High-resilience anti-fouling sponge material and preparation method thereof

Abstract

The invention discloses a high-resilience anti-fouling sponge material and a preparation method thereof, belongs to the technical field of preparation of anti-fouling sponges, and aims to solve the technical problem that the resilience and thermal aging resistance of anti-fouling sponges in the prior art need to be further improved. The preparation method specifically comprises the following steps: mixing polyethylene glycol, modified polysilanediol, flexible aerogel, a polyurethane foam stabilizer, deionized water and stannous octoate to obtain mixed alcohol; modified polysilanediol and flexible aerogel are introduced to construct a multi-scale collaborative network, the integrated design of structure enhancement and body pollution resistance of the polyurethane elastomer is achieved, and different from a traditional surface coating means, according to the scheme, pollution resistance and mechanical properties are embedded in a material system, so that the structural enhancement and body pollution resistance of the polyurethane elastomer are improved, and the structural enhancement and body pollution resistance of the polyurethane elastomer are improved. Long-term stability and complex working condition adaptability are both considered, and the flexible aerogel and the organic framework form a uniformly dispersed structure, and meanwhile, the framework is supported to improve toughness and rebound resilience.

Description

Technical Field

[0001] This invention relates to the field of anti-fouling sponge preparation technology, specifically to a highly resilient anti-fouling sponge material and its preparation method. Background Technology

[0002] The performance development of high-resilience anti-fouling sponges has evolved from single-function to synergistic optimization. Early anti-fouling technologies mainly relied on surface coatings, but these had the drawback of easy wear. Later, the focus shifted to intrinsic material modification, achieving durable hydrophobic effects through molecular structure design and micropore control, and introducing nanotechnology to enhance self-cleaning capabilities. Advances in high-resilience performance stem from the optimization of cell structure and the application of novel crosslinking agents, which improve rebound rate and durability while maintaining low density, meeting dynamic usage requirements. In recent years, technological development has focused more on the synergistic optimization of anti-fouling and high resilience, using integrated structural design to balance rapid rebound with anti-fouling and wear-resistant properties, enabling the material to be widely used in high-end fields such as medical and transportation. Future trends will continue to focus on innovation in environmental protection, functional integration, and intelligence.

[0003] For example, prior art CN113201170B discloses a graphene polyurethane composite sponge material with excellent stain resistance and its application. The graphene polyurethane composite sponge material includes a polyurethane sponge matrix and an anti-stain coating disposed on the polyurethane sponge matrix. The anti-stain coating is obtained by curing an anti-stain slurry. The anti-stain slurry, by weight, includes: 1-5 parts graphene nanosheets, 2-10 parts nano titanium dioxide, 5-15 parts silicon micropowder, 0.2-8 parts highly branched polysiloxane, 0.1-5 parts hydroxyl silicone oil, and 40-60 parts acrylic emulsion. This invention endows the graphene polyurethane composite sponge material with excellent stain resistance and antibacterial properties by setting a layer of anti-stain coating of specific materials on the polyurethane sponge matrix. It has a good protective effect against stains such as tea, vinegar, and markers. Moreover, it has high resilience, a soft feel, good strength and heat dissipation, and can be applied to high-performance mattresses, cushions, backrests and other home furnishings.

[0004] However, the inventions mentioned above achieve composite antifouling effects of functional components such as graphene and TiO2, but the overall design is still mainly based on surface functional construction and lacks a structural synergistic mechanism from the inside of the material system. Specifically, there is a lack of effective interfacial cross-linking between the coating and the polyurethane matrix. The fillers such as graphene are mainly empowered by physical doping and are easily detached or migrated under thermal stress or mechanical shear, resulting in the decay of antifouling performance over time. Meanwhile, the material does not have a multi-scale interlocking or interpenetrating network, and the coating and the matrix lack a stable chemical connection structure, making it difficult to achieve synergistic regulation of structural toughness and interface stability. In addition, no flexible support phase or dynamically adjustable chain segment is introduced, resulting in insufficient rigidity and rapid fatigue accumulation in terms of stress release and thermal aging response. The mechanical properties, anti-fouling properties and anti-aging properties of the composite sponge material need to be further improved. Summary of the Invention

[0005] The purpose of this invention is to provide a highly resilient anti-fouling sponge material and its preparation method, in order to solve the technical problem that the resilience and heat aging resistance of anti-fouling sponges in the prior art need to be further improved.

[0006] The objective of this invention can be achieved through the following technical solution: a method for preparing a highly resilient, stain-resistant sponge material, comprising the following steps: S1. After mixing polyethylene glycol, modified polysiloxane glycol, flexible aerogel, polyurethane foam stabilizer, deionized water and stannous octoate, a mixed alcohol is obtained. S2. Add the mixed alcohol to the reactor, purge with nitrogen for protection, raise the reactor temperature to 40-60℃, add the calculated amount of isophorone diisocyanate to the reactor, stir at 3000-3200 rpm for 10-15 seconds, transfer the reaction solution to the foaming box, and cure at room temperature for 4-6 hours. After post-treatment, the anti-fouling sponge is obtained.

[0007] The reaction principle for preparing the anti-fouling sponge is as follows: polyethylene glycol and modified polysiloxane glycol, as the main polyol components, undergo an addition reaction between hydroxyl groups and isophorone diisocyanate to form a polyurethane cross-linked network. The flexible aerogel further reacts through the aminoisophorone diisocyanate on its surface, enhancing the overall stability of the network structure. Deionized water reacts with the residual isocyanate groups in the reaction system, releasing carbon dioxide gas, thereby initiating the foaming process. The porous structure of the flexible aerogel plays a slow-release role during the foaming process, making the pores more uniform, thus preparing a porous anti-fouling sponge.

[0008] Furthermore, in step S1, the ratio of polyethylene glycol, modified polysiloxane glycol, flexible aerogel, polyurethane foam stabilizer, deionized water and stannous octoate is 20-30g:20-30g:5-6g:1-2g:2-3g:1-2g. Furthermore, in step S2, the amount of isophorone diisocyanate added is 0.60-0.65 times the sum of the molar amounts of hydroxyl and amino groups in the mixed alcohol. The post-treatment includes: after curing, transferring the foam material to a drying oven at 80°C and vacuum drying it to constant weight to obtain an anti-fouling sponge.

[0009] Furthermore, the preparation method of modified polysiloxane includes the following steps: A1. Hexamethylcyclotrisiloxane, trifluoropropylmethylcyclotrisiloxane and N,N-dimethylformamide are added to a reaction vessel. After the temperature of the reaction vessel is raised to 100-120℃, sodium hydroxide is added to the reaction vessel. After the reaction is kept at this temperature for 4-5 hours, 1,1,3,3-tetramethyldisiloxane-1,3-diamine is added to the reaction vessel. The reaction is kept at this temperature for 2-3 hours. After post-treatment, modified polysiloxane is obtained. A2. Add the modified polysiloxane, the calculated amount of propylene oxide and N,N-dimethylformamide to the reactor, raise the temperature of the reactor to 70-80℃, keep it at this temperature and stir for 1-2 hours, and then proceed with the post-treatment to obtain the modified polysiloxane.

[0010] The reaction equation for preparing modified polysiloxane is as follows:

[0011] In the formula: .

[0012] The reaction principle for preparing modified polysiloxane is as follows: First, hexamethylcyclotrisiloxane and trifluoropropylmethylcyclotrisiloxane undergo ring-opening polymerization under alkaline conditions, forming a linear polysiloxane backbone through Si-O-Si linkages of siloxane bonds. Subsequently, 1,1,3,3-tetramethyldisiloxane-1,3-diamine with a diamine structure is added as a chain end-capping agent, reacting with the end groups of the polysiloxane active intermediate to introduce terminal amino structures, generating modified polysiloxanes with fluorinated side groups in the backbone and amine-terminated end groups. Subsequently, the modified polysiloxane reacts with propylene oxide, and the terminal amino groups undergo nucleophilic ring-opening reactions with propylene oxide to generate polyether side chains with hydroxyl groups at the end groups, thereby forming a modified polysiloxane containing siloxane segments, fluoroalkyl groups, and terminal hydroxyl groups in its structure.

[0013] Further, in step A1, the ratio of hexamethylcyclotrisiloxane, trifluoropropylmethylcyclotrisiloxane, N,N-dimethylformamide, sodium hydroxide, and 1,1,3,3-tetramethyldisiloxane-1,3-diamine is 6-8g:3-5g:50-54mL:0.3-0.5g:1-2g. The post-treatment includes: after the reaction is completed, the reaction system is adjusted to neutrality with acetic acid, and then the reaction system is transferred to a rotary evaporator at a temperature of 80-100℃ and evaporated under reduced pressure until no liquid is collected, thereby obtaining modified polysiloxane; Further, in step A2, the ratio of modified polysiloxane to N,N-dimethylformamide is 6-8 g: 32-36 mL, wherein the amount of propylene oxide is 1.05-1.10 times the molar amount of amino group in the modified polysiloxane. The post-treatment includes: after the reaction is completed, the reaction system is transferred to a rotary evaporator at a temperature of 80-100℃, and evaporated under reduced pressure until no liquid is collected, to obtain modified polysiloxane.

[0014] Furthermore, the preparation method of flexible aerogel includes the following steps: B1. Modified graphite, hexadecyltrimethylammonium bromide and deionized water are added to the reaction vessel and stirred. After the temperature of the reaction vessel is raised to 40-60℃, the pH of the reaction system is adjusted to 4-5 with acetic acid and silicon source solution is added to the reaction vessel. After the reaction is kept at the temperature for 2-3 hours, silica sol is added to the reaction vessel and the reaction is kept at the temperature for 1-2 hours to obtain modified gel. B2. Transfer the modified gel to a drying oven, raise the temperature of the drying oven to 60-80℃, keep it at this temperature for 20-24 hours, take out the gel and wash it 3-5 times with anhydrous ethanol and deionized water. The post-treatment yields a flexible aerogel.

[0015] The reaction principle for preparing flexible aerogels is as follows: Methyl orthosilicate, tridecafluorooctyltrimethoxysilane, and 3-aminopropyltriethoxysilane undergo hydrolysis and condensation reactions in an aqueous system under the control of acetic acid to form a three-dimensional silicon-oxygen network precursor with multifunctional copolymerization. During this process, the cationic surfactant hexadecyltrimethylammonium bromide acts as a structure directing agent, guiding the silicon source components to directionally aggregate and synergistically assemble on the modified graphite surface, further promoting the construction of the composite network. Subsequently, silica sol is introduced as a secondary network reinforcing agent to enhance the gel skeleton structure through interparticle condensation and crosslinking reactions. Finally, under mild drying conditions, water and ethanol are gradually removed, and the three-dimensional network structure within the system is preserved, forming a flexible aerogel in which functional components are embedded in a porous matrix.

[0016] Furthermore, in step B1, the ratio of the modified graphite, hexadecyltrimethylammonium bromide, deionized water, silicon source solution, and silica sol is 3-5g:0.3-0.5g:80-100mL:10-15g:2-3g. The composite silicon source is obtained by mixing methyl orthosilicate, tridecafluorooctyltrimethoxysilane, and 3-aminopropyltriethoxysilane in a ratio of 6-8g:3-5g:1-2g.

[0017] Furthermore, in step B2, the post-processing includes: after washing, transferring the aerogel material to a drying oven at 80°C, vacuum drying to constant weight, and milling it through a 50-60 mesh sieve to obtain flexible aerogel.

[0018] Furthermore, the preparation method of modified graphite includes the following steps: C1. Add the pretreated expanded graphite dispersion, anhydrous ethanol and deionized water to the reaction vessel. After adjusting the pH of the reaction system to 4-5 with acetic acid, raise the temperature of the reaction vessel to 40-60℃ and keep it at this temperature for 4-6 hours with stirring. The modified graphite preform is then obtained through post-treatment. C2. Modified graphite preforms are added to a muffle furnace and calcined to obtain modified graphite.

[0019] The reaction principle for preparing modified graphite is as follows: Pretreated expanded graphite is obtained by calcining expanded graphite. Then, tetrabutyl titanate undergoes a hydrolysis reaction in a weakly acidic water-alcohol system adjusted by acetic acid to generate a titanium oxide intermediate with good dispersibility. Subsequently, the hydrolysis product undergoes a further condensation reaction to gradually form a TiO2 precursor sol. Under stirring conditions, the TiO2 precursor sol gradually deposits and coats the surface of the pretreated expanded graphite sheets, forming a uniform composite structure. After filtration and drying, the resulting modified graphite preform is calcined at high temperature, and the titanium oxide precursor is converted into crystalline TiO2, which firmly adheres to the graphite substrate, thereby preparing modified graphite.

[0020] Further, in step C1, the ratio of the pretreated expanded graphite dispersion, anhydrous ethanol, and deionized water is 2-3 mL: 20-30 mL: 10-12 mL. The pretreated expanded graphite dispersion is obtained by thoroughly mixing pretreated expanded graphite and tetrabutyl titanate at a ratio of 1 g: 2-3 mL. The post-treatment includes: after the reaction is completed, the temperature of the reaction vessel is lowered to room temperature, the reaction solution is filtered to collect the filter cake, the filter cake is washed 3-5 times with anhydrous ethanol and deionized water, and the filter cake is transferred to a drying oven at 80°C and vacuum dried to constant weight to obtain the modified graphite preform. Furthermore, the preparation method of pretreated expanded graphite is as follows: expanded graphite is added to a muffle furnace at a temperature of 500℃, heated in an air atmosphere for 5-6 minutes, and then ground through a 100-150 mesh sieve to obtain pretreated expanded graphite.

[0021] Furthermore, in step C2, the calcination operation is as follows: the modified graphite blank is added to a muffle furnace at a temperature of 500℃ and calcined in an air atmosphere for 4-6 hours to obtain modified graphite.

[0022] The present invention also proposes a highly resilient, stain-resistant sponge material, which is prepared by the above-mentioned method for preparing a highly resilient, stain-resistant sponge material.

[0023] The present invention has the following beneficial effects: 1. This invention significantly reduces the surface energy of the material by introducing fluorine-modified polysiloxane, making it difficult for water- and oily pollutants to spread and adhere to the surface upon contact, thus inhibiting pollution at its source. At the same time, the micro-nano-scale rough structure constructed by the three-dimensional silicon-oxygen network further enhances the rolling properties of droplets, making it easy for pollutants to slide off and be carried away. In addition, the introduction of titanium dioxide nanoparticles not only enhances the physical barrier effect of the surface but also endows the material with a certain photocatalytic ability, enabling it to continuously decompose adsorbed organic pollutants on the surface under light conditions, effectively preventing pollution residue. Finally, through this multi-component synergistic design, efficient coordination is achieved from multiple levels of "pollution rejection," "pollution discharge," and "pollution decontamination," giving the material excellent anti-fouling performance.

[0024] 2. This invention utilizes a rigid support network constructed through the synergistic interaction of graphite and inorganic oxides to provide overall deformation resistance and dimensional stability. Simultaneously, flexible silicon-oxygen segments and polyvinyl alcohol structures form an elastic continuous phase, endowing the material with excellent deformability and rapid recovery capabilities. Furthermore, the multifunctional silicon-oxygen network is uniformly distributed within the matrix, not only enhancing interfacial bonding but also playing a role in force transmission and buffering at the microscale. Additionally, the introduction of fluorine-modified side chains improves the material's low surface energy and interfacial lubricity, further reducing stress concentration and extending the synergistic deformation path during tensile deformation. Moreover, the porous structure serves as a macroscopic energy regulation layer, effectively mitigating internal stress during stretching and compression, preventing local structural collapse. Ultimately, through complementary structural and interfacial synergistic material design, the prepared sponge exhibits both extensibility and rapid recovery of its original shape under stress, demonstrating excellent resilience and tensile strength.

[0025] 3. This invention utilizes modified graphite as a skeleton material, leveraging its excellent thermal conductivity and structural stability to provide a fundamental platform for heat conduction and dispersion for the entire system. The TiO2 crystals coated on its surface not only exhibit high thermal stability but also maintain structural integrity under high-temperature environments, preventing skeleton oxidation and forming a dense protective layer. The three-dimensional silica-oxygen network in the flexible aerogel is tightly integrated with the modified graphite through a copolymer structure, enhancing interfacial bonding and preventing detachment or delamination under thermal stress. The Si-O bonds in the modified polysiloxane backbone possess excellent heat resistance, while the introduction of fluoroalkyl groups further enhances intermolecular repulsion and hydrophobicity, reducing the probability of thermo-oxidative reactions. Its terminal hydroxyl groups participate in cross-linking within the polyurethane network, reinforcing overall structural stability. Furthermore, the uniformly formed porous structure during foaming effectively alleviates microscopic stress caused by thermal expansion and contraction, improving the overall durability of the material. Ultimately, through the synergy between multiple components, the material's heat aging resistance is significantly improved. Detailed Implementation

[0026] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] In this invention, the polyethylene glycol used was purchased from Shanghai Maclean Biochemical Technology Co., Ltd., with the product number P815608; the polyurethane foam stabilizer used was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd., with the product number PB94976; the stannous octoate used was purchased from Shanghai Maclean Biochemical Technology Co., Ltd., with the product number T818482; and the expanded graphite used was purchased from Shanghai Maclean Biochemical Technology Co., Ltd., with the product number E698839.

[0028] Example 1 This embodiment provides a method for preparing flexible aerogel for high-resilience, stain-resistant sponge materials, including the following steps: Step ①: Preparation of pretreated expanded graphite Weigh 20.0g of expanded graphite and add it to a muffle furnace at 500℃. Heat it for 5 minutes in an air atmosphere, then grind it through a 100-mesh sieve to obtain pretreated expanded graphite.

[0029] Step 2: Preparation of modified graphite preform Weigh out 10.0g of pretreated expanded graphite and 20.0mL of tetrabutyl titanate and mix thoroughly to obtain a pretreated expanded graphite dispersion; Weigh out 20.0 mL of pretreated expanded graphite dispersion, 200.0 mL of anhydrous ethanol and 100.0 mL of deionized water and add them to the reaction vessel. After adjusting the pH of the reaction system to 5 with acetic acid, raise the temperature of the reaction vessel to 40°C and keep it at this temperature for 4 hours with stirring. After the reaction is completed, wait for the temperature of the reaction vessel to drop to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake three times with anhydrous ethanol and deionized water, and then transfer the filter cake to a drying oven at 80°C and vacuum dry it to constant weight to obtain the modified graphite preform.

[0030] Step 3: Preparation of modified graphite Weigh 10.0g of modified graphite preform and add it to a muffle furnace at 500℃. Calcine it in air for 4 hours to obtain modified graphite.

[0031] Step 4: Preparation of modified gel Weigh out 6.0g of methyl orthosilicate, 3.0g of tridecafluorooctyltrimethoxysilane and 1.0g of 3-aminopropyltriethoxysilane and mix them to obtain a composite silicon source; Weigh out 3.0g of modified graphite, 0.3g of hexadecyltrimethylammonium bromide and 80.0mL of deionized water and add them to the reaction vessel. Stir the mixture and raise the temperature of the reaction vessel to 40℃. Adjust the pH of the reaction system to 5 with acetic acid and add 10.0g of silicon source solution to the reaction vessel. After keeping the reaction vessel at this temperature for 2h, add 2.0g of silica sol to the reaction vessel and keep the reaction vessel at this temperature for 1h to obtain the modified gel.

[0032] Step 5: Preparation of flexible aerogel Weigh 10.0g of the modified gel and transfer it to a drying oven. The temperature of the drying oven is raised to 60℃ and kept at that temperature for 20h. After that, take out the gel and wash it three times with anhydrous ethanol and deionized water. After washing, transfer the aerogel material to a drying oven at 80℃ and vacuum dry it to constant weight. Then, grind it through a 50-mesh sieve to obtain a flexible aerogel.

[0033] Example 2 This embodiment provides a method for preparing flexible aerogel for high-resilience, stain-resistant sponge materials, including the following steps: Step ①: Preparation of pretreated expanded graphite Weigh 20.0g of expanded graphite and add it to a muffle furnace at 500℃. Heat it in air for 6 minutes and then grind it through a 150-mesh sieve to obtain pretreated expanded graphite.

[0034] Step 2: Preparation of modified graphite preform Weigh out 10.0g of pretreated expanded graphite and 30.0mL of tetrabutyl titanate and mix thoroughly to obtain a pretreated expanded graphite dispersion; Weigh out 30.0 mL of pretreated expanded graphite dispersion, 300.0 mL of anhydrous ethanol, and 120.0 mL of deionized water and add them to the reaction vessel. After adjusting the pH of the reaction system to 4 with acetic acid, raise the temperature of the reaction vessel to 60°C and keep it at this temperature for 6 hours with stirring. After the reaction is complete, wait for the temperature of the reaction vessel to drop to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake 5 times with anhydrous ethanol and deionized water, and then transfer the filter cake to a drying oven at 80°C and vacuum dry it to constant weight to obtain the modified graphite preform.

[0035] Step 3: Preparation of modified graphite Weigh 10.0g of modified graphite preform and add it to a muffle furnace at 500℃. Calcine it in air for 6 hours to obtain modified graphite.

[0036] Step 4: Preparation of modified gel Weigh out 8.0g of methyl orthosilicate, 5.0g of tridecafluorooctyltrimethoxysilane and 2.0g of 3-aminopropyltriethoxysilane and mix them to obtain a composite silicon source; Weigh out 5.0g of modified graphite, 0.5g of hexadecyltrimethylammonium bromide and 100.0mL of deionized water and add them to the reaction vessel. Stir the mixture and raise the temperature of the reaction vessel to 60℃. Adjust the pH of the reaction system to 4 with acetic acid and add 15.0g of silicon source solution to the reaction vessel. Keep the reaction at this temperature for 3h and then add 3.0g of silica sol to the reaction vessel. Keep the reaction at this temperature for 2h to obtain the modified gel.

[0037] Step 5: Preparation of flexible aerogel Weigh 10.0g of the modified gel and transfer it to a drying oven. The temperature of the drying oven is raised to 80℃ and kept at that temperature for 24 hours. After that, take out the gel and wash it 5 times with anhydrous ethanol and deionized water. After washing, transfer the aerogel material to a drying oven at 80℃ and vacuum dry it to constant weight. Then, grind it through a 60-mesh sieve to obtain a flexible aerogel.

[0038] Example 3 This embodiment provides a method for preparing flexible aerogel for high-resilience, stain-resistant sponge materials, including the following steps: Step ①: Preparation of pretreated expanded graphite Weigh 20.0g of expanded graphite and add it to a muffle furnace at 500℃. Heat it in air for 6 minutes and then grind it through a 120-mesh sieve to obtain pretreated expanded graphite.

[0039] Step 2: Preparation of modified graphite preform Weigh out 10.0g of pretreated expanded graphite and 24.0mL of tetrabutyl titanate and mix thoroughly to obtain a pretreated expanded graphite dispersion; Weigh out 24.0 mL of pretreated expanded graphite dispersion, 250.0 mL of anhydrous ethanol and 120.0 mL of deionized water and add them to the reaction vessel. After adjusting the pH of the reaction system to 4 with acetic acid, raise the temperature of the reaction vessel to 50°C and keep it at this temperature for 5 hours with stirring. After the reaction is completed, wait for the temperature of the reaction vessel to drop to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake 4 times with anhydrous ethanol and deionized water, and then transfer the filter cake to a drying oven at 80°C and vacuum dry it to constant weight to obtain the modified graphite preform.

[0040] Step 3: Preparation of modified graphite Weigh 10.0g of modified graphite preform and add it to a muffle furnace at 500℃. Calcine it in air for 5 hours to obtain modified graphite.

[0041] Step 4: Preparation of modified gel Weigh out 7.0g of methyl orthosilicate, 4.0g of tridecafluorooctyltrimethoxysilane and 1.0g of 3-aminopropyltriethoxysilane and mix them to obtain a composite silicon source; Weigh out 4.0g of modified graphite, 0.4g of hexadecyltrimethylammonium bromide and 96.0mL of deionized water and add them to the reaction vessel. Stir the mixture and raise the temperature of the reaction vessel to 50℃. Adjust the pH of the reaction system to 4 with acetic acid and add 12.0g of silicon source solution to the reaction vessel. Keep the reaction at this temperature for 3h and then add 3.0g of silica sol to the reaction vessel. Keep the reaction at this temperature for 2h to obtain the modified gel.

[0042] Step 5: Preparation of flexible aerogel Weigh 10.0g of the modified gel and transfer it to a drying oven. The temperature of the drying oven is raised to 70℃ and kept at that temperature for 21 hours. After that, take out the gel and wash it four times with anhydrous ethanol and deionized water. After washing, transfer the aerogel material to a drying oven at 80℃ and vacuum dry it to constant weight. Then, grind it through a 50-mesh sieve to obtain a flexible aerogel.

[0043] Example 4 This embodiment provides a method for preparing modified polysiloxane for the production of highly resilient, stain-resistant sponge materials, comprising the following steps: Step I: Preparation of modified polysiloxane Weigh out 30.0 g of hexamethylcyclotrisiloxane, 15.0 g of trifluoropropylmethylcyclotrisiloxane, and 250.0 mL of N,N-dimethylformamide and add them to a reaction vessel. After the temperature of the reaction vessel is raised to 100℃, add 1.5 g of sodium hydroxide to the reaction vessel and keep the reaction at this temperature for 4 h. Then add 5.0 g of 1,1,3,3-tetramethyldisiloxane-1,3-diamine to the reaction vessel and keep the reaction at this temperature for 2 h. After the reaction is completed, adjust the reaction system to be neutral with acetic acid and then transfer the reaction system to a rotary evaporator at a temperature of 80℃. Evaporate under reduced pressure until no liquid is collected to obtain modified polysiloxane.

[0044] Step II: Preparation of modified polysiloxane Weigh out 30.0 g of modified polysiloxane, propylene oxide (1.05 times the molar amount of amino group in the modified polysiloxane), and 160.0 mL of N,N-dimethylformamide and add them to a reaction vessel. Raise the temperature of the reaction vessel to 70°C and stir for 1 hour. After the reaction is complete, transfer the reaction system to a rotary evaporator at 80°C and evaporate under reduced pressure until no liquid is collected to obtain modified polysiloxane.

[0045] Example 5 This embodiment provides a method for preparing modified polysiloxane for the production of highly resilient, stain-resistant sponge materials, comprising the following steps: Step I: Preparation of modified polysiloxane Weigh out 40.0 g of hexamethylcyclotrisiloxane, 25.0 g of trifluoropropylmethylcyclotrisiloxane, and 270.0 mL of N,N-dimethylformamide and add them to a reaction vessel. After the temperature of the reaction vessel is raised to 120°C, add 2.5 g of sodium hydroxide to the reaction vessel and keep the reaction at this temperature for 5 h. Then add 10.0 g of 1,1,3,3-tetramethyldisiloxane-1,3-diamine to the reaction vessel and keep the reaction at this temperature for 3 h. After the reaction is completed, adjust the reaction system to be neutral with acetic acid and then transfer the reaction system to a rotary evaporator at a temperature of 100°C. Evaporate the system under reduced pressure until no liquid is collected to obtain modified polysiloxane.

[0046] Step II: Preparation of modified polysiloxane Weigh out 40.0 g of modified polysiloxane, propylene oxide (1.10 times the molar amount of amino group in the modified polysiloxane), and 180.0 mL of N,N-dimethylformamide and add them to a reaction vessel. Raise the temperature of the reaction vessel to 80°C and stir for 2 hours. After the reaction is complete, transfer the reaction system to a rotary evaporator at 100°C and evaporate under reduced pressure until no liquid is collected to obtain modified polysiloxane.

[0047] Example 6 This embodiment provides a method for preparing modified polysiloxane for the production of highly resilient, stain-resistant sponge materials, comprising the following steps: Step I: Preparation of modified polysiloxane Weigh out 35.0 g of hexamethylcyclotrisiloxane, 20.0 g of trifluoropropylmethylcyclotrisiloxane, and 250.0 mL of N,N-dimethylformamide and add them to a reaction vessel. After the temperature of the reaction vessel is raised to 110℃, add 2.0 g of sodium hydroxide to the reaction vessel and keep the reaction at this temperature for 5 h. Then add 8.0 g of 1,1,3,3-tetramethyldisiloxane-1,3-diamine to the reaction vessel and keep the reaction at this temperature for 3 h. After the reaction is completed, adjust the reaction system to be neutral with acetic acid and then transfer the reaction system to a rotary evaporator at a temperature of 90℃. Evaporate under reduced pressure until no liquid is collected to obtain modified polysiloxane.

[0048] Step II: Preparation of modified polysiloxane Weigh out 35.0 g of modified polysiloxane, propylene oxide (1.08 times the molar amount of amino group in the modified polysiloxane), and 160.0 mL of N,N-dimethylformamide and add them to a reaction vessel. Raise the temperature of the reaction vessel to 75°C and stir for 2 hours. After the reaction is complete, transfer the reaction system to a rotary evaporator at 90°C and evaporate under reduced pressure until no liquid is collected to obtain modified polysiloxane.

[0049] Example 7 This embodiment provides a method for preparing a highly resilient, stain-resistant sponge material, including the following steps: Step 1: Preparation of mixed alcohols Weigh out 20.0g of polyethylene glycol, 20.0g of the modified polysiloxane prepared in Example 4, 5.0g of the flexible aerogel prepared in Example 1, 1.0g of polyurethane foam stabilizer, 2.0g of deionized water and 1.0g of stannous octoate, mix them to obtain a mixed alcohol.

[0050] Step 2: Preparation of anti-fouling sponge Weigh 36.0g of mixed alcohol and add it to the reaction vessel. After purging with nitrogen for protection, raise the temperature of the reaction vessel to 40℃ and add isophorone diisocyanate at 0.60 times the sum of the molar amounts of hydroxyl and amino groups in the mixed alcohol. Stir at 3000rpm for 10s and then transfer the reaction solution to a foaming box. After curing at room temperature for 4 hours, transfer the foam material to a drying oven at 80℃ and vacuum dry it to constant weight to obtain the anti-fouling sponge.

[0051] Example 8 This embodiment provides a method for preparing a highly resilient, stain-resistant sponge material, including the following steps: Step 1: Preparation of mixed alcohols Weigh out 30.0g of polyethylene glycol, 30.0g of the modified polysiloxane glycol prepared in Example 5, 6.0g of the flexible aerogel prepared in Example 2, 2.0g of polyurethane foam stabilizer, 3.0g of deionized water and 2.0g of stannous octoate, mix them to obtain a mixed alcohol.

[0052] Step 2: Preparation of anti-fouling sponge Weigh 48.0g of mixed alcohol and add it to the reaction vessel. After purging with nitrogen, raise the temperature of the reaction vessel to 60℃ and add isophorone diisocyanate, which is 0.65 times the sum of the molar amounts of hydroxyl and amino groups in the mixed alcohol. Stir at 3200rpm for 15s and then transfer the reaction solution to a foaming box. After curing at room temperature for 6 hours, transfer the foam material to a drying oven at 80℃ and vacuum dry it to constant weight to obtain an anti-fouling sponge.

[0053] Example 9 This embodiment provides a method for preparing a highly resilient, stain-resistant sponge material, including the following steps: Step 1: Preparation of mixed alcohols Weigh out 24.0g of polyethylene glycol, 24.0g of the modified polysiloxane prepared in Example 6, 6.0g of the flexible aerogel prepared in Example 3, 2.0g of polyurethane foam stabilizer, 3.0g of deionized water and 2.0g of stannous octoate, mix them to obtain a mixed alcohol.

[0054] Step 2: Preparation of anti-fouling sponge Weigh 42.0g of mixed alcohol and add it to the reaction vessel. After purging with nitrogen, raise the temperature of the reaction vessel to 50℃ and add isophorone diisocyanate, which is 0.64 times the sum of the molar amounts of hydroxyl and amino groups in the mixed alcohol. Stir at 3200rpm for 12s and then transfer the reaction solution to a foaming box. After curing at room temperature for 5 hours, transfer the foam material to a drying oven at 80℃ and vacuum dry it to constant weight to obtain the anti-fouling sponge.

[0055] Comparative Example 1 The difference between this comparative example and Example 9 is that steps ② and ③ are omitted in the preparation of the flexible aerogel used in step two, and pretreated expanded graphite is used to replace the modified graphite in an equal amount in step ④.

[0056] Comparative Example 2 The difference between this comparative example and Example 9 is that the flexible aerogel is omitted in step two.

[0057] Comparative Example 3 The difference between this comparative example and Example 9 is that the modified polysiloxane was omitted in step two.

[0058] Performance testing: The stain resistance levels of the stain-resistant sponges prepared in Examples 7-9 and Comparative Examples 1-3 were tested in accordance with the standard QB / T 5070-2017 "Test Methods for Stain Resistance of Artificial Leather and Synthetic Leather". The resilience of the stain-resistant sponges prepared in Examples 7-9 and Comparative Examples 1-3 was tested according to the standard HG / T 4993-2016 "Test Method for Resilience of Microporous Materials for Footwear". The tensile strength of the antifoams prepared in Examples 7-9 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 6344-2008 "Determination of tensile strength and elongation at break of flexible foam polymer materials". According to standard GB / T 7141-2008 "Test Method for Thermal Aging of Plastics", the composite polypropylene prepared in Examples 7-9 and Comparative Examples 1-3 was placed at 90℃ for 500h. The resilience of the material was determined according to standard HG / T 4993-2016, and the resilience retention rate was calculated. The tensile strength of the material was determined according to standard GB / T 6344-2008, and the tensile strength retention rate was calculated. The specific data are shown in Table 1. Table 1 - Performance Test Data for Each Sample

[0059] Data Analysis: Comparative analysis of the data in Table 1 reveals that the anti-fouling sponge prepared in this invention has a stain resistance level of 5, a resilience rate of 99.2%, and a tensile strength of 0.63 MPa. After heat aging, the anti-fouling sponge retains a resilience rate of 98.9% and a tensile strength of 99.3%. All these data are superior to the comparative example, indicating that: Comparative Example 1 used expanded graphite without tetrabutyl titanate treatment as a filler. The lack of a surface titanium oxide layer resulted in poor dispersibility in the organic phase and a lack of effective interfacial compatibility with siloxane matrices. During foaming and crosslinking, graphite particles easily aggregated, forming local defects that weakened the continuity and stability of the foam network structure. Due to insufficient interfacial bonding, graphite could not provide effective support within the foam and might even act as a stress concentration point, leading to a decrease in elastic modulus and tensile strength. Furthermore, the absence of a dense inorganic coating layer on the surface weakened the material's surface hydrophobicity and anti-fouling ability. In addition, under thermal aging conditions, interfacial debonding and microcrack propagation were prone to occur, further reducing the material's mechanical retention and resilience. Flexible aerogel plays a role in the system as a skeletal support and pore structure regulation. Its three-dimensional porous network helps to stabilize the cells during the foaming process, control the cell size distribution, and enhance the overall strength and flexibility of the structure after curing. In Comparative Example 2, after the aerogel was removed, the cell structure tended to be irregular, the closed-cell rate decreased, and it was easy to form collapse or adhesion, resulting in a decrease in the resilience of the material. At the same time, the lack of aerogel support makes the material more prone to irreversible deformation under external force, and the tensile strength and durability decrease. During the thermal aging process, due to the loose internal structure, the overall performance of the material deteriorates more significantly. Although the system still retains hydrophobic silica groups, the surface roughness and pore size are uncontrollable, and the stain resistance level is also affected to a certain extent. In Comparative Example 3, modified polysiloxane was removed, and only flexible aerogel was retained as the network support material. Although the porous structure of the aerogel can stabilize the cell morphology and maintain a certain structural integrity during the foaming process, avoiding large-area collapse, the overall elasticity of the system is significantly reduced due to the lack of flexible main chain and surface regulation groups in modified polysiloxane. The material's rebound ability after repeated compression is insufficient. In addition, modified polysiloxane usually contains tunable siloxane segments and functional groups, which not only endow the system with flexibility but also improve the interfacial bonding strength between the aerogel and the organic phase. In Comparative Example 3, due to the lack of such compatibility modifiers, the aerogel is prone to interfacial discontinuity or microcracks in the matrix, resulting in significant structural degradation of the foam during mechanical loading or thermal aging. At the same time, this comparative example also lost the low surface energy groups introduced in modified polysiloxane, such as fluorine-containing or alkyl-containing segments, thereby weakening the hydrophobicity and anti-fouling ability of the material. The surface is prone to hydrophilic transformation after long-term use or contamination, pollutants adhere firmly, are difficult to clean, and the overall stain resistance level decreases. Ultimately, it is demonstrated that while introducing modified polysiloxane alone can improve the material's elasticity, it is slightly insufficient in terms of mechanical strength and thermal stability. Using flexible aerogel alone is also difficult to achieve a balanced performance, especially in terms of durability and elastic recovery. However, when the two work synergistically, the modified polysiloxane softens the skeleton and improves interfacial affinity, while the flexible aerogel provides stable support and inorganic reinforcement. This effectively reconciles the contradiction between elasticity and strength. The material maintains a high level of retention after thermal aging, indicating that its internal structure is more stable, its skeleton network is denser, and it has good long-term service capability. Through this mutual integration and functional complementarity of organic and inorganic components in the microstructure, not only are the mechanical properties and stain resistance improved, but the material also maintains excellent elastic recovery and structural integrity when facing high temperatures and external impacts.

[0060] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a highly resilient, stain-resistant sponge material, characterized in that, Includes the following steps: S1. After mixing polyethylene glycol, modified polysiloxane glycol, flexible aerogel, polyurethane foam stabilizer, deionized water and stannous octoate, a mixed alcohol is obtained. S2. Add the mixed alcohol to the reactor, purge with nitrogen for protection, raise the reactor temperature to 40-60℃, add the calculated amount of isophorone diisocyanate to the reactor, stir at 3000-3200 rpm for 10-15 seconds, transfer the reaction solution to the foaming box, and cure at room temperature for 4-6 hours. After post-treatment, the anti-fouling sponge is obtained.

2. The method for preparing a highly resilient, stain-resistant sponge material according to claim 1, characterized in that, In step S1, the ratio of polyethylene glycol, modified polysiloxane, flexible aerogel, polyurethane foam stabilizer, deionized water, and stannous octoate is 20-30g:20-30g:5-6g:1-2g:2-3g:1-2g; in step S2, the amount of isophorone diisocyanate added is 0.60-0.65 times the sum of the molar amounts of hydroxyl and amino groups in the mixed alcohol.

3. The method for preparing a highly resilient, stain-resistant sponge material according to claim 1, characterized in that, The method for preparing the modified polysiloxane includes the following steps: A1. Hexamethylcyclotrisiloxane, trifluoropropylmethylcyclotrisiloxane and N,N-dimethylformamide are added to a reaction vessel. After the temperature of the reaction vessel is raised to 100-120℃, sodium hydroxide is added to the reaction vessel. After the reaction is kept at this temperature for 4-5 hours, 1,1,3,3-tetramethyldisiloxane-1,3-diamine is added to the reaction vessel. The reaction is kept at this temperature for 2-3 hours. After post-treatment, modified polysiloxane is obtained. A2. Add the modified polysiloxane, the calculated amount of propylene oxide and N,N-dimethylformamide to the reactor, raise the temperature of the reactor to 70-80℃, keep it at this temperature and stir for 1-2 hours, and then proceed with the post-treatment to obtain the modified polysiloxane.

4. The method for preparing a highly resilient, stain-resistant sponge material according to claim 3, characterized in that, In step A1, the ratio of hexamethylcyclotrisiloxane, trifluoropropylmethylcyclotrisiloxane, N,N-dimethylformamide, sodium hydroxide, and 1,1,3,3-tetramethyldisiloxane-1,3-diamine is 6-8g:3-5g:50-54mL:0.3-0.5g:1-2g; in step A2, the ratio of modified polysiloxane to N,N-dimethylformamide is 6-8g:32-36mL, wherein the amount of propylene oxide is 1.05-1.10 times the molar amount of amino group in the modified polysiloxane.

5. The method for preparing a highly resilient, stain-resistant sponge material according to claim 1, characterized in that, The preparation method of the flexible aerogel includes the following steps: B1. Modified graphite, hexadecyltrimethylammonium bromide and deionized water are added to the reaction vessel and stirred. After the temperature of the reaction vessel is raised to 40-60℃, the pH of the reaction system is adjusted to 4-5 with acetic acid and silicon source solution is added to the reaction vessel. After the reaction is kept at the temperature for 2-3 hours, silica sol is added to the reaction vessel and the reaction is kept at the temperature for 1-2 hours to obtain modified gel. B2. Transfer the modified gel to a drying oven, raise the temperature of the drying oven to 60-80℃, keep it at this temperature for 20-24 hours, take out the gel and wash it 3-5 times with anhydrous ethanol and deionized water. The post-treatment yields a flexible aerogel.

6. The method for preparing a highly resilient, stain-resistant sponge material according to claim 5, characterized in that, In step B1, the ratio of modified graphite, hexadecyltrimethylammonium bromide, deionized water, silicon source solution and silica sol is 3-5g:0.3-0.5g:80-100mL:10-15g:2-3g. The composite silicon source is obtained by mixing methyl orthosilicate, tridecafluorooctyltrimethoxysilane and 3-aminopropyltriethoxysilane in a ratio of 6-8g:3-5g:1-2g.

7. The method for preparing a highly resilient, stain-resistant sponge material according to claim 5, characterized in that, The method for preparing the modified graphite includes the following steps: C1. Add the pretreated expanded graphite dispersion, anhydrous ethanol and deionized water to the reaction vessel. After adjusting the pH of the reaction system to 4-5 with acetic acid, raise the temperature of the reaction vessel to 40-60℃ and keep it at this temperature for 4-6 hours with stirring. The modified graphite preform is then obtained through post-treatment. C2. Modified graphite preforms are added to a muffle furnace and calcined to obtain modified graphite.

8. The method for preparing a highly resilient, stain-resistant sponge material according to claim 7, characterized in that, In step C1, the ratio of the pretreated expanded graphite dispersion, anhydrous ethanol, and deionized water is 2-3 mL: 20-30 mL: 10-12 mL. The pretreated expanded graphite dispersion is obtained by thoroughly mixing pretreated expanded graphite and tetrabutyl titanate at a ratio of 1 g: 2-3 mL.

9. A highly resilient, stain-resistant sponge material, characterized in that, The high resilience anti-fouling sponge material is prepared using the preparation method of the high resilience anti-fouling sponge material as described in any one of claims 1-8.

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