Fluorine-free waterproof and oil-proof agent for fabric and preparation method thereof

Abstract

The invention belongs to the technical field of textile chemicals, and discloses a fluoride-free waterproof and oil-proof agent for fabrics and a preparation method thereof. The fluorine-free waterproof and oil-proof agent is prepared from the following raw material components: an emulsifier, a basic monomer, a functional monomer and an initiator, the basic monomer comprises octadecyl methacrylate and / or butyl methacrylate, and the functional monomer comprises adamantyl methacrylate and triisopropyl methacrylic acid estersil. Specific functional monomers including methacrylic acid adamantyl ester and triisopropyl methacrylic acid silicone ester are introduced, so that the oil-proof performance of the fabric can be effectively improved, the waterproof and oil-proof grades can reach grade 4, and the contact angle is greater than or equal to 120 degrees; after the fabric is washed for 50 times, the waterproof grade and the oil-proof grade can still be kept at the level 3 or above; and the stable storage period under the accelerated test condition of 50 DEG C is more than 6 months.

Description

Technical Field

[0001] This invention belongs to the field of textile chemicals technology, specifically relating to a fluorine-free waterproof and oil-repellent agent for fabrics and its preparation method. Background Technology

[0002] In the field of fabric finishing, water and oil repellency is a key indicator for enhancing product added value. Traditional water and oil repellent agents mainly rely on fluorinated monomers, such as perfluoroalkyl acrylate compounds, which achieve excellent water and oil repellency through the low surface energy characteristics of fluorocarbon chains. However, these fluorinated compounds have environmental persistence, bioaccumulation, and potential toxicity, and their use has been restricted or banned by environmental regulations in many countries, including the EU REACH regulation and the US EPA.

[0003] The development of fluorine-free waterproof and oil-repellent agents has become an inevitable trend in the industry's transformation. Currently, fluorine-free systems are mainly based on long-chain alkyl acrylate monomers, such as octadecyl methacrylate and butyl methacrylate. These monomers can impart a certain degree of waterproofing to fabrics through the hydrophobic effect of long-chain alkyl groups; however, due to their relatively high surface energy, their oil-repellent performance is generally poor when used alone, typically only reaching level 1-2 (according to AATCC 118 standard), which is insufficient to meet the oil-repellent requirements of high-end textiles.

[0004] Therefore, there is an urgent need to develop a fluorine-free waterproof and oil-repellent agent that can simultaneously possess excellent waterproof and oil-repellent properties while being environmentally friendly and safe. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a fluorine-free waterproof and oil-repellent agent for fabrics and its preparation method. The fluorine-free waterproof and oil-repellent agent simultaneously possesses excellent waterproof and oil-repellent properties, good wash resistance, is environmentally friendly and safe, and the process is stable and controllable.

[0006] To solve the above-mentioned technical problems, the first aspect of the present invention provides a fluorine-free waterproof and oil-repellent agent, the raw material components of which include an emulsifier, a basic monomer, a functional monomer and an initiator, wherein the basic monomer includes octadecyl methacrylate and / or butyl methacrylate, and the functional monomer includes adamantane methacrylate and triisopropylsilyl methacrylate.

[0007] Specifically, this invention uses octadecyl methacrylate and / or butyl methacrylate, long-chain alkyl acrylate monomers, as base monomers. The long-chain alkyl groups in these monomers form a hydrophobic layer on the fabric surface, hindering water molecule penetration and providing basic waterproofing. To enhance the oil-repellent properties of the base monomers, this invention introduces the composite functional monomers adamantane methacrylate and triisopropyl methacrylate. Specifically, adamantane methacrylate possesses a unique adamantane ring structure, which generates a steric hindrance effect, reducing the polymer's surface energy and enhancing intermolecular forces, thereby improving the fabric's resistance to oils. Triisopropyl methacrylate contains siloxane segments, exhibiting low surface energy and good surface migration, forming a uniform low-energy layer on the fabric surface, similarly contributing to improved resistance to oils. Furthermore, when adamantane methacrylate and triisopropyl methacrylate are used together, the siloxane segments fill the gaps between the adamantane rings, optimizing surface energy distribution. The synergistic effect of both further enhances the fabric's oil-repellent properties.

[0008] In some embodiments of the present invention, the mass ratio of adamantane methacrylate to triisopropylsilyl methacrylate is 1:(2-3).

[0009] In some embodiments of the present invention, the emulsifier includes sulfonate surfactants and fatty alcohol polyoxyethylene ethers.

[0010] In some embodiments of the present invention, the sulfonate surfactant is selected from at least one of sodium dodecylbenzenesulfonate, sodium α-alkenylsulfonate, and sodium fatty acid methyl ester sulfonate; preferably sodium dodecylbenzenesulfonate.

[0011] In some embodiments of the present invention, the fatty alcohol polyoxyethylene ether is selected from at least one of fatty alcohol polyoxyethylene ether-7 (AOE-7) and fatty alcohol polyoxyethylene ether-9 (AOE-9); preferably AOE-7.

[0012] In some embodiments of the present invention, the initiator is selected from inorganic peroxide initiators, such as potassium perthioester, sodium persulfate, etc.

[0013] In some embodiments of the present invention, the raw material components include, by weight: 1-7 parts emulsifier, 5-27 parts base monomer, 2-10 parts adamantyl methacrylate, 4-30 parts triisopropylsilyl methacrylate, and 0.1-0.5 parts initiator.

[0014] In some embodiments of the present invention, the raw material components include, by weight: 1-7 parts emulsifier, 15-25 parts base monomer, 2.5-9.2 parts adamantyl methacrylate, 9.2-18.3 parts triisopropyl methacrylate, and 0.1-0.3 parts initiator.

[0015] In some embodiments of the present invention, the raw material components further include at least one of crosslinking monomers and pH adjusters.

[0016] In some embodiments of the present invention, the crosslinking monomer includes hydroxymethylacrylamide, and the amount used is 1-5 parts by weight; preferably 1-3 parts by weight. Adding a certain amount of hydroxymethylacrylamide is beneficial to improving the wash resistance of the fabric.

[0017] In some embodiments of the present invention, the pH adjuster includes ammonium persulfate.

[0018] A second aspect of the present invention provides a method for preparing the above-mentioned fluorine-free waterproof and oil-repellent agent, comprising the following steps:

[0019] (1) Dissolve the emulsifier to prepare an emulsion; then divide the emulsion into two parts, add the basic monomer and the functional monomer to each part respectively, and perform pre-emulsification to obtain pre-emulsified liquid A and pre-emulsified liquid B;

[0020] (2) Initiator was added to the preemulsion A and preemulsion B respectively, mixed, and pH value was adjusted to obtain emulsion A and emulsion B;

[0021] (3) The emulsion A is heated to perform prepolymerization to obtain prepolymer A;

[0022] (4) Add emulsion B dropwise to the prepolymer A to carry out a polymerization reaction and obtain the fluorine-free waterproof and oil-repellent agent.

[0023] Specifically, the fluorine-free waterproof and oil-repellent agent of the present invention is prepared using an emulsification-polymerization process. First, the base monomer and functional monomer are pre-emulsified separately to obtain pre-emulsion A and pre-emulsion B. Then, an initiator is added to pre-emulsion A, the pH value is adjusted, and the mixture is heated to undergo preliminary polymerization to form polymer chains with a certain structure, yielding prepolymer A. Next, functional monomer emulsion B is added dropwise to prepolymer A to continue the reaction. This stepwise preparation process facilitates the uniform copolymerization of monomers. Compared to traditional one-time polymerization methods, it allows each monomer to participate fully and uniformly in the polymerization, thereby effectively improving product stability, reducing performance fluctuations, and ultimately enhancing the overall performance of the product.

[0024] In some embodiments of the present invention, in step (1), the preparation process of the emulsion is as follows: dissolve the emulsifier in deionized water and stir at a speed of 200-300 rpm until completely dissolved to obtain the emulsion.

[0025] In some embodiments of the present invention, in step (1), the pre-emulsification process conditions are: stirring at 200-300 rpm for 20-40 minutes at a temperature of 60-80°C.

[0026] In some embodiments of the present invention, step (1) further includes adding a crosslinking monomer when preparing the preemulsion B.

[0027] In some embodiments of the present invention, in step (2), the pH value is adjusted to 7.2-7.8, for example, 7.2, 7.3, 7.4, 7.5, 7.6, 7.8, etc. A suitable pH value can ensure the activity of the initiator and the stability of the polymerization reaction.

[0028] In some embodiments of the present invention, in step (3), the prepolymerization process conditions are: stirring at 200-300 rpm for 1.5-2.5 hours at a temperature of 78-80°C.

[0029] In some embodiments of the present invention, in step (4), the dropping rate is 1-2 mL / min.

[0030] In some embodiments of the present invention, in step (4), the polymerization reaction takes 1.5-2.5 hours.

[0031] A third aspect of the present invention provides a fabric in which the raw materials for preparing the fabric include the above-mentioned fluorine-free waterproof and oil-repellent agent, or include the fluorine-free waterproof and oil-repellent agent prepared by the above-mentioned preparation method.

[0032] Compared with the prior art, the above-described technical solution of the present invention has at least the following technical effects or advantages:

[0033] (1) The fluorine-free waterproof and oil-repellent agent of the present invention uses octadecyl methacrylate and / or butyl methacrylate as the base monomers. The long-chain alkyl groups in the molecules form a hydrophobic layer on the fabric surface, which hinders the penetration of water molecules through hydrophobic interaction, thus providing basic waterproof performance for the fabric. At the same time, functional monomers adamantane methacrylate and triisopropyl methacrylate are introduced. On the one hand, adamantane methacrylate has a unique adamantane ring structure, which generates a steric hindrance effect, reduces the surface energy of the polymer, and enhances the intermolecular forces. On the other hand, the siloxane segments in triisopropyl methacrylate have low surface energy and good surface migration, forming a uniform low-energy layer on the fabric surface. Moreover, the siloxane segments can fill the gaps between the adamantane rings, optimize the surface energy distribution, and the combined effect of all these factors effectively improves the oil-repellent performance of the fabric.

[0034] (2) In the preparation of the fluorine-free waterproof and oil-repellent agent of the present invention, an emulsification-polymerization process is adopted. The basic monomer is first pre-emulsified, heated, and then initially polymerized to form a polymer chain with a certain structure. Then, the functional monomer pre-emulsion is slowly added dropwise to continue the reaction, so as to achieve uniform copolymerization of the monomer. Compared with the traditional method of adding monomers at one time for polymerization, it can effectively improve the stability of the product, reduce performance fluctuations, and thus improve the overall performance of the product.

[0035] (3) The fluorine-free waterproof and oil-repellent agent prepared by this invention has both good waterproof and oil-repellent properties, wash resistance, and storage stability. It is completely free of fluorine and has no toxic or harmful residues, complying with domestic and international environmental regulations and textile product safety standards. It achieves a waterproof and oil-repellent rating of 4, with a contact angle ≥120°. After 50 washes, the waterproof and oil-repellent ratings of the fabric remain at 3 or higher. Under accelerated testing at 50°C, the stable storage period is >6 months. Detailed Implementation

[0036] The present invention will now be described in detail with reference to embodiments to facilitate understanding of the invention by those skilled in the art. It is particularly important to note that the embodiments are merely illustrative of the invention and should not be construed as limiting the scope of protection of the invention. Non-essential improvements and adjustments made to the invention by those skilled in the art based on the above description should still fall within the scope of protection of the invention. Furthermore, all raw materials mentioned below, unless otherwise specified, are commercially available products; all process steps or preparation methods not mentioned in detail are process steps or preparation methods known to those skilled in the art.

[0037] Example 1

[0038] A method for preparing a fluorine-free waterproof and oil-repellent agent includes the following steps:

[0039] (1) Dissolve 2.5g sodium dodecylbenzenesulfonate and 1.0g AEO-7 in 100mL deionized water and stir at a stirring rate of 200-300rpm until completely dissolved to obtain an emulsion.

[0040] (2) Take 67 mL of emulsion, add 22 g of butyl methacrylate, and stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion A;

[0041] (3) Take 33 mL of emulsion, add 5 g adamantane methacrylate, 15 g triisopropyl methacrylate and 2.2 g hydroxymethyl acrylamide, stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion B.

[0042] (4) Dissolve 0.15g of ammonium persulfate in 16g of deionized water to prepare an initiator solution; dissolve 0.17g of ammonium persulfate in 16g of deionized water to prepare a pH adjustment solution;

[0043] (5) Divide the initiator solution into two equal parts and add them to preemulsion A and preemulsion B respectively. Add pH adjustment solution to adjust the pH value to 7.5 to obtain emulsion A and emulsion B.

[0044] (6) Heat emulsion A to 78-80℃ and carry out a prepolymerization reaction for 2 hours to obtain prepolymer A;

[0045] (7) Add pre-emulsion B dropwise to prepolymer A at a rate of 1.5 mL / min. After the addition is complete, continue the polymerization reaction for 2 hours and cool to room temperature to obtain the fluorine-free waterproof and oil-repellent agent of this embodiment.

[0046] Example 2

[0047] A method for preparing a fluorine-free waterproof and oil-repellent agent includes the following steps:

[0048] (1) Dissolve 2.5g sodium dodecylbenzenesulfonate and 1.0g AEO-7 in 100mL deionized water and stir at a stirring rate of 200-300rpm until completely dissolved to obtain an emulsion.

[0049] (2) Take 67 mL of emulsion, add 20 g of octadecyl methacrylate, and stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion A.

[0050] (3) Take 33 mL of emulsion, add 6 g of adamantane methacrylate, 12 g of triisopropyl methacrylate and 2.2 g of hydroxymethyl acrylamide, and stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion B.

[0051] (4) Dissolve 0.15g of ammonium persulfate in 16g of deionized water to prepare an initiator solution; dissolve 0.17g of ammonium persulfate in 16g of deionized water to prepare a pH adjustment solution;

[0052] (5) Divide the initiator solution into two equal parts and add them to preemulsion A and preemulsion B respectively. Add pH adjustment solution to adjust the pH value to 7.5 to obtain emulsion A and emulsion B.

[0053] (6) Heat emulsion A to 78-80℃ and carry out a prepolymerization reaction for 2 hours to obtain prepolymer A;

[0054] (7) Add pre-emulsion B dropwise to prepolymer A at a rate of 1.5 mL / min. After the addition is complete, continue the polymerization reaction for 2 hours and cool to room temperature to obtain the fluorine-free waterproof and oil-repellent agent of this embodiment.

[0055] Example 3

[0056] A method for preparing a fluorine-free waterproof and oil-repellent agent includes the following steps:

[0057] (1) Dissolve 2.5g sodium dodecylbenzenesulfonate and 1.0g AEO-7 in 100mL deionized water and stir at a stirring rate of 200-300rpm until completely dissolved to obtain an emulsion.

[0058] (2) Take 67 mL of emulsion, add 10 g of octadecyl methacrylate and 10 g of butyl methacrylate, and stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion A.

[0059] (3) Take 33 mL of emulsion, add 6 g adamantane methacrylate, 15 g triisopropyl methacrylate and 2.2 g hydroxymethyl acrylamide, stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion B.

[0060] (4) Dissolve 0.15g of ammonium persulfate in 16g of deionized water to prepare an initiator solution; dissolve 0.17g of ammonium persulfate in 16g of deionized water to prepare a pH adjustment solution;

[0061] (5) Divide the initiator solution into two equal parts and add them to preemulsion A and preemulsion B respectively. Add pH adjustment solution to adjust the pH value to 7.5 to obtain emulsion A and emulsion B.

[0062] (6) Heat emulsion A to 78-80℃ and carry out a prepolymerization reaction for 2 hours to obtain prepolymer A;

[0063] (7) Add pre-emulsion B dropwise to prepolymer A at a rate of 1.5 mL / min. After the addition is complete, continue the polymerization reaction for 2 hours and cool to room temperature to obtain the fluorine-free waterproof and oil-repellent agent of this embodiment.

[0064] Comparative Example 1

[0065] The difference between the preparation method of the fluorine-free waterproof and oil-repellent agent in Comparative Example 1 and Example 1 is that in step (3), only adamantane methacrylate is added as a functional monomer, and triisopropylsilyl methacrylate is not added.

[0066] Step (3) of Comparative Example 1 is as follows: Take 33 mL of emulsion, add 20 g of adamantane methacrylate and 2.2 g of hydroxymethylacrylamide, and stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion B.

[0067] Comparative Example 2

[0068] The difference between the preparation method of the fluorine-free waterproof and oil-repellent agent in Comparative Example 2 and Example 1 is that in step (3), only triisopropylsilyl methacrylate is added as a functional monomer, and adamantane methacrylate is not added.

[0069] Step (3) of Comparative Example 1 is as follows: Take 33 mL of emulsion, add 20 g of triisopropyl methacrylate and 2.2 g of hydroxymethyl acrylamide, and stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion B.

[0070] Comparative Example 3

[0071] The preparation method of the fluorine-free water and oil repellent agent in Comparative Example 3 differs from that in Example 1 in that no functional monomer is added, and its preparation method includes the following steps:

[0072] (1) Dissolve 2.5g sodium dodecylbenzenesulfonate and 1.0g AEO-7 in 100mL deionized water and stir at a stirring rate of 200-300rpm until completely dissolved to obtain an emulsion.

[0073] (2) Take 67 mL of emulsion, add 27 g of butyl methacrylate, and stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion A;

[0074] (3) Dissolve 0.15g of ammonium persulfate in 16g of deionized water to prepare an initiator solution; dissolve 0.17g of ammonium persulfate in 16g of deionized water to prepare a pH adjustment solution;

[0075] (4) Add the initiator solution to the pre-emulsion A, and then add the pH adjustment solution to adjust the pH value to 7.5 to obtain the emulsion A;

[0076] (5) Heat emulsion A to 78-80℃ and carry out a prepolymerization reaction for 2 hours to obtain the fluorine-free waterproof and oil-repellent agent of this comparative example.

[0077] Comparative Example 4

[0078] The preparation method of the fluorine-free water and oil repellent agent in Comparative Example 4 differs from that in Example 2 in that no functional monomer is added, and its preparation method includes the following steps:

[0079] (1) Dissolve 2.5g sodium dodecylbenzenesulfonate and 1.0g AEO-7 in 100mL deionized water and stir at a stirring rate of 200-300rpm until completely dissolved to obtain an emulsion.

[0080] (2) Take 67 mL of emulsion, add 27 g of octadecyl methacrylate, and stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion A;

[0081] (3) Dissolve 0.15g of ammonium persulfate in 16g of deionized water to prepare an initiator solution; dissolve 0.17g of ammonium persulfate in 16g of deionized water to prepare a pH adjustment solution;

[0082] (4) Add the initiator solution to the pre-emulsion A, and then add the pH adjustment solution to adjust the pH value to 7.5 to obtain the emulsion A;

[0083] (5) Heat emulsion A to 78-80℃ and carry out a prepolymerization reaction for 2 hours to obtain the fluorine-free waterproof and oil-repellent agent of this comparative example.

[0084] Comparative Example 5

[0085] The difference between the preparation method of the waterproof and oil-repellent agent in Comparative Example 5 and Example 1 is that in step (3), the functional monomer is replaced by the fluorinated monomer tridecylfluorooctyl acrylate instead of adamantyl methacrylate.

[0086] Step (3) of Comparative Example 5 is as follows: Take 33 mL of emulsion, add 5 g of tridecyl fluorooctyl acrylate, 15 g of triisopropyl methacrylate and 2.2 g of hydroxymethyl acrylamide, and stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion B.

[0087] Comparative Example 6

[0088] The difference between the preparation method of the waterproof and oil-repellent agent in Comparative Example 6 and Example 1 is that in step (3), the functional monomer is replaced by the fluorinated monomer perfluoropolyether methacrylate instead of triisopropylsilyl methacrylate.

[0089] Step (3) of Comparative Example 6 is as follows: Take 33 mL of emulsion, add 5 g adamantane methacrylate, 15 g perfluoropolyether methacrylate and 2.2 g hydroxymethylacrylamide, and stir at 70 °C and 250 rpm for 30 min to obtain pre-emulsion B.

[0090] Comparative Example 7

[0091] The preparation method of the fluorine-free water and oil repellent agent in Comparative Example 7 differs from that in Example 1 in that it employs a traditional one-step polymerization process, and its preparation method includes the following steps:

[0092] (1) Dissolve 2.5g sodium dodecylbenzenesulfonate and 1.0g AEO-7 in 100mL deionized water and stir at a stirring rate of 200-300rpm until completely dissolved to obtain an emulsion.

[0093] (2) Add 22g butyl methacrylate, 5g adamantane methacrylate, 15g triisopropyl methacrylate and 2.2g hydroxymethyl acrylamide to the emulsion, and stir at 70°C and 250 rpm for 30 min to obtain a pre-emulsion.

[0094] (3) Dissolve 0.15g of ammonium persulfate in 16g of deionized water to prepare an initiator solution; dissolve 0.17g of ammonium persulfate in 16g of deionized water to prepare a pH adjustment solution;

[0095] (4) Add an initiator solution to the pre-emulsion, add a pH adjustment solution to adjust the pH value to 7.5, heat to 78-80℃, carry out the polymerization reaction for 2 hours, cool to room temperature, and obtain the fluorine-free waterproof and oil-repellent agent of this comparative example.

[0096] Performance testing

[0097] The waterproof and oil-repellent agent samples prepared in Examples 1-3 and Comparative Examples 1-7 were used to treat cotton fabrics (80% padding rate, curing at 120℃ for 3 min) for waterproofing, oil repellency, and wash resistance tests after 50 washes. The test results are shown in Table 1. Meanwhile, the waterproof and oil-repellent agent samples prepared in Examples 1-3 were subjected to accelerated testing at 50℃ for 6 months, and no significant changes were observed.

[0098] The waterproof performance is tested according to AATCC 22 standard (Water Repellency: Spray Test). This standard applies to any textile fabric, regardless of whether it has undergone water-repellent treatment, and aims to determine the fabric's resistance to water wetting. The specific procedure involves spraying water onto a stretched sample under specified conditions, creating a wetted pattern on its surface. The fabric's water repellency is evaluated by comparing it to a standard pattern. The spraying time must be strictly controlled between -25 and 30 seconds. The test results are related to the initial water repellency and wetting properties of the fibers, yarns, and fabric finishing, and are not significantly affected by the fabric structure. Waterproof ratings are divided into 5 levels: Level 5 indicates almost no wetting on the fabric surface, with excellent water repellency; Level 4 indicates a few discontinuous wetting spots on the fabric surface; Level 3 indicates many continuous wetting spots on the fabric surface; Level 2 indicates a large area of ​​the fabric surface is wetted; and Level 1 indicates the fabric surface is completely wetted.

[0099] Oil repellency is tested according to AATCC 118 standard (Test Method for Oil Repellency: Hydrocarbon Resistance). This standard is used to determine the presence of finishing compounds on fabrics that impart low-energy surfaces. Oil repellency is assessed by evaluating the fabric's resistance to wetting by a range of standard liquid hydrocarbons with varying surface tensions. During testing, droplets of a selected range of standard test solutions (composed of hydrocarbons with different surface tensions) are dropped onto the fabric surface, and wetting, wicking, and contact angle are observed. Oil repellency levels range from 0 to 8, from lowest to highest. Level 0 indicates failure to pass Level 1, meaning the fabric surface will be wetted by Level 1 test solution; Level 1 indicates the fabric can only resist oils with high surface tension, such as vegetable oils; as the level increases, the surface tension of oils the fabric can resist gradually decreases. For example, Level 2 can only resist kerosene, Level 3 can resist kerosene and n-dodecane, Level 4 can resist n-hexadecane, and Level 8 can resist oils with extremely low surface tension, such as n-heptane.

[0100] Table 1:

[0101]

[0102] As shown in Table 1, the waterproof and oil-repellent samples prepared in Examples 1-3 all have a contact angle greater than 120°, achieving a waterproof rating of 4, demonstrating excellent waterproof performance; they also achieve an oil-repellent rating of 4, exhibiting good oil-repellent performance; and the monomer conversion rate is as high as 98.0-98.5%. After 50 washes, the waterproof and oil-repellent rating can still reach 3, demonstrating good wash resistance; the overall performance is excellent.

[0103] Compared to Examples 1 or 2, Comparative Examples 1-7, due to the use of a single functional monomer, the absence of added functional monomers, the use of other types of functional monomers, and the traditional one-time polymerization process, all failed to achieve good waterproof, oil-repellent, and wash-resistant properties, and the contact angle and monomer conversion rate also decreased. This demonstrates that the functional monomers adamantane methacrylate and triisopropylsilyl methacrylate of the present invention, after polymerization with the base monomers, provide fabrics with stronger waterproof, oil-repellent, and wash-resistant properties, as well as a higher monomer conversion rate, thereby endowing the fabrics with excellent comprehensive properties.

[0104] For those skilled in the art, several simple deductions or substitutions can be made without departing from the inventive concept, without requiring creative effort. Therefore, any simple improvements made to this invention by those skilled in the art based on the disclosure of this invention should be within the scope of protection of this invention. The above embodiments are preferred embodiments of this invention, and all processes similar to this invention and equivalent changes should fall within the scope of protection of this invention.

Claims

1. A fluorine-free waterproof and oil-repellent agent, characterized in that, Its raw material components include emulsifiers, base monomers, functional monomers and initiators. The base monomers include octadecyl methacrylate and / or butyl methacrylate, and the functional monomers include adamantane methacrylate and triisopropylsilyl methacrylate.

2. The fluorine-free waterproof and oil-repellent agent according to claim 1, characterized in that, The mass ratio of adamantane methacrylate to triisopropylsilyl methacrylate is 1:(2-3).

3. The fluorine-free waterproof and oil-repellent agent according to claim 1, characterized in that, The emulsifiers include sulfonate surfactants and fatty alcohol polyoxyethylene ethers.

4. The fluorine-free waterproof and oil-repellent agent according to claim 1, characterized in that, The initiator is selected from inorganic peroxide initiators.

5. The fluorine-free waterproof and oil-repellent agent according to claim 1, characterized in that, The raw material components, by weight, include: 1-7 parts emulsifier, 5-27 parts basic monomer, 2-10 parts adamantyl methacrylate, 4-30 parts triisopropylsilyl methacrylate, and 0.1-0.5 parts initiator.

6. The fluorine-free waterproof and oil-repellent agent according to claim 5, characterized in that, The raw material components also include at least one of a crosslinking monomer and a pH adjuster, wherein the crosslinking monomer includes hydroxymethylacrylamide and the pH adjuster includes ammonium persulfate.

7. A method for preparing a fluorine-free waterproof and oil-repellent agent as described in any one of claims 1-6, characterized in that, Includes the following steps: (1) Dissolve the emulsifier to prepare an emulsion; then divide the emulsion into two parts, add the basic monomer and the functional monomer to each part respectively, and perform pre-emulsification to obtain pre-emulsion A and pre-emulsion B; (2) Initiator was added to the preemulsion A and preemulsion B respectively, mixed, and pH value was adjusted to obtain emulsion A and emulsion B; (3) The emulsion A is heated to perform prepolymerization to obtain prepolymer A; (4) Add emulsion B dropwise to the prepolymer A to carry out a polymerization reaction and obtain the fluorine-free waterproof and oil-repellent agent.

8. The method for preparing the fluorine-free waterproof and oil-repellent agent according to claim 7, characterized in that, In step (1), the pre-emulsification process conditions are: stirring at 200-300 rpm for 20-40 minutes at a temperature of 60-80℃.

9. The method for preparing the fluorine-free waterproof and oil-repellent agent according to claim 7, characterized in that, In step (3), the prepolymerization process conditions are: stirring at 200-300 rpm for 1.5-2.5 hours at a temperature of 78-80℃.

10. A fabric, characterized in that, The raw materials for preparing the fabric include the fluorine-free waterproof and oil-repellent agent according to any one of claims 1-6, or the fluorine-free waterproof and oil-repellent agent prepared by the preparation method according to any one of claims 7-9.

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