Super-hydrophobic polyester fabric and preparation method thereof

Abstract

The invention belongs to the field of spinning, and particularly relates to a super-hydrophobic polyester fabric and a preparation method thereof.The preparation method comprises the following steps that the polyester fabric is soaked in an adhesive solution, the adhesive is polymerized in the solution and deposited on the surface of the polyester fabric, then the polyester fabric is added into a low-surface-energy modifier solution for hydrophobic modification, and the super-hydrophobic polyester fabric is obtained. The super-hydrophobic polyester fabric is obtained. The preparation method is simple and convenient, and the super-hydrophobic fabric which is free of fluorine, good in durability and free of damage to the performance of the fabric can be obtained.

Description

Technical Field

[0001] This invention belongs to the field of textiles, and particularly relates to a superhydrophobic polyester fabric and its preparation method, specifically to a superhydrophobic polyester fabric with ultra-durable properties obtained by fiber surface polymerization modification and its preparation method. Background Technology

[0002] Polyester fabrics possess excellent mechanical properties and durability, making them widely used in daily life and industrial production, particularly in medical, hygiene, filtration, and separation fields. Superhydrophobic modification of polyester fabrics with low surface energy materials can impart superhydrophobic properties and low bioadhesion, broadening their application prospects in anti-icing, anti-corrosion, self-cleaning, antibacterial, and oil-water separation applications. However, the chemical inertness of polyester fabrics makes it difficult for hydrophobic coatings to bond reliably. Currently, alkaline etching or plasma etching is commonly used to introduce reactive groups onto the polyester fabric surface, providing reaction sites for subsequent modification. However, these methods severely damage the inherent physicochemical properties of the fabric, and the durability is often unsatisfactory, failing to meet the needs of daily use.

[0003] Furthermore, existing modification methods require complex processes, including modification with fluorinated chemicals and etching of fiber surfaces with strong alkalis. These methods are not only difficult to implement on a large scale but also pose environmental safety risks. Therefore, there is a need to develop a simple, mass-producible method for preparing fluorine-free, durable, and non-damaging superhydrophobic fabric modification techniques. Summary of the Invention

[0004] To overcome the shortcomings of existing technologies, this invention provides a method for preparing superhydrophobic polyester fabric, comprising the following steps:

[0005] Polyester fabric is immersed in an adhesive solution, the adhesive polymerizes in the solution and deposits onto the surface of the polyester fabric, and then a low surface energy modifier solution is added for hydrophobic modification to obtain a superhydrophobic polyester fabric.

[0006] According to an embodiment of the present invention, the polyester fabric is polyester fiber, also known as polyester fiber.

[0007] According to an embodiment of the present invention, the preparation method includes the following steps:

[0008] 1) The polyester fabric is immersed in a buffer solution of the adhesive to react, wherein the adhesive polymerizes in the buffer solution to generate nanoparticles and deposits them on the surface of the polyester fabric, and is dried to obtain the adhesive-modified polyester fabric.

[0009] 2) The adhesive-modified polyester fabric is soaked in an organic solvent and then dried. It is then soaked in a solution of a low surface energy modifier. The low surface energy modifier is hydrolyzed and self-assembled onto the fiber surface of the bio-adhesive-modified polyester fabric. After drying, a superhydrophobic polyester fabric is obtained.

[0010] According to an embodiment of the present invention, the adhesive is selected from compounds that can self-polymerize and adhere to and deposit on the surface of polyester fabrics. The compounds have at least hydrogen bond interactions with the polyester fabrics and can penetrate into the network of the polyester fabrics through impregnation. The compounds can also polymerize in situ to form polymer chains that combine with the polyester fabric network to cover the surface of the polyester fabrics and form a modified layer.

[0011] According to an embodiment of the present invention, the adhesive is selected from biological adhesives, which refer to biocompatible adhesives.

[0012] According to an embodiment of the present invention, the bio-adhesive is selected from one or more of dopamine, tannic acid, dopamine-quinone, and 5,6-dihydroxyindole. For example, the bio-adhesive is dopamine. Dopamine can impregnate and penetrate into the fabric network and polymerize in situ into polydopamine. There are π-π interactions and hydrogen bond interactions between polydopamine and polyester fabric, so as to achieve a reliable bond between polydopamine molecular chains and fabric network without destroying the original structure of polyester fabric.

[0013] According to an embodiment of the present invention, the low surface energy modifier is selected from compounds capable of forming low surface energy microstructures on the surface of the modified layer.

[0014] According to an embodiment of the present invention, the low surface energy modifier is a fluorine-free and environmentally friendly low surface energy modifier.

[0015] According to an embodiment of the present invention, the low surface energy modifier is selected from one or more of octadecyltrichlorosilane and hexadecyltrichlorosilane, for example, octadecyltrichlorosilane.

[0016] According to an embodiment of the present invention, the octadecyltrichlorosilane and hexadecyltrichlorosilane contain three hydrolyzable groups, which can be hydrolyzed to self-assemble into micro- and nano-particles on the surface of bio-adhesive modified polyester fabrics to construct surface microstructures, and their long alkyl chains can provide low surface energy.

[0017] According to an embodiment of the present invention, the buffer solution in step 1) is selected from Tris-HCl buffer solution.

[0018] According to an embodiment of the present invention, in step 1), the buffer solution is a Tris-HCl buffer solution, and the mass ratio of Tris-HCl salt to deionized water in the Tris-HCl buffer solution is (0.0001 to 0.005):1, for example, 0.001:1.

[0019] According to an embodiment of the present invention, in step 1), the mass ratio of the bio-adhesive to deionized water is (0.0005 to 0.003):1, for example, 0.002:1.

[0020] According to an embodiment of the present invention, in step 1), the area ratio of the polyester fabric to the volume ratio of deionized water is (0.1-0.5):1cm². 2 / mL, for example, 0.16:1cm 2 / mL.

[0021] According to an embodiment of the present invention, step 1) includes the following steps: immersing a polyester fabric in a buffer solution, adjusting the pH value to alkaline, adding a bio-adhesive to react, wherein the adhesive polymerizes in the buffer solution to generate nanoparticles and deposits them onto the surface of the polyester fabric, and drying to obtain an adhesive-modified polyester fabric.

[0022] According to an embodiment of the present invention, adjusting the pH value to alkaline includes adjusting the pH value of the buffer solution soaking the polyester fabric to 8-10, preferably 8.5-9, for example 8.5.

[0023] According to an embodiment of the present invention, the bio-adhesive is reacted at a temperature of 20-30°C for a time of 2-8 hours, for example, 6 hours.

[0024] According to an embodiment of the present invention, the reaction in step 1) is carried out under stirring conditions, wherein the stirring speed is 400 to 800 r / min, for example 550 r / min.

[0025] According to an embodiment of the present invention, the drying temperature in step 1) is 70-80°C, for example 75°C.

[0026] According to an embodiment of the present invention, step 1) further includes the following step before drying: cleaning the polyester fabric deposited with polymer nanoparticles, preferably the cleaning includes cleaning several times with water and / or ethanol.

[0027] According to an embodiment of the present invention, the organic solvent in step 2) is selected from n-hexane and / or ethanol, for example, n-hexane.

[0028] According to an embodiment of the present invention, in step 2), the adhesive-modified polyester fabric is soaked in an organic solvent for 0.5 to 3 hours, for example, 1 hour.

[0029] According to an embodiment of the present invention, in step 2), the immersion in an organic solvent followed by drying is carried out under vacuum conditions.

[0030] According to an embodiment of the present invention, the temperature for drying after soaking in the organic solvent in step 2) is 30 to 60°C, for example, 50°C.

[0031] According to an embodiment of the present invention, the drying time after soaking in the organic solvent in step 2) is 2 to 6 hours, for example, 3 hours.

[0032] According to an embodiment of the present invention, in step 2), the low surface energy modifier is selected from at least one of octadecyltrichlorosilane and hexadecyltrichlorosilane, for example, octadecyltrichlorosilane.

[0033] According to an embodiment of the present invention, in step 2), the solvent in the solution of the low surface energy modifier is selected from n-hexane and / or ethanol, for example, n-hexane.

[0034] According to an embodiment of the present invention, in the solution of the low surface energy modifier in step 2), the mass ratio of the low surface energy modifier to the solvent is (0.01 to 0.05):1, for example, 0.02:1.

[0035] According to an embodiment of the present invention, in step 2), the ratio of the area of ​​the fabric after soaking in the organic solvent to the volume of the solvent is (0.2 to 0.6):1, for example, 0.4:1.

[0036] According to an embodiment of the present invention, in step 2), the modification temperature of the low surface energy modifier is 20-30°C, and the modification time is 2-8 hours, preferably 6 hours.

[0037] According to an embodiment of the present invention, in step 2), the drying after modification is carried out under vacuum conditions.

[0038] According to an embodiment of the present invention, in step 2), the drying temperature after modification is 40-60°C, for example, 50°C.

[0039] The present invention also provides a superhydrophobic polyester fabric with superior durability prepared by the above method, wherein the polyester fabric has a hydrophobic surface.

[0040] According to an embodiment of the present invention, the superhydrophobic polyester fabric has essentially the following properties: Figure 1 The electron microscope image shown in c.

[0041] According to an embodiment of the present invention, the static contact angle of the superhydrophobic polyester fabric is greater than 160°, for example, 162.76°.

[0042] Beneficial effects

[0043] (1) This invention develops a method for preparing a superhydrophobic polyester fabric that does not damage the original physicochemical properties of polyester fabric (polyester fabric) and has super durability. Starting from the structure of the polyester fabric itself, since the benzene ring in the structure of polyester gives the polyester fabric rigidity, it has excellent mechanical properties. However, the stability of the benzene ring also causes the chemical inertness of the polyester fabric surface, making it difficult to introduce active groups. Dopamine, tannic acid, dopamine-quinone, 5,6-dihydroxyindole, etc., can be polymerized in situ on the polyester fabric under appropriate conditions, thereby allowing polymers such as polydopamine to penetrate into the polyester fabric network, which is beneficial for constructing polydopamine. The effective binding force between polydopamine and polyester fabrics is demonstrated by the polymer's strong adhesion. It can form at least hydrogen bonds with the benzene rings and ester groups of polyester fabrics. For example, polydopamine can also interact with polyester fabrics via π-π interactions, thereby effectively binding to the polyester surface and providing a large number of active groups. This not only improves the durability of polyester fabrics but also overcomes the modification difficulties caused by the chemical inertness of polyester fabrics. A superhydrophobic polyester fabric with ultra-durability is prepared without damaging the inherent physicochemical properties of polyester fabrics. It has excellent mechanical, chemical, and environmental durability and is suitable for various practical application environments.

[0044] (2) The superhydrophobic modifier used in this invention is octadecyltrichlorosilane / hexadecyltrichlorosilane, which has strong reactivity, simple reaction conditions, and can self-assemble on the surface of polydopamine-modified polyester fabric through simple hydrolysis to form micro-nano particles, thereby constructing the rough structure required to achieve superhydrophobicity. Through the hydrolytic self-assembly of octadecyltrichlorosilane / hexadecyltrichlorosilane on the surface of polyester fabric modified with polymers such as polydopamine, the grafting of low surface energy materials on the fabric surface is realized. In addition, the hydrolysis of octadecyltrichlorosilane can form micro-nano particles on the fabric surface, which is beneficial to improving the superhydrophobic performance. It successfully realizes the simultaneous grafting of low surface energy materials and the construction of microstructures on the fabric surface using a simple method. Compared with the methods for constructing rough structures in the prior art (such as etching, introducing micro-nano particles, etc.), the method of this invention is simple, and the formed micro-nano particles and hydrophobic long chains are connected to polydopamine through covalent bonds, which has good durability.

[0045] (3) A simple two-step impregnation method was used to prepare superhydrophobic polyester fabric with super durability. It is efficient, energy-saving, and can be manufactured on a large scale. The superhydrophobic modifier used in the method of the present invention is octadecyltrichlorosilane / hexadecyltrichlorosilane, which is a fluorine-free low surface energy modifier and is safe and environmentally friendly. The polymer used as an adhesive, such as polydopamine, is also a non-toxic material with good biocompatibility. Therefore, the method of the present invention can be used for large-scale preparation and can be used in the daily footwear and apparel industry.

[0046] (4) The purpose of using polydopamine as a binder to modify polyester fabrics in this invention is to introduce active groups on the surface of polyester fabrics without damaging the fabric's structure. Furthermore, this invention does not damage the structure of the polyester fabric during the subsequent superhydrophobic modification process. Although there are existing inventions that use polydopamine as a binder to modify polyester fabrics before hydrophobic modification, the operations performed in these superhydrophobic modification steps, such as surface etching, can damage the structure of the polyester fabric. This results in poor fabric performance after surface modification with polydopamine as a binder. Attached Figure Description

[0047] Figure 1 a is an electron microscope image of the original polyester fabric. Figure 1 b is an electron microscope image of the fabric prepared in Comparative Example 1. Figure 1 c is an electron microscope image of the superhydrophobic polyester fabric prepared in Example 1;

[0048] Figure 2 a represents the static contact angle of the fabric prepared in Comparative Example 1. Figure 2 b represents the static contact angle of the fabric prepared in Example 1;

[0049] Figure 3 The changes in contact angle and shedding angle of the fabric prepared in Example 1 during mechanical durability testing. Figure 3 a: Changes in contact angle and detachment angle during the tape adhesion-peel cycle test; Figure 3 b: Changes in contact angle and drop angle during sandpaper wear cycles;

[0050] Figure 4 The changes in contact angle and shedding angle of the fabric prepared for Comparative Example 1 during the sandpaper abrasion cycle;

[0051] Figure 5 The contact angle and shedding angle of the fabric prepared in Example 1 during chemical durability testing. Figure 5 a: Contact angle and roll-off angle after soaking in solutions of different pH values ​​for 72 hours; Figure 5 b: Contact angle and roll-off angle after immersion in different organic solvents for 72 hours; Figure 5 c: Changes in contact angle and detachment angle during ultraviolet treatment; Figure 5 d: Contact angle and roll-off angle after 72 hours of treatment at different temperatures; Figure 5 e: Changes in contact angle and shedding angle during the washing cycle;

[0052] Figure 6 The contact angle and shedding angle of the fabric prepared in Example 1 after the high-speed water flow impact test and the self-healing test;

[0053] Figure 7 The physical properties of the original polyester fabric and the fabric prepared in Example 1 were tested. Figure 7 a is a comparison chart of the water vapor transmission rate of the fabric prepared in Example 1 and the original fabric: Figure 7 b is a comparison diagram of the tensile strength of the fabric prepared in Example 1 and the original fabric; Figure 7 c is a comparison diagram of the flexibility of the fabric prepared in Example 1 and the original fabric (the original fabric is on top, and the fabric prepared in Example 1 is on the bottom). Detailed Implementation

[0054] The preparation method of the superhydrophobic polyester fabric of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0055] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0056] Example 1

[0057] 4×4cm 2 Polyester fabric immersed in 100mL 10×10 -3 In a Tris-HCl buffer solution, the pH was adjusted to 8.5 with 0.5M sodium hydroxide solution. 200 mg of dopamine hydrochloride was added to this solution, and the reaction was carried out at ambient temperature. The in-situ polymerization of dopamine lasted for 6 hours with a stirrer speed of 550 rpm. After the reaction, the mixture was thoroughly washed with water and ethanol, and then dried in a 75℃ oven to obtain a 4×4 cm sample. 2 Polydopamine-modified polyester fabric.

[0058] 4×4cm 2 Polydopamine-modified polyester fabric was first soaked in n-hexane for 1 hour, then dried in a vacuum oven at 50°C for 3 hours, and then soaked in a n-hexane solution of octadecyltrichlorosilane (mass ratio of octadecyltrichlorosilane to n-hexane was 0.02:1) at ambient temperature for 6 hours. Finally, it was dried in a vacuum oven at 50°C for 3 hours to obtain superhydrophobic polyester fabric.

[0059] Example 2: The specific experimental steps in this example are basically the same as those in Example 1, except that the soaking time in the hexane solution of octadecyltrichlorosilane is 2 hours.

[0060] Example 3: The specific experimental steps in this example are basically the same as those in Example 1, except that the soaking time in the hexane solution of octadecyltrichlorosilane is 4 hours.

[0061] Example 4: The specific experimental steps in this example are basically the same as those in Example 1, except that the soaking time in the hexane solution of octadecyltrichlorosilane is 8 hours.

[0062] Comparative Example 1: A 4×4cm 2 The polyester fabric was soaked in n-hexane for 1 hour, dried in a vacuum oven at 50°C for 3 hours, and then soaked in a n-hexane solution of octadecyltrichlorosilane (mass ratio of octadecyltrichlorosilane to n-hexane was 0.02:1) at ambient temperature for 6 hours, and then dried in a vacuum oven at 50°C for 3 hours.

[0063] Table 1. Data on superhydrophobic polyester fabrics prepared under different conditions.

[0064]

[0065] See Figure 1 As shown, the surface of the superhydrophobic polyester fabric prepared in Example 1 is relatively smooth. The surface of the polyester fabric in Example 1 contains a large number of micro-nano particles, and the surface of the polyester fabric in Comparative Example 1 contains micro-nano particles.

[0066] See Figure 2 As shown in Table 1, after dopamine polymerization, the static contact angle of the fabric can reach 162.76° when the hydrolysis time of octadecyltrichlorosilane is 6h, which indicates good hydrophobicity.

[0067] See Figure 3 As shown, in the mechanical durability test of the superhydrophobic polyester fabric prepared in Example 1, during the tape adhesion-peel cycle test, when the number of cycles reached 100, the contact angle was still greater than 150° and the peeling angle was less than 10°; during the sandpaper abrasion cycle test, when the number of cycles reached 1000, the contact angle was still greater than 150°; see also Figure 4 As shown, the fabric prepared in Comparative Example 1, when subjected to sandpaper abrasion cycles, exhibited a contact angle of less than 140° and a shedding angle of greater than 10° when the number of cycles reached 600.

[0068] See Figure 5 As shown, the fabric prepared in Example 1 had a contact angle greater than 150° and a roll-off angle less than 10° after soaking in different pH solutions for 72 hours; a contact angle greater than 150° and a roll-off angle less than 10° after soaking in different organic solvents for 72 hours; a contact angle greater than 150° and a roll-off angle less than 10° after ultraviolet treatment for 100 minutes; a contact angle greater than 150° and a roll-off angle less than 10° after treatment at different temperatures for 72 hours; and a contact angle greater than 150° and a roll-off angle less than 10° after 1000 washing cycles.

[0069] See Figure 6As shown, the fabric prepared in Example 1 had a contact angle greater than 140° and a roll-off angle less than 12° after the high-speed water flow impact test; and a contact angle greater than 150° and a roll-off angle less than 10° after the self-healing test.

[0070] See Figure 7 As shown, the water vapor permeability of the fabric prepared in Example 1 is significantly lower than that of the original fabric; the tensile strength is significantly higher than that of the original fabric; and the flexibility is better.

[0071] The specific embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above exemplary embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a superhydrophobic polyester fabric, characterized in that, Includes the following steps: Polyester fabric is immersed in an adhesive solution, the adhesive polymerizes in the solution and deposits onto the surface of the polyester fabric, and then a low surface energy modifier solution is added for hydrophobic modification to obtain a superhydrophobic polyester fabric.

2. The method for preparing the hydrophobic polyester fabric according to claim 1, characterized in that, The preparation method includes the following steps: 1) The polyester fabric is immersed in a buffer solution of the adhesive to react, wherein the adhesive polymerizes in the buffer solution to generate nanoparticles and deposits them on the surface of the polyester fabric, and is dried to obtain the adhesive-modified polyester fabric. 2) The adhesive-modified polyester fabric is soaked in an organic solvent and then dried. It is then soaked in a solution of a low surface energy modifier. The low surface energy modifier is hydrolyzed and self-assembled onto the fiber surface of the bio-adhesive-modified polyester fabric. After drying, a superhydrophobic polyester fabric is obtained.

3. The method for preparing the hydrophobic polyester fabric according to claim 1, characterized in that, The adhesive is selected from bio-adhesives, which are biocompatible adhesives selected from one or more of dopamine, tannic acid, dopamine-quinone, and 5,6-dihydroxyindole. Preferably, the low surface energy modifier is selected from compounds that can form low surface energy microstructures on the surface of the modified layer, and the low surface energy modifier is a fluorine-free and environmentally friendly low surface energy modifier. Preferably, the low surface energy modifier is selected from octadecyltrichlorosilane and / or hexadecyltrichlorosilane.

4. The method for preparing the hydrophobic polyester fabric according to any one of claims 1-3, characterized in that, In step 1), the mass ratio of the bio-adhesive to deionized water is (0.0005~0.003):

1. Preferably, in step 1), the area ratio of the polyester fabric to the volume ratio of deionized water is (0.1-0.5):1cm³. 2 / mL.

5. The method for preparing the hydrophobic polyester fabric according to claim 2, characterized in that, Step 1) includes the following steps: immersing the polyester fabric in a buffer solution, adjusting the pH to alkaline, adding a bio-adhesive to react, wherein the adhesive polymerizes in the buffer solution to generate nanoparticles and deposits them onto the surface of the polyester fabric, and drying to obtain the adhesive-modified polyester fabric. Preferably, adjusting the pH to alkaline involves adjusting the pH of the buffer solution soaking the polyester fabric to 8-10.

6. The method for preparing the hydrophobic polyester fabric according to claim 2, characterized in that, The reaction temperature of the bio-adhesive is 20-30℃, and the reaction time is 2-8h.

7. The method for preparing the hydrophobic polyester fabric according to any one of claims 1-3, characterized in that, The organic solvent mentioned in step 2) is selected from n-hexane and / or ethanol. Preferably, in step 2), the adhesive-modified polyester fabric is soaked in an organic solvent for 0.5 to 3 hours, for example, 1 hour. Preferably, in step 2), the drying after soaking in the organic solvent is carried out under vacuum conditions, the temperature of the drying after soaking in the organic solvent is 30-60°C, and the drying time is 2-6 hours.

8. The method for preparing the hydrophobic polyester fabric according to any one of claims 1-3, characterized in that, In step 2), the low surface energy modifier is selected from octadecyltrichlorosilane and / or hexadecyltrichlorosilane. Preferably, in step 2), the solvent in the solution of the low surface energy modifier is selected from n-hexane and / or ethanol. Preferably, in the solution of the low surface energy modifier in step 2), the mass ratio of the low surface energy modifier to the solvent is (0.01 to 0.05): 1, for example, 0.02:

1.

9. The method for preparing the hydrophobic polyester fabric according to any one of claims 1-3, characterized in that, In step 2), the ratio of the fabric area to the solvent volume after soaking in the organic solvent is (0.2-0.6):

1. Preferably, the modification temperature of the low surface energy modifier is 20-30℃, and the modification time is 2-8h. Preferably, in step 2), the modified drying is carried out under vacuum conditions, and the drying temperature is 40-60°C.

10. A superhydrophobic polyester fabric with superior durability prepared by the method according to any one of claims 1-9, wherein the polyester fabric has a hydrophobic surface. Preferably, the static contact angle of the superhydrophobic polyester fabric is greater than 160°.

Images