≤2。

[0034] In step S1, the reaction formulas for octamethylcyclotetrasiloxane, N-cyclohexyl-r-aminopropyldimethoxysilane, methacryloyloxypropyldimethylmethoxysilane, and methylphenyldimethoxysilane can be represented as follows: Where m, n, e are integers, and 0 <m≤45,0<n≤45,1≤e≤2。

[0035] In step S2, the reaction formula for the side-containing silicone oil, the first product, and the α-olefin can be represented as: Where x, y, z, a, b, c, d, m, n, e are integers, and 6 ≤ x ≤ 9, 156 ≤ y ≤ 235, 1 ≤ z ≤ 2, 13 ≤ a ≤ 17, 1 ≤ b ≤ 2, 4 ≤ c ≤ 5, 156 ≤ d ≤ 235, 0 <m≤45,0<n≤45,1≤e≤2。

[0036] This application utilizes the cracking and rearrangement of polysiloxane under alkaline catalyst conditions to introduce structures and groups such as methacryloyloxypropyl, phenyl, and N-cyclohexyl-r-aminopropyl into the polysiloxane structure, and uses a hydrosilylation reaction to react long-chain alkanes and the first product material containing the above groups with hydrogen-containing silicone oil to obtain a silicone resin modified waterproof material.

[0037] In some embodiments, the α-olefin in step S2 is a long-chain olefin with at least 16 carbon atoms in the chain.

[0038] In specific embodiments, the α-olefin is any one or a combination of 1-hexadecene, 1-octadecene, and 1-eicosene.

[0039] In some embodiments, the number average molecular weight of the hydrogen-containing silicone oil in step S2 is 12,000 to 18,000, and the hydrogen content is in the range of 0.033% to 0.075%.

[0040] In some embodiments, the solvent in step S2 can be any one or a combination of more than one of isopropanol, ethylene glycol monobutyl ether, isopentyl glycol, and diethylene glycol monobutyl ether.

[0041] In some embodiments, the platinum catalyst is any one or a combination of chloroplatinic acid, Karstedt catalyst, and Ashby catalyst.

[0042] In some embodiments, this application provides a specific method for preparing a silicone resin-modified waterproof material, wherein the following steps are in parts by weight: S1: Add 2270~3116 parts of octamethylcyclotetrasiloxane, 200~300 parts of N-cyclohexyl-r-aminopropyldimethoxysilane, 400~500 parts of methacryloyloxypropyldimethylmethoxysilane and 154~308 parts of methylphenyldimethoxysilane to a reaction vessel, heat to 120~140 ℃, add 2~3 parts of KOH catalyst, keep at this temperature for 6~12 hours, add 2~3 parts of phosphoric acid to the system for neutralization, cool down and filter to obtain the first product; S2: Add 1200-1800 parts of hydrogen-containing silicone oil, 300-800 parts of the first product, 224-560 parts of long-chain α-olefin, 1724-3160 parts of solvent, and 2-4 parts of platinum catalyst with a mass fraction of 2% to a reaction vessel. Heat to 70-80℃ in an inert gas environment and keep at that temperature for 6-8 hours to obtain silicone resin modified waterproof material.

[0043] This application also provides a fluorine-free waterproofing finishing agent, the raw materials of which include: hexadecyltrimethylammonium chloride, fatty alcohol polyoxyethylene ether, and the above-mentioned silicone resin modified waterproofing material.

[0044] This application also provides a method for preparing a fluorine-free waterproof finishing agent: a silicone resin modified waterproof material, hexadecyltrimethylammonium chloride and fatty alcohol polyoxyethylene ether are emulsified in the presence of a solvent and a catalyst to obtain a fluorine-free waterproof finishing agent.

[0045] In the specific preparation method, 100-120 parts by weight of silicone resin modified waterproof material, 10-20 parts by weight of hexadecyltrimethylammonium chloride and 10-20 parts by weight of fatty alcohol polyoxyethylene ether are mixed, and then 100-140 parts by weight of water and 0.2-0.3 parts by weight of Karstedt catalyst are added for emulsification to obtain the fluorine-free waterproof finishing agent of this application.

[0046] The overall process of the fluorine-free waterproofing finishing agent in this application is simple and without complex steps. Each preparation stage only involves basic operations such as stirring, heating, heat preservation, neutralization, filtration, and emulsification. There is no need to design customized reaction steps or post-processing, resulting in low technical control requirements for operators and significantly reducing the operational difficulty and management costs in the production process. Furthermore, the raw materials used in this technology are all readily available industrial raw materials from the organosilicon and textile auxiliary industries. Core raw materials such as octamethylcyclotetrasiloxane, various silane coupling agents, side-containing hydrogen silicone oil, and long-chain α-olefins do not require customized synthesis, and are widely available and inexpensive in the market. No significant side reactions occur in each step of the reaction, and the material loss rate is low, further reducing raw material costs. The preparation process of this technology is highly compatible with industrial production. The process parameters of each reaction step are within the easily controllable range for industrial applications. It avoids harsh reaction conditions such as high temperature, high pressure, oxygen-free, and anhydrous environments, and can be directly used in existing organosilicon product or textile auxiliary production lines for large-scale production. No modification to existing production equipment is required, resulting in zero equipment modification costs. No toxic or harmful byproducts are generated during the production process, and emissions of waste are low, meeting environmental protection requirements for industrial production and facilitating environmental approval. Furthermore, the waterproofing emulsion prepared by this technology exhibits excellent stability, facilitating industrial storage and transportation. Its application is compatible with the existing padding-pre-baking conventional fabric finishing process in the textile industry, requiring no changes to existing production line operations. It can be directly integrated into the textile enterprise's production system, achieving a seamless transition from laboratory preparation to large-scale industrial production and application. The difficulty of industrialization is low, demonstrating strong industrial promotion value and market application prospects.

[0047] Example 1 To prepare a fluorine-free waterproofing finishing agent, the following steps are performed in parts by weight: S1: 2270 parts of octamethylcyclotetrasiloxane, 245 parts of N-cyclohexyl-r-aminopropyldimethoxysilane, 433 parts of methacryloyloxypropyldimethylmethoxysilane and 154 parts of methylphenyldimethoxysilane were added to a reaction vessel, stirred thoroughly, heated to 130°C, and then 3 parts of KOH catalyst were added. After maintaining the temperature for 8 hours, 3 parts of phosphoric acid were added to the system for neutralization, the temperature was lowered and filtered to obtain the first product. S2: 1200 parts of side-hydrogenated silicone oil with a number average molecular weight of 12000 and a hydrogen content of 0.05%, 300 parts of the first product, 224 parts of 1-hexadecene, 1724 parts of isopropanol, and 3 parts of chloroplatinic acid catalyst with a mass fraction of 2% were added to the reaction vessel, stirred thoroughly, and purged with nitrogen. The temperature was raised to 75°C and kept at that temperature for 8 hours to obtain a silicone resin modified fluorine-free waterproof material. S3: Mix 100 parts of silicone resin modified fluorine-free waterproof material, 10 parts of hexadecyltrimethylammonium chloride and 10 parts of fatty alcohol polyoxyethylene ether, add 120 parts of water for emulsification, and add 0.2~0.3 parts of Karstedt catalyst and continue stirring to react, to obtain the fluorine-free waterproof finishing agent of Example 1.

[0048] Example 2 In step S1, the amount of octamethylcyclotetrasiloxane added was adjusted to 3116 parts by mass, and in step S2, the amount of the first product added was adjusted to 385 parts by mass. At the same time, the amount of isopropanol solvent added was adjusted to 1809 parts by mass. Other preparation steps were consistent with the preparation steps in Example 1, and the fluorine-free waterproof finishing agent of Example 2 was obtained.

[0049] Example 3 In step S2, the amount of the first product added was adjusted to 600 parts by mass, and the amount of the solvent isopropanol added was adjusted to 2024 parts by mass. The other preparation steps were consistent with the preparation steps in Example 1, and the fluorine-free waterproof finishing agent of Example 3 was obtained.

[0050] Example 4 In step S2, the amount of 1-hexadecene added was adjusted to 448 parts by mass, and the amount of solvent isopropanol added was adjusted to 1948 parts by mass. Other preparation steps were consistent with the preparation steps in Example 1, and the fluorine-free waterproof finishing agent of Example 4 was obtained.

[0051] Example 5 In step S2, the side-containing hydrogen silicone oil was replaced with side-containing hydrogen silicone oil with a hydrogen content of 0.075%, and the other preparation steps were kept consistent with the preparation steps in the examples to obtain the fluorine-free waterproof finishing agent of Example 5.

[0052] Example 6 In step S2, the side-containing hydrogen silicone oil was replaced with 1800 parts by mass of side-containing hydrogen silicone oil with a number average molecular weight of 18000. The other preparation steps were the same as those in Example 1, and the fluorine-free waterproof finishing agent of Example 6 was obtained.

[0053] Example 7 In step S2, the α-olefin is selected as 1-eicosene, and the amount added is 280 parts by mass. At the same time, the amount of solvent isopropanol added is adjusted to 1780 parts by mass. The other preparation steps are consistent with the preparation steps in Example 1, and the fluorine-free waterproof finishing agent of Example 7 is obtained.

[0054] Example 8 In step S2, the catalyst was changed to Ashby catalyst, and the amount of solvent isopropanol added was adjusted to 1780 parts by mass. Other preparation steps were consistent with the preparation steps in Example 1, and the fluorine-free waterproof finishing agent of Example 8 was obtained.

[0055] Example 9 In step S2, the solvent was replaced with 1724 parts by mass of ethylene glycol monobutyl ether, and the other preparation steps were consistent with those in Example 1, thus obtaining the fluorine-free waterproof finishing agent of Example 9.

[0056] Example 10 In step S1, the amount of methylphenyldimethoxysilane added was adjusted to 308 parts by mass, and in step S2, the amount of the first product added was adjusted to 315 parts by mass. At the same time, the amount of solvent isopropanol added was adjusted to 1739 parts by mass. Other preparation steps were consistent with the preparation steps in Example 1, and the fluorine-free waterproof finishing agent of Example 10 was obtained.

[0057] Example 11 The side-containing hydrogen silicone oil in step S2 was replaced with 1800 parts by mass of side-containing hydrogen silicone oil with a number average molecular weight of 18000, and the amount of solvent isopropanol added was adjusted to 2339 parts by mass. Other preparation steps were kept consistent with the preparation steps in Example 10, and the fluorine-free waterproof finishing agent of Example 10 was obtained.

[0058] Example 12 In step S2, the side-containing hydrogen silicone oil was replaced with side-containing hydrogen silicone oil with a hydrogen content of 0.075%, and the other preparation steps were kept the same as those in Example 11, to obtain the fluorine-free waterproof finishing agent of Example 12.

[0059] Example 13 The amount of the first product added in step S2 was adjusted to 630 parts by mass, and the amount of solvent isopropanol added was adjusted to 2654 parts by mass. Other preparation steps were kept consistent with the preparation steps in Example 12, and the fluorine-free waterproof finishing agent of Example 13 was obtained.

[0060] Example 14 The amount of 1-hexadecene added in step S2 was adjusted to 448 parts by mass, and the amount of isopropanol added as solvent was adjusted to 2878 parts by mass. Other preparation steps were kept consistent with the preparation steps in Example 13, and the fluorine-free waterproof finishing agent of Example 14 was obtained.

[0061] Example 15 In step S2, the α-olefin is selected as 1-eicosene, and the amount added is 560 parts by mass. At the same time, the amount of solvent isopropanol added is adjusted to 2990 parts by mass. The other preparation steps are consistent with the preparation steps in Example 14, and the fluorine-free waterproof finishing agent of Example 15 is obtained.

[0062] Comparative Example 1 In step S1, N-cyclohexyl-r-aminopropyldimethoxysilane was replaced with 3-aminopropylmethyldimethoxysilane in the same proportion, and the other preparation steps were kept the same as those in Example 15 to obtain the finishing agent of Comparative Example 1.

[0063] Comparative Example 2 In step S1, the methacryloyloxypropyl dimethylmethoxysilane was replaced with a vinyl end-capping agent in the same proportion, and the other preparation steps were kept consistent with the preparation steps in Example 15 to obtain the finishing agent of Comparative Example 2.

[0064] Comparative Example 3 In step S1, no methylphenyldimethoxysilane was added to prepare the first product, and the other preparation steps were the same as those in Example 15, thus obtaining the finishing agent of Comparative Example 3.

[0065] Comparative Example 4 The commercially available fluorine-free waterproofing agent was purchased. Its main component is polyacrylic acid with octadecyl acrylate as the core structure.

[0066] Fabric finishing processes Polyester or cotton woven fabrics were selected for padding with the working solution, with a padding rate of 80%. The working solution was 50 g / L of the fabric finishing agent prepared in the above examples and comparative examples. The fabrics were pre-baked at 180 °C for 45-60 s and then rehydrated for 1 hour before performance evaluation tests were conducted.

[0067] Performance evaluation test The fabrics treated with the finishing agents of Examples 1-15 and Comparative Examples 1-4 were subjected to the following performance evaluation tests. The test results for cotton woven fabrics are summarized in Table 1, and the test results for polyester fabrics are summarized in Table 2. The wash resistance of the fabrics treated with the finishing agents of Examples 15 and Comparative Examples 1-4 were tested, and the test results are summarized in Table 3.

[0068] 1. Water resistance test: According to AATCC 22-2010 "Water repellency: Spray test", the score is 0 for completely wetted fabric surface, 50 for completely wetted fabric surface, 80 for wetted fabric surface with sprayed spots, 90 for fabric surface with sporadic wetted spots, and 100 for no wetted fabric surface.

[0069] 2. Contact Angle Test: Place a drop of water and vegetable oil on the treated fabric, and then test it with a contact angle tester. When the contact angle is >90°, it indicates that the fabric has water and oil repellency; when the contact angle is >150°, it indicates that the fabric has super water and oil repellency.

[0070] 3. Softness Test: According to GB / T18318 "Textiles - Determination of Bending Length of Fabrics", a long strip sample is placed on a platform, with a ruler pressed on the sample. The long axis of the sample is parallel to the length direction of the ruler. The ruler and the long axis of the sample move simultaneously on the platform, causing the portion of the sample extending beyond the platform to be suspended in the air and bend under its own weight. When the downward bending end of the sample touches an inclined plane at a 41.5° angle to the horizontal, half of the extended length of the sample is considered the bending length. The bending stiffness of the sample is calculated by the bending length and the mass per unit area.

[0071] Samples: 6 pieces each of 25 mm * 25 mm warp and weft knitted fabrics, each sample was measured 4 times, and the average value was taken; Bending stiffness calculation: G=mC 3 10 -2 Where: G—bending stiffness per unit width, mN·cm; m—mass per unit area of ​​the specimen, g / m 2 C—average bending length of the specimen, in cm.

[0072] 4. Hand feel evaluation test: The overall hand feel is evaluated by touch, using a 1-5 point rating system, with 1 point being the worst and 5 points being the best. Ten people evaluate at the same time, and the average value is taken.

[0073] 5. Washability and durability test: The finished fabric was washed in accordance with GB / T 8629-2017 "Home washing and drying procedures for textile testing" and the water repellency was tested.

[0074] Table 1. Performance test results of cotton woven fabrics treated with finishing agents in each example and comparative example.

[0075] Table 2. Performance test results of polyester fabrics treated with finishing agents in each example and comparative example.

[0076] Table 3. Test results of the washing performance of fabrics in Example 15 and Comparative Examples 1 to 4

[0077] The fluorine-free waterproofing agent prepared in this application can achieve efficient waterproof and oil-repellent modification of cotton and polyester fabrics. At the same time, it can significantly reduce the bending stiffness of the fabric, improve its softness and hand feel, fundamentally improve the wearing comfort of cotton and polyester fabrics, and achieve a dual improvement in waterproof and oil-repellent performance and comfort.

[0078] Increasing the amount of methylphenyldimethoxysilane and α-long-chain olefins improves the water and oil repellency of the finished fabric, but negatively impacts its wearing comfort. Changing the type of catalyst and solvent has almost no effect on the various performance indicators of the finished fabric. Increasing the number-average molecular weight of α-long-chain olefins and side-hydrogen-containing silicone oil improves the water and oil repellency of the finished fabric, but slightly reduces its wearing comfort. The higher the number-average molecular weight of the prepared methacryloxypropyldimethyl end-capped silicone oil, the better the water and oil repellency of the finished fabric, with less impact on its wearing comfort. Increasing the amount of methacryloxypropyldimethyl end-capped silicone oil improves the water and oil repellency of the finished fabric, but significantly affects its softness and hand feel. Increasing the hydrogen content of hydrogen-containing silicone oil can effectively increase the crosslinking degree of silicone resin-modified fluorine-free waterproofing agent during the setting process, which can improve the water and oil repellency of the finished fabric to a certain extent, and has little impact on the softness and feel of the fabric.

[0079] N-cyclohexyl-r-aminopropyl, methacryloyloxypropyl, and phenyl are the core groups that enable the product to achieve excellent waterproof and oil-repellent effects. The synergistic introduction of these three groups is the fundamental reason why this technology product has excellent waterproof and oil-repellent effects. The absence or replacement of any group will lead to a significant reduction in the waterproof and oil-repellent effects.

[0080] N-cyclohexyl-r-aminopropyl and methacryloxypropyl are the core structures that enable the product to have excellent wash resistance. The presence of N-cyclohexyl-r-aminopropyl allows the product to form a stable bond with the fabric fibers, resulting in a stronger bond compared to the simple physical adsorption of traditional fluorine-free waterproofing agents. The presence of methacryloxypropyl allows it to form a dense, three-dimensional film on the fabric surface, increasing the product's wash resistance and durability, significantly outperforming commercially available products.

[0081] In summary, the silicone resin-modified fluorine-free waterproof material developed in this technology effectively reduces surface energy by precisely introducing functional groups such as methacryloyloxypropyl, N-cyclohexyl-r-aminopropyl, phenyl, and long-chain alkyl groups, utilizing the synergistic effect between these groups. Simultaneously, a secondary crosslinking reaction enhances film-forming properties and adhesion, imparting high-level waterproof and oil-repellent performance to cotton and polyester fabrics while maintaining their softness and hand feel. This solves the core pain point of traditional fluorine-free waterproof agents, which struggle to balance performance and comfort. Its preparation process is simple and controllable, using readily available industrially produced raw materials, requiring no modification to existing equipment, resulting in low production costs and environmental friendliness. It is compatible with conventional finishing processes in the textile industry, making industrialization easy. It can effectively replace fluorine-containing waterproof agents and possesses strong market promotion value and application prospects.

[0082] The basic principles, main features, and advantages of this application have been described above. Those skilled in the art should understand that this application is not limited to the above embodiments. The embodiments and descriptions in the specification are merely the principles of this application. Various changes and modifications can be made to this application without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claims. The scope of protection claimed by this application is defined by the appended claims and their equivalents.

Claims

1. A silicone resin-modified waterproof material, characterized in that, Its general structural formula is: Where z, a, b, c, d, m, n, e are integers, and 1 ≤ z ≤ 2, 13 ≤ a ≤ 17, 1 ≤ b ≤ 2, 4 ≤ c ≤ 5, 156 ≤ d ≤ 235, 0 <m≤45,0<n≤45,1≤e≤2。 2. A method for preparing a silicone resin-modified waterproof material, characterized in that, Includes the following steps: S1: Octamethylcyclotetrasiloxane, N-cyclohexyl-r-aminopropyldimethoxysilane, methacryloyloxypropyldimethylmethoxysilane and methylphenyldimethoxysilane are reacted to prepare the first product; S2: Hydrogen-containing silicone oil, the first product, and α-olefin are reacted in a catalyst and solvent to obtain the silicone resin-modified waterproof material; The structural formula of the first product is: Where m, n, e are integers, and 0 <m≤45,0<n≤45,1≤e≤2, The structural formula of the silicone resin modified waterproof material is: Where z, a, b, c, d, m, n, e are integers, and 1 ≤ z ≤ 2, 13 ≤ a ≤ 17, 1 ≤ b ≤ 2, 4 ≤ c ≤ 5, 156 ≤ d ≤ 235, 0 <m≤45,0<n≤45,1≤e≤2。 3. The preparation method according to claim 2, characterized in that, The α-olefin has a carbon chain with a carbon number of not less than 16.

4. The preparation method according to claim 3, characterized in that, The α-olefin is any one or a combination of 1-hexadecene, 1-octadecene, and 1-eicosene.

5. The preparation method according to claim 2, characterized in that, The number average molecular weight of the hydrogen-containing silicone oil is 12,000 to 18,000.

6. The preparation method according to claim 2, characterized in that, The hydrogen content of the hydrogen-containing silicone oil is 0.033%~0.075%.

7. The preparation method according to claim 2, characterized in that, The solvent is any one or a combination of more of isopropanol, ethylene glycol monobutyl ether, isopentyl glycol, and diethylene glycol monobutyl ether.

8. The preparation method according to claim 2, characterized in that, Includes the following steps: S1: 2270-3116 parts by mass of the octamethylcyclotetrasiloxane, 200-300 parts by mass of the N-cyclohexyl-r-aminopropyldimethoxysilane, 400-500 parts by mass of the methacryloyloxypropyldimethylmethoxysilane, and 154-308 parts by mass of the methylphenyldimethoxysilane are heated to 120-140 °C, and then 2-3 parts by mass of an alkaline catalyst are added. After maintaining the temperature for 6-12 hours, 2-3 parts by mass of phosphoric acid are added to the system for neutralization. The mixture is then cooled and filtered to obtain the first product. S2: The silicone resin modified waterproof material is prepared by heating 1200-1800 parts by mass of the hydrogen-containing silicone oil, 300-800 parts by mass of the first product, 224-560 parts by mass of the α-olefin, 1724-3160 parts by mass of the solvent, and 2-4 parts by mass of a 2% platinum catalyst in an inert gas environment to 70-80 °C and holding at that temperature for 6-8 hours.

9. A waterproof finishing agent, characterized in that, The raw materials include: hexadecyltrimethylammonium chloride and fatty alcohol polyoxyethylene ether, as well as the silicone resin modified waterproof material as described in claim 1 or the silicone resin modified waterproof material prepared by any of the preparation methods described in claims 2 to 8.

10. The method for preparing the waterproof finishing agent as described in claim 9, characterized in that, The waterproof finishing agent is prepared by mixing 100-120 parts by weight of the silicone resin modified waterproof material, 10-20 parts by weight of the hexadecyltrimethylammonium chloride and 10-20 parts by weight of the fatty alcohol polyoxyethylene ether, adding 100-140 parts by weight of water and 0.2-0.3 parts by weight of Karstedt catalyst.

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