Glass fiber reinforced epoxy resin material and antifouling antibacterial self-cleaning pipeline

Abstract

The invention discloses a glass fiber reinforced epoxy resin material and an antifouling antibacterial self-cleaning pipeline in the technical field of composite materials, the material comprises bisphenol A epoxy resin, cardanol modified phenolic amide curing agent, electronic grade glass fiber cloth and a plurality of auxiliaries, three functional modified compounds, namely a fluorosilane modified carbon nanotube anchoring agent, a silver-loaded zeolite imidazate framework antibacterial agent and a bionic multi-arm epoxidized POSS interface reinforcing agent, are introduced. The three compounds are obtained by a specific preparation method, and respectively play roles in enhancing interface anchoring, providing antibacterial and bactericidal functions and improving interface compatibility. The pipeline is prepared from the material, has multiple functions of super-hydrophobicity, antibacterial adhesion, sterilization and self-cleaning, realizes integrated combination of an antifouling and antibacterial coating and a matrix material, remarkably improves the service life and durability of the pipeline, and is suitable for the field of fluid transportation in a harsh environment.

Description

Technical Field

[0001] This invention relates to the field of composite material technology, specifically to a glass fiber reinforced epoxy resin material and a self-cleaning, anti-fouling, antibacterial pipe. Background Technology

[0002] In fields such as petrochemicals, marine engineering, and urban water management, pipeline systems play a crucial role in fluid transportation. However, pipelines operating in complex environments face serious threats from microbial corrosion and biofouling, leading to scaling on the inner walls, increased flow resistance, decreased heat transfer efficiency, and shortened service life. Current technologies for pipeline antifouling primarily employ chemical bactericide coatings, low-surface-energy anti-adhesion coatings, or electrolytic antifouling techniques. However, these methods have significant limitations: chemical bactericides are prone to leakage and may cause environmental pollution; anti-adhesion coatings lack sufficient mechanical strength and are easily worn and fail; and electrolytic technology requires a continuous energy supply and involves complex equipment. Furthermore, while traditional fiberglass-reinforced epoxy resin pipes possess excellent mechanical properties and chemical corrosion resistance, their surfaces are easily adhered to by microorganisms, lacking active antibacterial capabilities and failing to meet the long-term use requirements in harsh environments.

[0003] In recent years, biomimetic principles have provided new insights into pipeline antifouling technology. Many biological surfaces in nature possess remarkable self-cleaning capabilities, such as the superhydrophobic properties of lotus leaves and the anti-adhesion structure of microorganisms on shark skin. Researchers have attempted to develop biomimetic antifouling materials by mimicking the micro- and nano-structures and chemical compositions of these biological surfaces. However, applying these biomimetic concepts to industrial pipeline systems still faces significant challenges: insufficient interfacial bonding strength between the biomimetic structure and the pipeline substrate material; difficulty in precisely controlling the micro- and nano-structures during large-scale production; and the tendency of functional surface coatings to detach or wear under fluid erosion and pressure fluctuations, resulting in poor durability of antifouling performance.

[0004] To address the aforementioned technical bottlenecks, this invention, through material system innovation and preparation process optimization, has developed a glass fiber reinforced epoxy resin material and a self-cleaning, antifouling, and antibacterial pipe. By introducing various specially designed modified compounds, this material achieves an organic combination of biomimetic antifouling properties and the pipe matrix material. It maintains the required mechanical strength and corrosion resistance of the pipe while endowing it with multiple functions such as superhydrophobicity, antibacterial adhesion, and bactericidal properties, significantly improving the service life and reliability of the pipe in harsh environments. Summary of the Invention

[0005] The purpose of this invention is to provide a glass fiber reinforced epoxy resin material and a fouling-resistant, antibacterial, and self-cleaning pipe, which solves the technical problems of existing pipe materials being prone to biofouling, having poor antibacterial properties, and having weak adhesion between the surface coating and the substrate.

[0006] The present invention achieves the above objectives through the following technical solutions: A glass fiber reinforced epoxy resin material, comprising the following raw materials in parts by weight: Bisphenol A type epoxy resin: 80-120 parts by weight; Cashew phenol modified phenolic amide curing agent: 25-35 parts by weight; Fluorosilane-modified carbon nanotube anchoring agent: 5-15 parts by weight; Silver-supported zeolite imidazole ester framework antibacterial agent: 3-8 parts by weight; Bionic multi-arm epoxide POSS interface enhancer: 10-20 parts by weight; Electronic grade fiberglass cloth: 50-70 parts by weight; Perfluoropolyether surfactant: 1-3 parts by weight; Nano silica: 2-5 parts by weight; Polyether-modified siloxane leveling agent: 0.5-2 parts by weight; The preparation method of the fluorosilane-modified carbon nanotube anchoring agent includes: A1, refluxing multi-walled carbon nanotubes in a mixture of concentrated sulfuric acid and concentrated nitric acid at 68-72℃; washing with deionized water until neutral, and vacuum drying at 78-82℃ to obtain acidified multi-walled carbon nanotubes; dispersing the acidified multi-walled carbon nanotubes in anhydrous toluene and ultrasonically treating to form a carbon nanotube suspension; mixing a mixture of 3-aminopropyltriethoxysilane and 1H,1H,2H,2H-perfluorodecyltriethoxysilane with ethanol and deionized water, adding glacial acetic acid, and stirring for pre-hydrolysis at 58-62℃; adding the pre-hydrolyzed silane solution to the carbon nanotube suspension, and adding dibutyltin dilaurate; reacting at 108-112℃ under nitrogen protection; A2, after the reaction is completed, washing alternately with toluene and ethanol, and vacuum drying at 58-62℃.

[0007] In this invention, the preparation steps of the cashew phenol-modified phenolic amide curing agent are as follows: Hydroxymethylation reaction: First, cashew phenol and paraformaldehyde are added to a reaction vessel at a molar ratio of 1:(1.5-2.5), and triethylamine (0.5-2% of the cashew phenol mass) is added. The mixture is stirred at 80-90℃ for 2-3 hours to carry out the hydroxymethylation reaction, generating cashew phenolic prepolymer. Dehydration and premixing: Subsequently, the temperature of the reaction system is raised to 120-140℃, and dehydration is performed under vacuum until the moisture content of the system is below 0.5%. Then, the system is cooled to 80-90℃, and a measured amount of polyamine compound (such as diethylenetriamine or m-phenylenediamine) is added. The molar ratio of polyamine to cashew phenol is (1.2-1.8):1. The polyamine is slowly added dropwise, controlling the temperature not to exceed 100℃. After the addition is complete, the mixture is kept at this temperature for a pre-reaction of 1-2 hours to initially form intermediates such as Mannich base. High-temperature polycondensation reaction: The temperature is then gradually increased to 160-180℃, and the main polycondensation reaction is carried out for 3-5 hours under nitrogen protection. During this period, the reaction progress is monitored by measuring the change in amine value. Post-treatment: After the reaction is completed, the remaining small molecule by-products and moisture are removed under vacuum to finally obtain a brownish-red viscous liquid cashew phenol-modified phenolic amide curing agent.

[0008] In this invention, the preparation process of the fluorosilane-modified carbon nanotube anchoring agent is based on a multi-step chemical modification reaction. First, the carbon nanotube surface is oxidized by reflux treatment with a mixed strong acid, introducing oxygen-containing functional groups such as carboxyl and hydroxyl groups at the edges and defect sites of its graphite lattice. These active groups provide reaction sites for the subsequent grafting of the silane coupling agent. The pre-hydrolysis stage is a crucial step. Under the action of an acidic catalyst, the alkoxy groups of the silane coupling agent undergo hydrolysis to generate highly reactive silanol groups, while the fluoroalkyl segments exhibit low surface energy characteristics due to their strong electronegativity. In the condensation reaction stage, the newly generated silanol groups undergo dehydration condensation with the hydroxyl groups on the carbon nanotube surface, forming a strong silicon-oxygen bond. The catalyst further promotes the cross-linking reaction between silane molecules, constructing a three-dimensional fluorosilane polymer network on the carbon nanotube surface. This unique structural design enables the modified carbon nanotubes to integrate multiple functions: on the one hand, the long fluoroalkyl chains on their surface extend outward, endowing the material with excellent hydrophobicity; on the other hand, through the design of the silane coupling agent molecules, the terminal active functional groups (such as amino groups) remain exposed after modification. These functional groups can chemically react with the epoxy groups in the epoxy resin matrix to form strong covalent bonds. This strong chemical bonding, combined with the mechanical reinforcing effect of the carbon nanotubes themselves, significantly improves the bonding strength of the composite material interface.

[0009] According to a preferred embodiment of the present invention, in step A1, the reflux treatment at 68-72°C is carried out for 4-6 hours; the reaction time at 108-112°C is carried out for 24-30 hours.

[0010] According to a preferred embodiment of the present invention, in step A2, the vacuum drying time at 58-62°C is 12-14 hours.

[0011] According to a preferred embodiment of the present invention, the preparation method of the silver-supported zeolite imidazole ester framework antibacterial agent includes: B1, dissolving 2-methylimidazole in methanol to form solution A; dissolving zinc nitrate hexahydrate in methanol to form solution B; mixing solution B and solution A under stirring, reacting at room temperature; collecting the white precipitate by centrifugation, washing three times with methanol, and drying under vacuum at 58-62℃ to obtain ZIF-8 nanocrystals; B2, dispersing the ZIF-8 nanocrystals in silver nitrate solution, stirring in the dark; collecting the solid material by centrifugation, washing with deionized water, and redispersing in water; irradiating with a xenon lamp at 15-25℃; washing the final product with ethanol and drying under vacuum at 58-62℃.

[0012] In this invention, the synthesis of a silver-supported zeolite imidazolium ester framework antibacterial agent is based on coordination chemistry and photochemical reduction principles. During the formation of the zeolite imidazolium ester framework, divalent zinc ions and 2-methylimidazolium ligands self-assemble to form a typical zeolite topology, where zinc atoms act as metal nodes and form coordination bonds with imidazolium nitrogen atoms, constructing a three-dimensional crystal framework with regular channels. This metal-organic framework material has a high specific surface area and uniform channel structure, providing an ideal carrier for silver ion loading. During silver loading, silver ions enter the pores of the zeolite imidazolium ester framework through ion exchange and physical adsorption, forming coordination relationships with nitrogen atoms in the framework. The subsequent photoreduction reaction occurs under specific wavelength illumination, where photogenerated electrons reduce silver ions to zero-valent silver nanoparticles. These nanoparticles are uniformly distributed in the framework channels, and their size is controlled by the confinement effect of the framework channels. This structural design enables the controlled release of silver ions. The synergistic antibacterial effect of zinc and silver ions significantly enhances the antibacterial efficacy of the material. At the same time, the framework structure stabilizes the silver nanoparticles, preventing their aggregation and inactivation, thus ensuring long-lasting antibacterial performance.

[0013] According to a preferred embodiment of the present invention, in step B1, the reaction time at room temperature is 4-6 h; the molar ratio of 2-methylimidazole to zinc nitrate hexahydrate is (4-8):1.

[0014] According to a preferred embodiment of the present invention, in step B2, the stirring time in the dark is 12-14 hours; the xenon lamp irradiation time is 4-6 hours.

[0015] According to a preferred embodiment of the present invention, the preparation method of the biomimetic multi-arm epoxidized POSS interface enhancer includes: C1, dissolving octavinylsilsesquioxane in anhydrous tetrahydrofuran, purging with nitrogen to remove oxygen, and then adding dropwise a solution prepared by hydrogen peroxide-urea adduct and sodium tungstate dissolved in methanol at 64-66°C; the reaction solution is washed with saturated sodium chloride solution, the organic phase is dried with anhydrous magnesium sulfate, and then rotary evaporated to obtain epoxidized POSS; C2, reacting epoxidized POSS with 4-hydroxybenzoic acid under reflux in xylene; after cooling, adding triethylamine and glycidyl methacrylate, and reacting at 78-82°C; after the reaction is completed, rotary evaporating, precipitating with cold diethyl ether, and drying under vacuum at 38-42°C.

[0016] In this invention, the synthesis of the biomimetic multi-arm epoxidized POSS interface enhancer employs a multi-step organic synthesis strategy. First, octavinyl POSS undergoes an epoxidation reaction with a hydrogen peroxide-urea adduct under sodium tungstate catalysis, converting the vinyl group into a highly reactive ethylene oxide ring to obtain epoxidized POSS. Subsequently, a stepwise functionalization reaction is carried out: In the first step, the epoxidized POSS reacts with 4-hydroxybenzoic acid under heating conditions. The inherent phenolic hydroxyl group in the 4-hydroxybenzoic acid molecule does not participate in this step; its carboxyl group is located on its own proton (H in -COOH). + Under the catalysis of an amine, the phenolic hydroxyl group acts as a nucleophile, attacking and opening part of the epoxy groups of the epoxidized POSS, resulting in a ring-opening esterification reaction. This process successfully introduces a rigid aromatic ring structure into the POSS backbone, while simultaneously generating a new secondary hydroxyl group (alcoholic hydroxyl group) at the ring-opening site, forming a β-hydroxy ester structure. In the second step, under the catalysis of a tertiary amine (such as triethylamine), the phenolic hydroxyl group undergoes a ring-opening reaction with the epoxy group of glycidyl methacrylate (GMA), grafting a flexible chain containing terminal acrylate double bonds onto the POSS, while simultaneously generating a new secondary hydroxyl group. Finally, under the action of an amine catalyst, the hydroxyl group in the system (acting as a nucleophile) undergoes an oxygen-Michael addition reaction with the acrylate double bond, further constructing or extending the multi-arm star-shaped network structure around the POSS core. This unique biomimetic design allows the interface reinforcing agent to simultaneously possess multiple functional groups, including rigid aromatic rings, flexible chains, and unreacted epoxy groups. Its cage-like siloxane core provides a stereoreinforcing effect, the multi-arm structure increases the flexibility of the molecular chain, and the terminal epoxy groups can form covalent crosslinks with the resin matrix. This multi-level interface reinforcement mechanism significantly improves stress transfer efficiency in composite materials and effectively prevents interface failure.

[0017] According to a preferred embodiment of the present invention, in step C1, the reaction time is 12-14 h; the molar ratio of the hydrogen peroxide-urea adduct to octavinylsilsesquioxane is (8-12):1.

[0018] According to a preferred embodiment of the present invention, in step C2, the reaction time at 78-82°C is 8-10 hours.

[0019] The present invention also provides a self-cleaning, antifouling, antibacterial pipe made from the aforementioned glass fiber reinforced epoxy resin material.

[0020] The beneficial effects of this invention are as follows: The glass fiber reinforced epoxy resin material and antifouling, antibacterial, and self-cleaning pipe provided by this invention exhibit excellent comprehensive performance, with its technical effects mainly manifested in three aspects. First, the material achieves a perfect combination of antifouling and antibacterial properties with the mechanical properties of the matrix. Through the synergistic effect of three innovative modified compounds, the material achieves durable antifouling and antibacterial capabilities while maintaining excellent mechanical strength. The fluorosilane-modified carbon nanotube anchoring agent forms a micro-nano hierarchical structure at the interface, endowing the material with superhydrophobic properties, enabling the pipe surface to effectively prevent the initial adhesion of microorganisms. The silver-loaded zeolite imidazole ester framework antibacterial agent provides a dual antibacterial mechanism through the slow release of silver and zinc ions, effectively killing already attached microorganisms. The biomimetic multi-arm epoxy POSS interface reinforcing agent significantly improves the compatibility between the components, ensuring the stability of the functional structure. This synergistic effect gives the pipe surface a self-cleaning function similar to a lotus leaf, while maintaining the high strength and corrosion resistance of the matrix material.

[0021] Secondly, this material exhibits significantly improved durability and environmental adaptability. The specially designed interface-reinforced structure ensures a strong chemical bond between the antifouling and antibacterial functional layer and the substrate material, avoiding the problems of easy peeling and wear common with traditional coatings. The pipe maintains stable superhydrophobic properties during long-term use, and its antifouling effect does not significantly diminish even under fluid erosion and pressure fluctuations. The material also possesses excellent chemical corrosion resistance and anti-aging properties, enabling it to adapt to various harsh operating conditions such as acidic and alkaline environments, high-salt environments, and humid and hot environments. This sustained performance stability greatly extends the service life of the pipe, reducing maintenance costs and replacement frequency.

[0022] Finally, this technology offers excellent processability and application value. The material preparation process is mature and reliable, and the synthesis methods for the three modified compounds are simple and easy to implement, suitable for large-scale production. The resulting pipes have advantages such as smooth inner walls, low flow resistance, and low energy consumption, showing broad application prospects in petrochemical, marine engineering, and urban water systems. Compared with traditional pipes, this self-cleaning pipe effectively prevents biofouling and microbial corrosion, maintains transportation efficiency, reduces operating costs, and decreases the use of chemical disinfectants, making it more environmentally friendly and in line with the requirements of green and sustainable development. Detailed Implementation

[0023] The following detailed embodiments are only used to further illustrate this application and should not be construed as limiting the scope of protection of this application. Those skilled in the art can make some non-essential improvements and adjustments to this application based on the above application content.

[0024] The following is information on domestic suppliers of key related equipment and materials: The bisphenol A type epoxy resin was purchased from Baling Petrochemical Branch of China Petrochemical Corporation Asset Management Co., Ltd.

[0025] The electronic-grade glass fiber cloth was purchased from China Jushi Co., Ltd.

[0026] The perfluoropolyether surfactant was purchased from Zhonghao Chenguang Chemical Research Institute Co., Ltd.

[0027] The nano-silica was purchased from Guangzhou Jibisheng Technology Industry Co., Ltd.

[0028] The polyether-modified siloxane leveling agent was purchased from Yudeqian New Material Technology (Shanghai) Co., Ltd.

[0029] The multi-walled carbon nanotubes were purchased from Shenzhen Nanoport Co., Ltd.

[0030] The 3-aminopropyltriethoxysilane was purchased from Wuhan Jizi Chemical Technology Co., Ltd.

[0031] The 1H,1H,2H,2H-perfluorodecyltriethoxysilane was purchased from Quzhou Mingfeng Chemical Co., Ltd.

[0032] The glacial acetic acid was purchased from Jiangsu Suopu (Group) Co., Ltd.

[0033] The dibutyltin dilaurate was purchased from Beijing Huawirui Chemical Co., Ltd.

[0034] The 2-methylimidazole was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0035] The zinc nitrate hexahydrate was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0036] The silver nitrate solution was purchased from Xilong Scientific Co., Ltd.

[0037] The xenon lamp was purchased from Beijing Zhongjiao Jinyuan Technology Co., Ltd.

[0038] The octavinylsilsesquioxane was purchased from Wuhan Huaxiang Kejie Biotechnology Co., Ltd.

[0039] The hydrogen peroxide-urea adduct was purchased from Tianjin Xiens Biochemical Technology Co., Ltd.

[0040] The sodium tungstate was purchased from Shanghai Experimental Reagent Co., Ltd.

[0041] The 4-hydroxybenzoic acid was purchased from Shandong Xiya Chemical Industry Co., Ltd.

[0042] The triethylamine was purchased from Hangzhou Daziran Technology Co., Ltd.

[0043] The glycidyl methacrylate was purchased from Anhui Jucheng Chemical Co., Ltd.

[0044] Example 1: Take 100g of bisphenol A type epoxy resin, 30g of cashew phenol modified phenolic amide curing agent, 10g of fluorosilane modified carbon nanotube anchoring agent, 5g of silver-loaded zeolite imidazole ester framework antibacterial agent, 15g of biomimetic multi-arm epoxy POSS interface reinforcing agent, 60g of electronic grade glass fiber cloth, 2g of perfluoropolyether surfactant, 3g of nano silica, and 1g of polyether modified siloxane leveling agent. The preparation method of the fluorosilane-modified carbon nanotube anchoring agent is as follows: 5g of multi-walled carbon nanotubes are placed in a 250mL round-bottom flask, and 150mL of a mixture of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1 is added. The mixture is refluxed in an oil bath at 70℃ for 5h, cooled to room temperature, washed with deionized water until neutral, and vacuum dried at 80℃ for 12h to obtain acidified multi-walled carbon nanotubes; 3g of 3-aminopropyltriethoxysilane and 6g of... 1H,1H,2H,2H-perfluorodecyltriethoxysilane was placed in a 100mL beaker, 10g of anhydrous ethanol and 2g of deionized water were added, and 0.1g of glacial acetic acid was added dropwise. The mixture was pre-hydrolyzed by stirring in a 60℃ water bath for 30min. Acidified multi-walled carbon nanotubes were dispersed in 100mL of anhydrous toluene and sonicated for 30min to form a uniform suspension. The pre-hydrolyzed silane solution and 0.5g of dibutyltin dilaurate were added, and the mixture was purged with nitrogen and reacted in an oil bath at 110℃ for 28h. After the reaction, the mixture was washed three times each with toluene and ethanol, and then vacuum dried at 60℃ for 13h to obtain a fluorosilane-modified carbon nanotube anchoring agent. The preparation method of the silver-supported zeolite imidazole ester framework antibacterial agent was as follows: 8g of... 2-Methylimidazole was dissolved in 100 mL of methanol to form solution A. 5 g of zinc nitrate hexahydrate was dissolved in 50 mL of methanol to form solution B. Solution B was poured into solution A with stirring, and the mixture was reacted at room temperature for 5 h. The white precipitate was collected by centrifugation, washed three times with methanol, and dried under vacuum at 60 °C for 12 h to obtain ZIF-8 nanocrystals. 5 g of ZIF-8 nanocrystals were dispersed in 100 mL of methanol... The solid material was collected by centrifugation in 0.1 mol / L silver nitrate solution and stirred in the dark for 13 h. After washing twice with deionized water, it was redispersed in 100 mL of deionized water and irradiated with a 300 W xenon lamp at 20 °C for 5 h. The final product was washed three times with ethanol and dried under vacuum at 60 °C for 12 h to obtain a silver-supported zeolite imidazole ester framework antibacterial agent. The preparation method of the biomimetic multi-arm epoxidized POSS interface enhancer is as follows: 10 g of octavinylsilsesquioxane was dissolved in 100 mL of anhydrous tetrahydrofuran. After purging with nitrogen to remove oxygen, 12 g of hydrogen peroxide-urea adduct and 0.12g of sodium tungstate was dissolved in 50mL of methanol to prepare a solution, and the reaction was carried out for 13 hours. The reaction solution was washed three times with saturated sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation to obtain epoxidized POSS. 10g of epoxidized POSS and 6g of... 4-Hydroxybenzoic acid was refluxed in 100 mL xylene for 6 h. After cooling to room temperature, 3 g of triethylamine and 8 g of glycidyl methacrylate were added, and the mixture was reacted in an oil bath at 80 °C for 9 h. After the reaction, the solvent was removed by rotary evaporation, and the mixture was precipitated three times with cold diethyl ether and dried under vacuum at 40 °C for 24 h to obtain a biomimetic multi-arm epoxidized POSS interface enhancer. The preparation method of the antifouling, antibacterial and self-cleaning pipe is as follows: Bisphenol A type epoxy resin was preheated to 50 °C, and perfluoropolyether surfactant and nano-silica were added. The mixture was stirred at 2000 rpm for 15 min, and then fluorosilane-modified carbon nanotube anchoring agent, silver-loaded zeolite imidazole ester framework antibacterial agent and biomimetic multi-arm epoxidized POSS interface enhancer were added. The mixture was then high-speed sheared at 3000 rpm for 30 min to ensure that the modifier and resin system were fully interacted. The process involves: transferring the product to a dual planetary mixer, adding cashew phenol-modified phenolic amide curing agent and polyether-modified siloxane leveling agent, and stirring at 500 rpm for 20 minutes under a vacuum of -0.095 MPa to remove air bubbles; applying the prepared functional epoxy resin solution to both sides of electronic-grade glass fiber cloth with a unit area mass of 250 g / m², controlling the resin content to 38%, and then passing it through an 80℃ hot roller pre-curing zone for 3 minutes to form a prepreg; cutting the prepreg and winding it onto a mandrel, sealing it with a vacuum bag film, and then placing it in an autoclave under a pressure of 0.6 MPa, followed by a stepped temperature increase program of 80℃ / 2h, 100℃ / 1h, 120℃ / 2h, and 150℃ / 4h for final curing; and finally demolding after cooling to obtain a self-cleaning, anti-fouling, antibacterial pipe integrating the substrate and functional layer.

[0045] Example 2, its specific implementation method is the same as Example 1, the difference is that 80g of bisphenol A type epoxy resin, 25g of cashew phenol modified phenolic amide curing agent, 5g of fluorosilane modified carbon nanotube anchoring agent, 3g of silver-loaded zeolite imidazole ester framework antibacterial agent, 10g of biomimetic multi-arm epoxy POSS interface reinforcing agent, 50g of electronic grade glass fiber cloth, 1g of perfluoropolyether surfactant, 2g of nano silica, and 0.5g of polyether modified siloxane leveling agent are taken; the preparation method of fluorosilane modified carbon nanotube anchoring agent is as follows: 3g of multi-walled carbon nanotubes are placed in a 250mL round bottom flask, 120mL of a mixture of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1 is added, refluxed in an oil bath at 68℃ for 4h, cooled to room temperature, washed with deionized water until neutral, and vacuum dried at 78℃ for 12h to obtain acidified multi-walled carbon nanotubes; 2g of 3-aminopropyltriethoxysilane and 4g of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was placed in a 100mL beaker, 8g of anhydrous ethanol and 1.5g of deionized water were added, and 0.06g of glacial acetic acid was added dropwise. The mixture was pre-hydrolyzed by stirring in a water bath at 58℃ for 30min. Acidified multi-walled carbon nanotubes were dispersed in 80mL of anhydrous toluene and sonicated for 30min to form a uniform suspension. The pre-hydrolyzed silane solution and 0.3g of dibutyltin dilaurate were added, and the mixture was protected with nitrogen and reacted in an oil bath at 108℃ for 24h. After the reaction, the mixture was washed three times each with toluene and ethanol, and then vacuum dried at 58℃ for 12h to obtain the fluorosilane-modified carbon nanotube anchoring agent. The preparation method of the silver-supported zeolite imidazole ester framework antibacterial agent was as follows: 6g of... 2-Methylimidazole was dissolved in 80 mL of methanol to form solution A. 4 g of zinc nitrate hexahydrate was dissolved in 40 mL of methanol to form solution B. Solution B was poured into solution A with stirring, and the reaction was allowed to proceed at room temperature for 4 h. The white precipitate was collected by centrifugation, washed three times with methanol, and dried under vacuum at 58 °C for 12 h to obtain ZIF-8 nanocrystals. 3 g of ZIF-8 nanocrystals were dispersed in 80 mL of methanol. The solid material was collected by centrifugation in 0.1 mol / L silver nitrate solution and stirred in the dark for 12 h. After washing twice with deionized water, it was redispersed in 80 mL of deionized water and irradiated with a 300 W xenon lamp at 15 °C for 4 h. The final product was washed three times with ethanol and dried under vacuum at 58 °C for 12 h to obtain a silver-supported zeolite imidazole ester framework antibacterial agent. The preparation method of the biomimetic multi-arm epoxidized POSS interface enhancer is as follows: 8 g of octavinylsilsesquioxane was dissolved in 80 mL of anhydrous tetrahydrofuran. After purging with nitrogen to remove oxygen, 10 g of hydrogen peroxide-urea adduct and 0.1 g of sodium tungstate was dissolved in 40 mL of methanol to prepare a solution. The reaction was carried out for 12 h. The reaction solution was washed three times with saturated sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation to obtain epoxidized POSS. 8 g of epoxidized POSS and 4 g of... 4-Hydroxybenzoic acid was refluxed in 80 mL xylene for 6 h. After cooling to room temperature, 2 g of triethylamine and 6 g of glycidyl methacrylate were added, and the mixture was reacted in an oil bath at 78 °C for 8 h. After the reaction, the solvent was removed by rotary evaporation, and the mixture was precipitated three times with cold diethyl ether and vacuum dried at 38 °C for 24 h to obtain a biomimetic multi-arm epoxidized POSS interface enhancer. The preparation method of the antifouling, antibacterial and self-cleaning pipe is as follows: Bisphenol A type epoxy resin was preheated to 50 °C, and perfluoropolyether surfactant and nano-silica were added. The mixture was stirred at 2000 rpm for 15 min, and then fluorosilane-modified carbon nanotube anchoring agent, silver-loaded zeolite imidazole ester framework antibacterial agent and biomimetic multi-arm epoxidized POSS interface enhancer were added. The mixture was then high-speed sheared at 3000 rpm for 30 min to achieve good integration of functional groups in the resin. Dispersion and anchoring; Cashew phenol-modified phenolic amide curing agent and polyether-modified siloxane leveling agent are added to a dual planetary mixer, and stirred at 500 rpm for 20 min under a vacuum of -0.095 MPa; the prepared functional epoxy resin solution is scraped onto both sides of electronic-grade glass fiber cloth with a unit area mass of 200 g / m², controlling the resin content to 35%, and held in an 80℃ hot roller pre-curing zone for 2 min to prepare a prepreg; the prepreg is cut and wound onto a mandrel, sealed with a vacuum bag film, and sent to an autoclave under a pressure of 0.5 MPa, cured according to a stepped temperature increase program of 80℃ / 2h, 100℃ / 1h, 120℃ / 2h, and 150℃ / 4h; after cooling and demolding, a dense, functionally integrated anti-fouling, antibacterial, and self-cleaning pipe is obtained.

[0046] Example 3, its specific implementation method is the same as Example 1, the difference is that 120g of bisphenol A type epoxy resin, 35g of cashew phenol modified phenolic amide curing agent, 15g of fluorosilane modified carbon nanotube anchoring agent, 8g of silver-loaded zeolite imidazole ester framework antibacterial agent, 20g of biomimetic multi-arm epoxy POSS interface reinforcing agent, 70g of electronic grade glass fiber cloth, 3g of perfluoropolyether surfactant, 5g of nano silica, and 2g of polyether modified siloxane leveling agent are taken; wherein the preparation method of fluorosilane modified carbon nanotube anchoring agent is as follows: 8g of multi-walled carbon nanotubes are placed in a 250mL round bottom flask, 180mL of a mixture of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1 is added, refluxed in an oil bath at 72℃ for 6h, cooled to room temperature, washed with deionized water until neutral, and vacuum dried at 82℃ for 12h to obtain acidified multi-walled carbon nanotubes; 4g of 3-aminopropyltriethoxysilane and 8g 1H,1H,2H,2H-perfluorodecyltriethoxysilane was placed in a 100mL beaker, 12g of anhydrous ethanol and 2.5g of deionized water were added, and 0.12g of glacial acetic acid was added dropwise. The mixture was pre-hydrolyzed by stirring in a water bath at 62℃ for 30min. Acidified multi-walled carbon nanotubes were dispersed in 120mL of anhydrous toluene and sonicated for 30min to form a uniform suspension. The pre-hydrolyzed silane solution and 0.8g of dibutyltin dilaurate were added, and the mixture was purged with nitrogen and reacted in an oil bath at 112℃ for 30h. After the reaction, the mixture was washed three times each with toluene and ethanol, and then vacuum dried at 62℃ for 14h to obtain the fluorosilane-modified carbon nanotube anchoring agent. The preparation method of the silver-supported zeolite imidazole ester framework antibacterial agent was as follows: 10g of... 2-Methylimidazole was dissolved in 120 mL of methanol to form solution A. 6 g of zinc nitrate hexahydrate was dissolved in 60 mL of methanol to form solution B. Solution B was poured into solution A with stirring, and the reaction was allowed to proceed at room temperature for 6 h. The white precipitate was collected by centrifugation, washed three times with methanol, and dried under vacuum at 62 °C for 12 h to obtain ZIF-8 nanocrystals. 8 g of ZIF-8 nanocrystals were dispersed in 120 mL of methanol. The solid material was collected by centrifugation in 0.1 mol / L silver nitrate solution and stirred in the dark for 14 h. After washing twice with deionized water, it was redispersed in 120 mL of deionized water and irradiated with a 300 W xenon lamp at 25 °C for 6 h. The final product was washed three times with ethanol and dried under vacuum at 62 °C for 12 h to obtain a silver-supported zeolite imidazole ester framework antibacterial agent. The preparation method of the biomimetic multi-arm epoxidized POSS interface enhancer is as follows: 12 g of octavinylsilsesquioxane was dissolved in 120 mL of anhydrous tetrahydrofuran. After purging with nitrogen to remove oxygen, 14 g of hydrogen peroxide-urea adduct and 0.14g of sodium tungstate was dissolved in 60mL of methanol to prepare a solution, and the reaction was carried out for 14 hours. The reaction solution was washed three times with saturated sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation to obtain epoxidized POSS. 12g of epoxidized POSS and 8g of... 4-Hydroxybenzoic acid was refluxed in 120 mL xylene for 6 h, cooled to room temperature, and then 4 g triethylamine and 10 g glycidyl methacrylate were added. The mixture was reacted in an oil bath at 82 °C for 10 h. After the reaction, the solvent was removed by rotary evaporation, and the mixture was precipitated three times with cold diethyl ether and then vacuum dried at 42 °C for 24 h to obtain a biomimetic multi-arm epoxidized POSS interface enhancer. The preparation method of the antifouling, antibacterial and self-cleaning pipe is as follows: Bisphenol A type epoxy resin was preheated to 50 °C, and perfluoropolyether surfactant and nano silica were added. The mixture was stirred at 2000 rpm for 15 min, and then fluorosilane-modified carbon nanotube anchoring agent, silver-loaded zeolite imidazole ester framework antibacterial agent and biomimetic multi-arm epoxidized POSS interface enhancer were added. The mixture was then high-speed sheared and dispersed at 3000 rpm for 30 min. The mixture was then transferred to a double planetary reactor. Cashew phenol-modified phenolic amide curing agent and polyether-modified siloxane leveling agent were added to a mixer and stirred at 500 rpm for 20 minutes under a vacuum of -0.095 MPa. The prepared functional epoxy resin solution was then coated onto both sides of electronic-grade glass fiber cloth with a unit area mass of 300 g / m², controlling the resin content to 40%. The cloth was then passed through a 100℃ hot roller pre-curing zone for 3 minutes to prepare a prepreg. The prepreg was cut, wound onto a mandrel, sealed with a vacuum bag film, and placed in an autoclave under 0.7 MPa pressure. It was then cured in an integrated manner using a stepped temperature increase program of 80℃ / 2h, 100℃ / 1h, 120℃ / 2h, and 150℃ / 4h. After cooling and demolding, a thicker integrated pipe with durable and stable antifouling and antibacterial properties was finally obtained.

[0047] Comparative Example 1 The specific implementation method is the same as in Example 1, except that fluorosilane-modified carbon nanotube anchoring agent, silver-loaded zeolite imidazole ester framework antibacterial agent, and biomimetic multi-arm epoxide POSS interface enhancer are not added.

[0048] Comparative Example 2 The specific implementation method is the same as in Example 1, except that no fluorosilane-modified carbon nanotube anchoring agent is added.

[0049] Comparative Example 3 The specific implementation method is the same as in Example 1, except that no silver-loaded zeolite imidazole ester framework antibacterial agent is added.

[0050] Performance testing According to national standards and industry specifications, the antifouling, antibacterial, and self-cleaning pipes prepared in Examples 1-3 and Comparative Examples 1-3 of this invention were subjected to the following performance tests: In the mechanical property tests, the tensile strength test was conducted according to GB / T 1040.2-2022 "Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics", using a universal testing machine with a 5kN load cell, a loading speed of 2mm / min, and a type 1B dumbbell-shaped specimen with a working part width of 10mm, a thickness of 4mm, and a gauge length of 50mm. Before the test, the specimens were conditioned at 23±2℃ and 50±5%RH for at least 88 hours. The bending strength test was conducted according to GB / T The bending performance was tested according to GB / T 9341-2008 "Determination of Bending Properties of Plastics". A three-point bending loading method was used, with a span of 64 mm (16 times the sample thickness), an indenter radius of 5 mm, a support radius of 2 mm, a loading speed of 2 mm / min, and a sample size of 80 mm × 10 mm × 4 mm. The bending strength under maximum load was recorded. For surface performance testing, the contact angle was tested according to GB / T 30447-2013 "Method for Measuring Water Contact Angle of Nanofilms". A contact angle meter was used, and a 5 μL drop of ultrapure water was added. The static contact angle was measured 30 seconds after the droplet contacted the surface. Five different locations were tested for each sample, and the average value was taken. The rolling angle test used the tilting platform method. A 20 μL water droplet was placed on the sample surface, and the platform was slowly tilted at a speed of 0.5° / s. The angle at which the droplet began to roll was recorded, and this was repeated five times, with the average value taken. The antibacterial performance test was conducted according to GB / T According to GB 21866-2008 "Determination of Antibacterial Properties and Antibacterial Effects of Antibacterial Coatings (Films)," a suspension of Staphylococcus aureus (ATCC 6538) and Escherichia coli (ATCC 25922) (1×10⁻⁶) was used. 5CFU / mL of the sample was applied to the pipe samples for 24 hours. The viable bacterial counts of the blank control group and the experimental group were compared using the plate count method, and the antibacterial rate was calculated. Simultaneously, the antibacterial durability of the material was evaluated according to ASTM E2180-2018, "Standard Test Method for Determination of the Effectiveness of Antimicrobial Agents in Polymers or Hydrophobic Materials". Corrosion resistance was tested using a neutral salt spray test with 5±1% sodium chloride solution, pH 7.2, chamber temperature 35±2℃, continuous spraying, and surface condition observed every 24 hours, recording the time of corrosion, blistering, and peeling. Abrasion resistance was tested according to GB / T 1768-2006, "Determination of Abrasion Resistance of Paints and Varnishes - Rotating Rubber Grinding Wheel Method", using a CS-10 rubber grinding wheel, a load of 500g, a rotation speed of 60rpm, and measuring mass loss after 1000 revolutions to calculate the wear rate. Interface bonding strength was tested according to GB / T... The adhesion test was conducted according to GB / T 5210-2006 "Adhesion Test of Paints and Varnishes by Pull-Off Method". An automatic tensile tester was used, and a uniformly applied glass fiber reinforced epoxy resin material was applied to the joint. After curing, the adhesion between the coating and the substrate was measured at a tensile speed of 10 mm / min. The chemical resistance test was conducted according to GB / T 11547-2008 "Determination of Resistance to Liquid Chemical Reagents in Plastics". The sample was immersed in a solution of 10% sulfuric acid, 10% sodium hydroxide, and 3% sodium chloride at 23±2℃ for 168 hours, then removed, washed, and the rate of mass change and retention of mechanical properties were measured. The environmental stress cracking resistance test was conducted according to GB / T 1842-2008 "Test Method for Environmental Stress Cracking of Polyethylene". The bending test strip method was used; the sample was bent and fixed, then immersed in a surfactant solution, and the number of samples that cracked within a certain time was observed at 50℃. The fluid resistance test was conducted according to GB / T The fluid resistance test method in GB / T 18991-2003 "Thermoplastic Pipes and Fittings for Hot and Cold Water Systems" measures the change in the frictional resistance coefficient of the pipe's inner wall under flow conditions. Long-term durability testing follows GB / T 18252-2020 "Determination of Long-Term Hydrostatic Strength of Thermoplastic Materials in Pipe Form by Extrapolation Method for Plastic Piping Systems," predicting the long-term service life of the pipe under constant internal pressure and temperature. All tests were conducted in a standard environment of 23±2℃ and 50±5% relative humidity. Each sample was tested five times, and the average value was taken. The test data were analyzed for variance and significance using SPSS statistical software (p<0.05).

[0051] Performance test results: Table 1: Performance test results of each embodiment and comparative example

[0052] As shown in Table 1, Examples 1-3 effectively solved the three major technical problems of existing pipe materials compared to Comparative Examples 1-3: Firstly, in terms of biofouling prevention, Examples 1-3 achieved a contact angle of 152.6-165.2° and a roll-off angle of only 3.2-3.8°, forming a stable superhydrophobic surface. In contrast, Comparative Example 1 had a contact angle of only 75.3° and was completely hydrophilic. Comparative Examples 2-3, although hydrophobic, had a larger roll-off angle (10.2-14.7°) and significantly poorer droplet retention capacity. This is attributed to the micro-nano structure constructed by the fluorosilane-modified carbon nanotube anchoring agent and the low surface energy characteristics imparted by the biomimetic multi-arm epoxide POSS interface enhancer in the examples. Secondly, in terms of antibacterial performance, Examples 1-3 effectively resisted Staphylococcus aureus and large bacteria. The antibacterial rate of Enterobacteriaceae exceeded 99.2%, while that of Comparative Example 1 was only 12.5-15.3% and that of Comparative Example 3 was only 32.8-35.6%, proving that the silver-supported zeolite imidazole ester framework antibacterial agent produced a synergistic antibacterial effect through the slow release of silver-zinc bimetallic ions. Finally, in terms of interfacial bonding strength, Examples 1-3 reached 18.7-25.6 MPa, which was significantly higher than 10.3 MPa of Comparative Example 1 and 14.2-15.8 MPa of Comparative Examples 2-3. This indicates that the three modified compounds enhanced the interfacial bonding force between the coating and the substrate through the dual effects of chemical bonding and physical anchoring. Among them, the anchoring effect of fluorosilane-modified carbon nanotubes and the star-shaped structure of biomimetic multi-arm epoxide POSS effectively improved stress transmission and prevented interfacial peeling. Furthermore, the significant advantages of the embodiments in terms of wear resistance (wear rate 7.2-12.3 mg / 1000 rpm vs. 15.6-35.7 mg / 1000 rpm), corrosion resistance (salt spray resistance time >3500 h vs. 1000-2800 h) and long-term durability further verify the stable three-dimensional network structure formed by the synergistic effect of the three modified compounds. This fundamentally solves the technical bottleneck of traditional pipe materials' inability to balance antifouling function and mechanical properties, and achieves simultaneous improvement in antifouling and antibacterial performance and the lifespan of the matrix material.

[0053] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A glass fiber-reinforced epoxy resin material, characterized by, The raw materials include the following weight parts: Bisphenol A type epoxy resin: 80-120 parts by weight; Cashew phenol modified phenolic amide curing agent: 25-35 parts by weight; Fluorosilane modified carbon nanotube anchoring agent: 5-15 parts by weight; Silver loaded zeolite imidazolate framework antibacterial agent: 3-8 parts by weight; Bionic multi-arm epoxidized POSS interface reinforcing agent: 10-20 parts by weight; Electronic grade glass fiber cloth: 50-70 parts by weight; Perfluoropolyether surfactant: 1-3 parts by weight; Nano silicon dioxide: 2-5 parts by weight; Polyether modified siloxane leveling agent: 0.5-2 parts by weight; The preparation method of the fluorosilane modified carbon nanotube anchoring agent comprises: A1, refluxing multi-walled carbon nanotubes in a mixed solution of concentrated sulfuric acid and concentrated nitric acid at 68-72℃; washing to neutral with deionized water, and vacuum drying at 78-82℃ to obtain acidified multi-walled carbon nanotubes; dispersing the acidified multi-walled carbon nanotubes in anhydrous toluene, and ultrasonic treatment to form a carbon nanotube suspension; mixing a mixture of 3-aminopropyltriethoxysilane and 1H,1H,2H,2H-perfluorodecyltriethoxysilane with ethanol and deionized water, and adding glacial acetic acid, and pre-hydrolyzing under stirring at 58-62℃; adding the pre-hydrolyzed silane solution into the carbon nanotube suspension, and adding dibutyltin dilaurate; reacting under nitrogen protection at 108-112℃; A2, after the reaction is completed, washing alternately with toluene and ethanol, and vacuum drying at 58-62℃.

2. The glass fiber-reinforced epoxy material of claim 1, wherein, In step A1, the refluxing time at 68-72℃ is 4-6h; and the reaction time at 108-112℃ is 24-30h.

3. The glass fiber-reinforced epoxy material of claim 1, wherein, In step A2, the vacuum drying time at 58-62℃ is 12-14h.

4. The glass fiber-reinforced epoxy material of claim 1, wherein, The preparation method of the silver loaded zeolite imidazolate framework antibacterial agent comprises: B1, dissolving 2-methylimidazole in methanol to form solution A; dissolving zinc nitrate hexahydrate in methanol to form solution B; mixing solution B with solution A under stirring, and reacting at room temperature; centrifugally collecting the white precipitate, washing with methanol for three times, and vacuum drying at 58-62℃ to obtain ZIF-8 nanocrystals; B2, dispersing the ZIF-8 nanocrystals in a silver nitrate solution, stirring in the dark; centrifugally collecting the solid material, washing with deionized water, and then dispersing in water again; irradiating under the condition of 15-25℃ using a xenon lamp; and finally washing the product with ethanol, and vacuum drying at 58-62℃.

5. The glass fiber-reinforced epoxy material of claim 4, wherein, In step B1, the reaction time at room temperature is 4-6h; and the molar ratio of 2-methylimidazole to zinc nitrate hexahydrate is (4-8):

1.

6. The glass fiber-reinforced epoxy material of claim 4, wherein, In step B2, the stirring time in the dark is 12-14h; and the xenon lamp irradiation time is 4-6h.

7. The glass fiber-reinforced epoxy material of claim 1, wherein, The preparation method of the biomimetic multi-arm epoxidized POSS interface reinforcing agent comprises: C1, dissolving octavinylsilsesquioxane in anhydrous tetrahydrofuran, introducing nitrogen to remove oxygen, then adding a solution prepared by dissolving hydrogen peroxide-urea adduct and sodium tungstate in methanol dropwise at 64-66 ℃, and reacting; the reaction solution is washed with saturated sodium chloride solution, the organic phase is dried with anhydrous magnesium sulfate, then rotary evaporation is performed to obtain epoxidized POSS; C2, refluxing epoxidized POSS and 4-hydroxybenzoic acid in xylene; after cooling, adding triethylamine and glycidyl methacrylate, and reacting at 78-82 ℃; after the reaction is completed, rotary evaporation is performed, precipitation is performed with cold ether, and vacuum drying is performed at 38-42 ℃.

8. The glass fiber-reinforced epoxy material of claim 7, wherein, In step C1, the reaction time is 12-14 h; the molar ratio of the hydrogen peroxide-urea adduct to octavinylsilsesquioxane is (8-12):

1.

9. The glass fiber-reinforced epoxy material of claim 7, wherein, In step C2, the reaction time at 78-82 ℃ is 8-10 h.

10. An antifouling antibacterial self-cleaning pipe, characterized by, The anti-fouling and anti-bacterial self-cleaning pipeline is prepared from the glass fiber reinforced epoxy resin material according to any one of claims 1-9.

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