High-stability non-fluorine polymer waterproof and oil-proof agent and preparation method thereof

Abstract

The invention discloses a high-stability non-fluorine polymer waterproof and oil-proof agent and a preparation method thereof, and belongs to the technical field of functional finishing of textiles. The waterproof and oil-proof agent is prepared by emulsion polymerization of a long-chain acrylate monomer, a cyclic acrylate monomer, alkylene-containing silane, a chlorine-containing monomer, epoxy-vinyl double-modified silicone oil, nanoparticles, a surfactant, a cosolvent, water and an initiator according to a specific proportion. Epoxy groups in the epoxy-vinyl double-modified silicone oil can neutralize acidic substances generated in the polymerization process, and the storage stability of the emulsion is remarkably improved; meanwhile, vinyl participates in copolymerization, epoxy groups enhance the binding force with the fabric, and the fabric is endowed with excellent waterproof, oil-proof and washable properties by cooperating with silane and nano particles. The product provided by the invention does not contain PFAS, is environment-friendly, and solves the technical problems that the existing fluorine-containing finishing agent is limited in environmental protection and the traditional vinyl chloride / vinylidene chloride emulsion is poor in stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of textile functional finishing technology, in particular to an environmentally friendly high-stability non-fluoropolymer waterproof and oil repellent agent and a preparation method thereof. BACKGROUND

[0002] Waterproof and oil repellent finishing is an important part of textile finishing, and is widely used in fields such as outdoor clothing, tents, luggage cloth, umbrellas, etc. Traditional waterproof and oil repellent agents are mainly divided into two categories: fluorine-containing and fluorine-free. Fluorine-containing finishing agents, especially C8 products based on perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), have been widely used because they impart excellent waterproof and oil repellent properties to textiles. However, due to the persistence, bioaccumulation and potential toxicity of PFOA / PFOS, its production and application have been strictly limited worldwide. As a substitute, C6 fluorine-containing products have improved environmental friendliness, but still belong to perfluoro or polyfluoroalkyl substances (PFAS), and their long-term environmental risks are increasingly concerned, and their use is gradually restricted. Therefore, the development of high-performance waterproof and oil repellent agents that are completely free of fluorine and environmentally friendly has become an urgent need in the industry.

[0003] Fluorine-free waterproof and oil repellent agents are mainly based on polymers of compounds such as acrylates, silicones, waxes, etc. Among them, the polymer emulsion prepared by using vinyl chloride or vinylidene chloride monomers is concerned due to its good barrier property. However, such monomers are prone to decomposition to produce hydrogen chloride during polymerization or storage, resulting in an acidic emulsion system. The acidic environment not only catalyzes the further degradation of the polymer chain, affecting the durability of the final product, but also exacerbates the instability of the emulsion, leading to problems such as demulsification, precipitation, and performance degradation, limiting its practical application.

[0004] Therefore, there are two major defects in the prior art: first, high-performance fluorine-containing waterproof and oil repellent agents face severe environmental regulation restrictions; second, the potential fluorine-free vinyl chloride / vinylidene chloride emulsion has the problems of poor stability and poor acid resistance. SUMMARY

[0005] Technical problems to be solved by the present application The present application aims to overcome the shortcomings of the prior art, and primarily solves the technical problem of the application limitation of existing C6 and C8 fluorine-containing waterproof and oil repellent agents due to environmental problems. Secondly, it solves the problem of poor stability and easy decomposition of existing fluorine-free polymers based on vinyl chloride / vinylidene chloride due to acidic environment.

[0006] Technical scheme of the present application To achieve the above-mentioned purpose, the present application provides a high-stability non-fluoropolymer waterproof and oil repellent agent and a preparation method thereof.

[0007] In a first aspect, the present invention provides a method for preparing a highly stable non-fluoropolymer waterproof and oil-repellent agent, comprising: pre-emulsifying raw materials including long-chain acrylate monomers, cyclic acrylate monomers, olefin-containing silanes, chlorine-containing monomers, epoxy-vinyl dual-modified silicone oil, nanoparticles, surfactants, co-solvents and water, and then carrying out a heat-preserving reaction in the presence of an initiator.

[0008] The epoxy-vinyl dual-modified silicone oil is a key component, which is prepared by a two-step hydrosilylation method: First, the hydrogen-containing silicone oil reacts with glycidyl methacrylate to introduce epoxy groups and retain some silane bonds; then, the remaining silane bonds react with a vinyl-containing compound (such as a vinyl dual-end) to introduce vinyl groups, finally obtaining a dual-modified silicone oil with both epoxy groups and vinyl groups.

[0009] In a preferred embodiment, the raw material composition, by weight, includes: (a) 10-20 parts of long-chain acrylate monomer (preferably 10-15 parts); (b) 3-6 parts of cyclic acrylate monomers (preferably 3-5 parts); (c) Containing 0.5-3 parts of olefin-based silane (preferably 0.5-2.5 parts); (d) 3-6 parts of chlorine-containing monomers; (e) 10-20 parts of epoxy-vinyl dual-modified silicone oil (preferably 10-15 parts); (f) 0.5-2 parts (preferably 0.5-1 parts) of nanoparticles, wherein the nanoparticles are octavinyl POSS or nano-silica modified with oleic acid / cocoacid; (g) 1-5 parts of surfactant (preferably 1-4 parts); (h) 3-6 parts of cosolvent (preferably 3-4 parts); (i) 65-70 parts water; (j) 0.5-5 parts of initiator (preferably 0.5-2 parts); (k) Optional pH adjuster.

[0010] The long-chain acrylate monomer is an acrylate or methacrylate with more than 14 carbon atoms; the cyclic acrylate monomer is at least one of isobornyl methacrylate and cyclohexyl methacrylate; the chlorine-containing monomer is vinyl chloride and / or vinylidene chloride; the nanoparticles are octavinyl cage-type silsesquioxane or nano-silica modified with oleic acid / cocoacid.

[0011] In the epoxy-vinyl dual-modified silicone oil, the initial hydrogen content of the hydrogen-containing silicone oil is 0.98%-1.6%, and the vinyl-containing compound is a vinyl dual-capping agent.

[0012] The amount of the vinyl-containing compound used is in excess relative to the remaining silane bonds in the epoxy silicone oil.

[0013] Secondly, the present invention provides a highly stable non-fluoropolymer waterproof and oil-repellent agent prepared by the above method.

[0014] Thirdly, the present invention provides the application of the above-mentioned waterproof and oil-repellent agent in textile finishing.

[0015] Fourthly, the present invention provides a textile whose surface is treated with the aforementioned waterproof and oil-repellent agent.

[0016] Beneficial effects of the present invention This invention does not use any fluorinated monomers, thus avoiding the introduction of PFAS-related substances at the source. The product is environmentally friendly and safe, and complies with the increasingly stringent global environmental regulations.

[0017] The innovatively introduced epoxy-vinyl dual-modified silicone oil has epoxy groups in its molecules that can effectively neutralize acidic substances such as hydrogen chloride produced by the decomposition of chlorine-containing monomers during emulsion polymerization and storage, maintaining the system in a relatively stable pH environment. This significantly inhibits the acidic degradation of polymer chains and greatly improves the chemical and storage stability of the emulsion.

[0018] In epoxy-vinyl dual-modified silicone oil, the vinyl groups participate in emulsion copolymerization, which anchors them firmly to the polymer backbone through chemical bonds. The epoxy groups can form stronger bonds by high-temperature baking after finishing or by reacting with groups on the fabric surface, which greatly enhances the bonding force between the finishing agent and the fabric, thus giving it excellent wash resistance.

[0019] The siloxane segments and long-chain acrylates together provide low surface energy, while nanoparticles (POSS or modified silica) construct a micro-rough structure on the fabric surface, synergistically improving waterproof and oil-repellent properties through the "lotus effect".

[0020] Olefin-containing silanes serve as crosslinking points, and modified groups on the surface of nanoparticles participate in the reaction, both enhancing the density of the entire coating network and its bonding strength with the fabric.

[0021] The additive of this invention (epoxy-vinyl dual-modified silicone oil) simultaneously solves the problems of stability, durability and functionality, and simplifies the formulation and production process. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments and comparative examples. The following embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified, the raw materials used in the embodiments are commercially available.

[0023] The performance testing method in this embodiment is as follows: Water resistance: Spray test according to AATCC 22 standard, rated from 1 to 5 (5 is the best).

[0024] Oil resistance: Record the time (in seconds) it takes for a specified edible oil droplet (peanut oil, olive oil, chili oil, corn oil) to begin to wet or wick onto the cloth surface.

[0025] Storage stability: The emulsion with a solid content of approximately 30 wt% was stored in a constant temperature incubator at 40°C for 3 months, and the precipitation was observed. ○: No precipitation; △: Small amount of precipitation; ×: Large amount of precipitation.

[0026] Wash life: Perform household washing according to AATCC 135 standard and record the number of washes before the water or oil resistance significantly decreases.

[0027] Example 1: Preparation of epoxy-vinyl dual-modified silicone oil A and its waterproof and oil-repellent agent Preparation of epoxy-vinyl dual-modified silicone oil A: (a) Under nitrogen protection, 50 g of hydrogen-containing silicone oil (0.98-1.0% hydrogen content), 100 g of toluene, and 15 g of glycidyl methacrylate (GMA) were added to a reaction flask, and the temperature was raised to 80 °C. A platinum catalyst solution (3 wt% Pt) was slowly added dropwise, and the reaction was maintained for 6 hours. After cooling, the catalyst was removed by adsorption with activated carbon, and then toluene and excess GMA were removed by vacuum distillation to obtain an epoxy-based silicone oil intermediate with an epoxy equivalent of approximately 0.75.

[0028] (b) The above intermediate, 50 g of toluene, and 5% excess vinyl bicapsulated resin relative to the remaining Si-H bond molar amount were added to a reaction flask. Under nitrogen protection, a platinum catalyst was added, and the reaction was carried out at 80 °C for 5 hours until the Si-H infrared characteristic peaks essentially disappeared. After activated carbon treatment and vacuum distillation, epoxy-vinyl bicapsulated silicone oil A was obtained.

[0029] Preparation of non-fluoropolymer water and oil repellent agents: In an emulsifying vessel, 36.9 g of octadecyl acrylate (C18 long-chain monomer), 1.2 g of isobornyl methacrylate (cyclic monomer), 1.5 g of vinyltriethoxysilane, 1.2 g of oleic acid-modified nano-silica, 4 g of the epoxy-vinyl dual-modified silicone oil A prepared above, 14.4 g of vinyl chloride, 4.2 g of cationic surfactant octadecyltrimethylammonium chloride, 9 g of cosolvent tripropylene glycol, and 140 g of distilled water were added sequentially. High-speed shear emulsification was performed for 30 minutes to form a stable pre-emulsion.

[0030] The pre-emulsion was transferred to a polymerization reactor, purged with nitrogen, and heated to 70°C. An aqueous solution of initiator azobisisobutylamidine hydrochloride (V-50) (containing 1.2 g of V-50) was then added dropwise at a uniform rate. After the addition was complete, the mixture was kept at 70-75°C with stirring for 6 hours. The mixture was cooled, and the pH was adjusted to 6-7 with a small amount of ammonia. The mixture was then filtered to obtain a white emulsion with a solid content of approximately 30%, designated as sample E1.

[0031] Example 2: Preparation of epoxy-vinyl dual-modified silicone oil B and its waterproof and oil-repellent agent Preparation of epoxy-vinyl dual-modified silicone oil B: The steps are the same as in Example 1, except that the hydrogen content of the starting hydrogen-containing silicone oil is 1.5-1.6%, and the amount of GMA used in step (a) is increased accordingly, resulting in an intermediate with an epoxy equivalent of approximately 1.35. Subsequent step (b) is the same, to obtain epoxy-vinyl dual-modified silicone oil B.

[0032] Preparation of non-fluoropolymer waterproof and oil-repellent agent: The formulation and steps are the same as in Example 1, except that epoxy-vinyl dual-modified silicone oil A is replaced with an equal amount of epoxy-vinyl dual-modified silicone oil B. The resulting emulsion is designated as sample E2.

[0033] Comparative Example 1: Epoxy-vinyl dual-modified silicone oil The preparation steps were exactly the same as in Example 1, but epoxy-vinyl dual-modified silicone oil A was not added, and an equal amount of octadecyl acrylate was added to maintain a basically consistent total solids content. The resulting emulsion was designated as sample C1.

[0034] Comparative Example 2: Contains ordinary epoxy silicone oil (vinyl-free) The preparation steps were basically the same as in Example 1, except that the epoxy-vinyl dual-modified silicone oil A was replaced with an equal amount of ordinary epoxy silicone oil (obtained by complete addition of hydrogen-containing silicone oil and GMA, without vinyl groups). The resulting emulsion was designated as sample C2.

[0035] Comparative Example 3: Contains ordinary vinyl silicone oil (without epoxy groups) The preparation steps were basically the same as in Example 1, except that the epoxy-vinyl dual-modified silicone oil A was replaced with an equal amount of vinyl silicone oil (obtained by reacting hydrogen-containing silicone oil with allyl glycidyl ether and then reacting it with vinyl dual-heading to obtain a vinyl-only silicone oil). The resulting emulsion was designated as sample C3.

[0036] Application examples and performance tests The waterproof and oil-repellent emulsions obtained in Examples 1-2 and Comparative Examples 1-3 were diluted with water to a working solution concentration of 30 g / L. Spring spun, taslon, and nylon fabrics were respectively immersed in the working solution (two dips and two nips, with a liquid retention rate of approximately 70%), and then shaped and dried at 150°C for 2 minutes.

[0037] Various performance tests were conducted on the finished fabric, and the results are summarized in the table below.

[0038] Table 1: Performance test results of finished fabrics for each sample

[0039] Results analysis: 1. Stability Comparison: The emulsions E1 and E2 of this invention exhibit excellent storage stability (○), while Comparative Example C1 (without functional silicone oil) shows a small amount of precipitation (△), and Comparative Example C3 (containing only vinyl silicone oil) shows extremely poor stability (×). This indicates that epoxy groups are crucial for neutralizing acidity and maintaining emulsion stability, and the dual-modified silicone oil of this invention possesses both stabilizing and reactive functions.

[0040] 2. Performance Comparison: The examples demonstrate superior performance compared to all comparative examples in terms of water and oil resistance (especially against low surface tension oils such as corn oil) and wash resistance. Comparative Example C1 exhibits the worst performance, confirming the synergistic contribution of the core components of this invention (epoxy-vinyl dual-modified silicone oil and nanoparticles). Comparative Example C2 (epoxy groups only) shows good stability, but its wash resistance and oil resistance are inferior to the examples, indicating that vinyl participation in copolymerization is crucial for improving durability. Comparative Example C3 (vinyl groups only) demonstrates poor performance and wash resistance, as well as deteriorated stability, conversely proving the irreplaceable role of epoxy groups.

[0041] 3. Overall Conclusion: This invention cleverly solves the problem of balancing stability and durability in fluorine-free systems by using epoxy-vinyl dual-modified silicone oil with a specific structure, while achieving excellent waterproof and oil-repellent properties.

Claims

1. A method for preparing a highly stable non-fluoropolymer waterproof and oil-repellent agent, characterized in that, Includes the following steps: The raw materials, including long-chain acrylate monomers, cyclic acrylate monomers, olefin-containing silanes, chlorinated monomers, epoxy-vinyl dual-modified silicone oil, nanoparticles, surfactants, cosolvents, and water, are pre-emulsified and then subjected to a heat-insulating reaction in the presence of an initiator to obtain the non-fluoropolymer waterproof and oil-repellent agent.

2. The preparation method according to claim 1, characterized in that, The epoxy-vinyl dual-modified silicone oil is prepared by the following steps: (a) Hydrogen-containing silicone oil and glycidyl methacrylate were subjected to a hydrosilylation reaction in the presence of a platinum catalyst to obtain an epoxy-based silicone oil containing remaining silane bonds; (b) The epoxy-based silicone oil obtained in step (a) is subjected to a hydrosilylation reaction with a vinyl-containing compound under the action of a platinum catalyst until the silane-hydrogen bond is basically eliminated, to obtain the epoxy-vinyl dual-modified silicone oil.

3. The preparation method according to claim 1, characterized in that, The raw materials for preparing the waterproof and oil-repellent agent, by weight, include: (a) 10-20 parts of long-chain acrylate monomers; (b) 3-6 parts of cyclic acrylate monomers; (c) Contains 0.5-3 parts of olefin-based silane; (d) 3-6 parts of chlorine-containing monomers; (e) 10-20 parts of epoxy-vinyl dual-modified silicone oil; (f) 0.5-2 parts of nanoparticles; (g) 1-5 parts surfactant; (h) 3-6 parts of cosolvent; (i) 65-70 parts water; (j) 0.5-5 parts of initiator.

4. The preparation method according to claim 3, characterized in that, The long-chain acrylate monomer is an acrylate or methacrylate with more than 14 carbon atoms; the cyclic acrylate monomer is at least one of isobornyl methacrylate and cyclohexyl methacrylate; the chlorine-containing monomer is vinyl chloride and / or vinylidene chloride; the nanoparticles are octavinyl cage-type silsesquioxane or nano-silica modified with oleic acid / cocoacid.

5. The preparation method according to claim 1, characterized in that, In the epoxy-vinyl dual-modified silicone oil, the initial hydrogen content of the hydrogen-containing silicone oil is 0.98%-1.6%, and the vinyl-containing compound is a vinyl dual-capping agent.

6. The preparation method according to claim 1 or 2, characterized in that, In step (b), the amount of the vinyl-containing compound used is in excess relative to the remaining silane bonds in the epoxy silicone oil.

7. A highly stable non-fluoropolymer waterproof and oil-repellent agent prepared by the preparation method according to any one of claims 1-6.

8. The application of the high-stability non-fluoropolymer waterproof and oil-repellent agent according to claim 7 in the waterproof and oil-repellent finishing of textiles.

9. A textile product, characterized in that, Its surface is treated with the high-stability non-fluoropolymer waterproof and oil-repellent agent as described in claim 7.

10. The textile according to claim 9, characterized in that, The textiles are made of spring spun, taslon, nylon or pure cotton.

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