A method for preparing high-performance antibacterial self-cleaning pipe

Abstract

The invention discloses a preparation method of a high-performance antibacterial self-cleaning pipe, comprising the following steps: using zinc gluconate as a zinc source to prepare a zeolite imidazolate skeleton structure material; compounding basic magnesium sulfate whiskers and zeolite imidazolate skeleton structure materials and modifying them with 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane to obtain a modified filler; mixing epoxy resin, a curing agent, a diluent, a leveling agent, and a modified filler to obtain a modified coating; adding polypropylene resin, an antioxidant, and nano-calcium carbonate into a mixer and blending to obtain a mixture, extruding the mixture through a pipe extruder, and then towing it into a vacuum setting machine for final shaping through a traction machine to obtain a polymer pipe matrix; spraying the above-mentioned modified coating on the surface of the polymer pipe matrix, drying, and obtaining an antibacterial self-cleaning pipe. The present invention effectively improves the antibacterial self-cleaning performance of the pipe by spraying the homemade coating on the pipe surface, and the coating has good bonding performance with the pipe matrix and excellent durability.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer pipes, and in particular to a method for preparing a high-performance antibacterial self-cleaning pipe. Background Art

[0002] Polymer pipe is a tubular product made primarily of polymer materials. In industry and construction, polymer pipes are widely used in piping systems for transporting liquids, gases, and solid particles. The emergence of polymer pipes primarily addresses the challenges of metal pipes in certain applications. Compared to metal pipes, polymer pipes offer the following advantages: 1. Lightweight and High-Strength: Polymer pipes are typically made from polymer materials, offering low density and good tensile strength, making them lightweight and easy to handle and install. 2. Good Corrosion Resistance: Compared to metal, polymer pipes exhibit superior corrosion resistance in harsh environments such as acidic and alkaline media, salt water, chemicals, and seawater, making them less susceptible to rust and corrosion. 3. Strong Wear Resistance: Polymer pipes exhibit excellent wear resistance, resisting damage from wear and friction over long-term use. 4. Long Lifespan: Due to their excellent aging and weather resistance, polymer pipes offer a long service life, meeting the long-term needs of engineering projects. 5. Easy construction: Polymer pipes are usually flexible and easy to bend, and the construction process is simple and convenient, reducing the time and cost of installation and maintenance. 6. Good insulation performance: Compared with metal pipes, polymer pipes have better insulation properties and can effectively block the conduction of current and heat. 7. Environmentally friendly and sustainable: Polymer pipes are mostly made of recyclable materials, have little impact on the environment, and can be reused. Due to the above advantages of polymer pipes, they have been widely used in municipal engineering, construction engineering, agricultural irrigation, water supply and drainage, chemical pipelines and other fields. With the continuous development of science and technology, the performance of polymer pipes will continue to improve, providing more reliable and efficient solutions for pipeline systems in various industries.

[0003] With the widespread use of polymer tubing, research on these materials is also facing new challenges. For example, as a common piping material, polymer tubing is widely used in food processing, healthcare, water supply and drainage systems, and other fields. However, due to its surface adsorption and roughness, it is easy for dirt to form inside the pipes and provide a substrate for microbial growth, which can easily breed bacteria, mold, and other microorganisms during use. The presence of these dirt and microorganisms not only affects the patency of the pipes but also poses a threat to human health. Therefore, there is a need to modify polymer tubing to enhance its antibacterial and self-cleaning properties.

[0004] Currently, several methods for modifying polymer tubing include the following: First, nanotechnology is used to introduce nano-antimicrobial agents onto the surface of polymer tubing. Nano-antimicrobial agents have high antimicrobial activity and can effectively kill bacteria, mold, and other microorganisms adhering to pipes. By combining nano-antimicrobial agents with polymer materials, pipes can be imbued with antimicrobial properties. Second, specialized surface coatings are used. By forming a self-cleaning coating on the surface of polymer tubing, the adhesion of dirt and microorganisms within the pipes is reduced, and the surface is automatically cleaned as fluid passes through the pipes, maintaining pipe hygiene. Furthermore, polymer tubing can be modified using physical methods, such as plasma treatment and ultraviolet irradiation. These physical methods can alter the chemical properties and texture of the tubing surface, thereby achieving antimicrobial and self-cleaning effects. These surface coating techniques are simple, have minimal impact on polymer tubing performance, and are low-cost, making them widely used. However, the main challenges with current surface coating technologies are poor adhesion between the coating material and the polymer tubing, poor mechanical properties, and the need for further improvement in the antimicrobial and self-cleaning properties of the coating. Summary of the Invention

[0005] The technical problem to be solved by the present invention is: in response to the deficiencies in the prior art, a method for preparing a high-performance self-cleaning pipe is provided. In the method, zinc gluconate is used as a zinc source to prepare a zeolite imidazolate skeleton structure material, which is then compounded with basic magnesium sulfate whiskers and modified with 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane. The prepared modified filler has excellent compatibility with an epoxy resin matrix and can effectively improve the superhydrophobicity and antibacterial properties of the pipe surface. The coating of the pipe has excellent bonding performance with the matrix and good durability.

[0006] In order to solve the above technical problems, the technical solution of the present invention is:

[0007] A method for preparing a high-performance antibacterial self-cleaning pipe comprises the following steps:

[0008] (1) dissolving zinc gluconate in DMF to obtain a zinc gluconate solution, dissolving benzimidazole in DMF to obtain a benzimidazole solution, and then adding the benzimidazole solution dropwise to the zinc gluconate solution. After the addition is completed, stirring is performed at room temperature, and then centrifugation is performed. The obtained precipitate is washed and dried to obtain a zeolite imidazole ester framework structure material;

[0009] (2) dispersing basic magnesium sulfate whiskers and zeolite imidazolate framework material in ethanol to prepare a dispersion, then adding an ammonia solution for stirring, then adding 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane to react, centrifuging after the reaction, washing the obtained precipitate and drying it to prepare a modified filler;

[0010] (3) adding epoxy resin, curing agent, diluent, leveling agent and the modified filler prepared above into a mixer, stirring and mixing them uniformly to obtain a modified coating;

[0011] (4) Adding polypropylene resin, antioxidant, and nano-calcium carbonate into a mixer for blending to obtain a mixture, extruding the mixture through a pipe extruder, and then pulling the mixture into a vacuum setting machine through a traction machine for setting to obtain a polymer pipe matrix; spraying the modified coating prepared above on the surface of the polymer pipe matrix, and drying it to obtain an antibacterial self-cleaning pipe.

[0012] As a preferred embodiment of the above technical solution, in step (1), the concentration of the zinc gluconate solution is 0.3-0.4 g / ml, the concentration of the benzimidazole solution is 1-2 g / ml, and the volume ratio of the zinc gluconate solution to the benzimidazole solution is 1:1.

[0013] As a preferred embodiment of the above technical solution, in step (1), the stirring treatment time is 40-50 hours; the centrifugal speed is 5000-10000 rpm, and the time is 5-10 minutes.

[0014] As a preferred embodiment of the above technical solution, in step (2), the diameter of the basic magnesium sulfate whiskers is 200-500 nm, and the aspect ratio is 50-100; the concentration of the ammonia solution is 25wt%; and the usage ratio of the basic magnesium sulfate whiskers, zeolite imidazolate skeleton structure material, ammonia solution, and 1H,1H,2H,2H-perfluorodecyltriethoxysilane is 0.5g:(0.5-1)g:(1-2)ml:100μL.

[0015] As a preferred embodiment of the above technical solution, in step (2), the stirring treatment time is 5-10 minutes, and the stirring reaction time is 1-2 hours.

[0016] As a preferred embodiment of the above technical solution, in step (3), the epoxy resin is bisphenol A epoxy resin, the curing agent is diethylenetriamine, the diluent is n-butanol, and the leveling agent is leveling agent GLP388.

[0017] As a preferred embodiment of the above technical solution, in step (3), the amounts of the components used, in parts by weight, are 20-30 parts of epoxy resin, 15-25 parts of curing agent, 10-15 parts of diluent, 1-1.5 parts of leveling agent, and 5-10 parts of modified filler.

[0018] As a preferred embodiment of the above technical solution, in step (4), the polypropylene resin is selected from at least one of homopolypropylene and copolymer polypropylene; the isotacticity of the homopolypropylene is above 90%; and the antioxidant is antioxidant HP136.

[0019] As a preferred embodiment of the above technical solution, in step (4), the mass ratio of the polypropylene resin, antioxidant and nano-calcium carbonate is 100:(0.2-0.5):(2-5).

[0020] As a preferred embodiment of the above technical solution, in step (4), the temperature of the blending treatment is 70-80°C and the time is 30-60 minutes; during extrusion, the temperature of each zone of the pipe extruder is 180-200°C.

[0021] Due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0022] The present invention uses cheaper zinc gluconate as a zinc source to produce a zeolite imidazolate framework material with good chemical stability. This is then compounded with basic magnesium sulfate whiskers and modified with low-surface-energy 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane to produce a super-hydrophobic modified filler. This filler is then added to an epoxy resin matrix to produce a modified coating. The benzimidazole organic ligand in the modified filler has good compatibility with the epoxy resin, and the imidazole group can also undergo a ring-opening reaction with the epoxy group, thereby anchoring the distribution of the modified filler in the epoxy resin matrix. This results in a coating with good mechanical stability and hydrophobicity, thereby forming a self-cleaning coating on the pipe surface. Furthermore, the modified coating produced by the present invention forms a super-hydrophobic coating on the pipe surface, which has a certain barrier effect on bacterial solutions. Furthermore, the zinc ions in the modified filler can effectively destroy bacterial cell membranes, thereby killing bacteria. These two factors contribute to the excellent antibacterial properties of the pipe produced by the present invention. DETAILED DESCRIPTION

[0023] The present invention will be further described below with reference to the following examples. It should be understood that these examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention.

[0024] In the following examples, the diameter of the basic magnesium sulfate whiskers is 300 nm and the aspect ratio is 60; the polypropylene resin is a homopolymer polypropylene with an isotacticity of more than 90%.

[0025] Example 1

[0026] (1) dissolving 0.184 g of zinc gluconate in 50 ml of DMF to prepare a zinc gluconate solution, dissolving 0.766 g of benzimidazole in 50 ml of DMF to prepare a benzimidazole solution, and then adding the benzimidazole solution dropwise to the zinc gluconate solution. After the addition is completed, stirring is performed at room temperature for 45 hours, and then centrifuging at a speed of 8000 rpm for 5 minutes. The obtained precipitate is washed and dried to obtain a zeolite imidazole ester framework structure material;

[0027] (2) 0.5 g of basic magnesium sulfate whiskers and 0.65 g of zeolite imidazole ester framework material were dispersed in 50 ml of ethanol to prepare a dispersion, and then 1.5 ml of a 25 wt% ammonia solution was added and stirred for 10 min. Then, 1100 μL of H,1H,2H,2H-perfluorodecyltriethoxysilane was added and reacted for 1 h. After the reaction, the mixture was centrifuged and the obtained precipitate was washed and dried to prepare a modified filler;

[0028] (3) Add 25 parts of bisphenol A epoxy resin, 20 parts of diethylenetriamine, 13 parts of n-butanol, 1 part of leveling agent GLP388 and 6 parts of the modified filler prepared above into a blender, and stir and mix them uniformly to prepare a modified coating;

[0029] (4) In parts by weight, 100 parts of polypropylene resin, 0.35 parts of antioxidant HP136, and 5 parts of nano-calcium carbonate are added to a mixer and blended at 75°C for 40 minutes to obtain a mixture. The mixture is extruded through a pipe extruder, and the temperature of each zone of the pipe extruder is controlled to be 180-200°C during extrusion. The mixture is then pulled into a vacuum setting machine for setting to obtain a polymer pipe matrix; the modified coating prepared above is sprayed on the surface of the polymer pipe matrix, and dried to obtain an antibacterial self-cleaning pipe with a 0.3mm coating deposited on the surface.

[0030] Example 2

[0031] (1) dissolving 0.184 g of zinc gluconate in 50 ml of DMF to prepare a zinc gluconate solution, dissolving 0.766 g of benzimidazole in 50 ml of DMF to prepare a benzimidazole solution, and then adding the benzimidazole solution dropwise to the zinc gluconate solution. After the addition is completed, stirring at room temperature for 48 hours, and then centrifuging at a speed of 6000 rpm for 10 minutes, washing the obtained precipitate and drying it to obtain a zeolite imidazole ester framework structure material;

[0032] (2) 0.5 g of basic magnesium sulfate whiskers and 0.55 g of zeolite imidazolate framework material were dispersed in 50 ml of ethanol to prepare a dispersion, and then 2 ml of a 25 wt% ammonia solution was added and stirred for 5 min. Then, 1100 μL of H,1H,2H,2H-perfluorodecyltriethoxysilane was added and reacted for 2 h. After the reaction, the mixture was centrifuged, and the obtained precipitate was washed and dried to prepare a modified filler;

[0033] (3) Add 28 parts of bisphenol A epoxy resin, 21 parts of diethylenetriamine, 12 parts of n-butanol, 1.5 parts of leveling agent GLP388 and 8 parts of the modified filler prepared above into a blender, and stir and mix them uniformly to prepare a modified coating;

[0034] (4) In parts by weight, 100 parts of polypropylene resin, 0.2 parts of antioxidant HP136, and 4 parts of nano-calcium carbonate are added to a mixer and blended at 75°C for 40 minutes to obtain a mixture. The mixture is extruded through a pipe extruder, and the temperature of each zone of the pipe extruder is controlled to be 180-200°C during extrusion. The mixture is then pulled into a vacuum setting machine for setting to obtain a polymer pipe matrix; the modified coating prepared above is sprayed on the surface of the polymer pipe matrix, and dried to obtain an antibacterial self-cleaning pipe with a 0.3mm coating deposited on the surface.

[0035] Example 3

[0036] (1) dissolving 0.184 g of zinc gluconate in 50 ml of DMF to prepare a zinc gluconate solution, dissolving 0.766 g of benzimidazole in 50 ml of DMF to prepare a benzimidazole solution, and then adding the benzimidazole solution dropwise to the zinc gluconate solution. After the addition is completed, stirring is performed at room temperature for 48 hours, and then centrifuging at a speed of 8000 rpm for 6 minutes. The obtained precipitate is washed and dried to obtain a zeolite imidazole ester framework structure material;

[0037] (2) 0.5 g of basic magnesium sulfate whiskers and 0.65 g of zeolite imidazolate framework material were dispersed in 50 ml of ethanol to prepare a dispersion, and then 1.5 ml of a 25 wt% ammonia solution was added and stirred for 7 min. Then, 1100 μL of H,1H,2H,2H-perfluorodecyltriethoxysilane was added and reacted for 2 h. After the reaction, the mixture was centrifuged and the obtained precipitate was washed and dried to prepare a modified filler;

[0038] (3) Add 27 parts of bisphenol A epoxy resin, 16 parts of diethylenetriamine, 15 parts of n-butanol, 1.3 parts of leveling agent GLP388 and 7 parts of the modified filler prepared above into a blender, and stir and mix them uniformly to prepare a modified coating;

[0039] (4) In parts by weight, 100 parts of polypropylene resin, 0.4 parts of antioxidant HP136, and 5 parts of nano-calcium carbonate are added to a mixer and blended at 80°C for 30 minutes to obtain a mixture. The mixture is extruded through a pipe extruder, and the temperature of each zone of the pipe extruder is controlled to be 180-200°C during extrusion. The mixture is then pulled into a vacuum setting machine for setting to obtain a polymer pipe matrix; the modified coating prepared above is sprayed on the surface of the polymer pipe matrix, and dried to obtain an antibacterial self-cleaning pipe with a 0.3mm coating deposited on the surface.

[0040] Example 4

[0041] (1) dissolving 0.184 g of zinc gluconate in 50 ml of DMF to prepare a zinc gluconate solution, dissolving 0.766 g of benzimidazole in 50 ml of DMF to prepare a benzimidazole solution, and then adding the benzimidazole solution dropwise to the zinc gluconate solution. After the addition is completed, stirring is carried out at room temperature for 48 hours, and then centrifuging at a speed of 8000 rpm for 5 minutes. The obtained precipitate is washed and dried to obtain a zeolite imidazole ester framework structure material;

[0042] (2) 0.5 g of basic magnesium sulfate whiskers and 0.7 g of zeolite imidazolate framework material were dispersed in 50 ml of ethanol to prepare a dispersion, and then 1.5 ml of a 25 wt% ammonia solution was added and stirred for 8 min. Then, 1100 μL of H,1H,2H,2H-perfluorodecyltriethoxysilane was added and reacted for 1 h. After the reaction, the mixture was centrifuged and the obtained precipitate was washed and dried to prepare a modified filler;

[0043] (3) Add 28 parts of bisphenol A epoxy resin, 22 parts of diethylenetriamine, 14 parts of n-butanol, 1.3 parts of leveling agent GLP388 and 6 parts of the modified filler prepared above into a blender, and stir and mix them uniformly to prepare a modified coating;

[0044] (4) In parts by weight, 100 parts of polypropylene resin, 0.3 parts of antioxidant HP136, and 4 parts of nano-calcium carbonate are added to a mixer and blended at 75°C for 40 minutes to obtain a mixture. The mixture is extruded through a pipe extruder, and the temperature of each zone of the pipe extruder is controlled to be 180-200°C during extrusion. The mixture is then pulled into a vacuum setting machine for setting to obtain a polymer pipe matrix; the modified coating prepared above is sprayed on the surface of the polymer pipe matrix, and dried to obtain an antibacterial self-cleaning pipe with a 0.3 mm coating deposited on the surface.

[0045] The performance of the coating on the surface of the antibacterial self-cleaning pipe prepared above was tested below, and the test results are shown in Table 1.

[0046] Table 1

[0047]

[0048]

[0049] It can be seen from the above test results that the coating on the pipe prepared by the present invention not only has good mechanical properties, but also has good bonding between the coating and the pipe substrate, and the prepared pipe has good antibacterial and self-cleaning properties.

[0050] In addition, it should be understood that after reading the contents of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. A method for preparing a high-performance antibacterial self-cleaning pipe, characterized in that: The following steps are involved: (1) dissolving zinc gluconate in DMF to obtain a zinc gluconate solution, dissolving benzimidazole in DMF to obtain a benzimidazole solution, and then adding the benzimidazole solution dropwise to the zinc gluconate solution. After the addition is completed, stirring is performed at room temperature, and then centrifugation is performed. The obtained precipitate is washed and dried to obtain a zeolite imidazole ester framework structure material; (2) dispersing basic magnesium sulfate whiskers and zeolite imidazolate framework material in ethanol to prepare a dispersion, then adding an ammonia solution for stirring, then adding 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane to react, centrifuging after the reaction, washing the obtained precipitate and drying it to prepare a modified filler; (3) adding epoxy resin, curing agent, diluent, leveling agent and the modified filler prepared above into a mixer, stirring and mixing them uniformly to obtain a modified coating; (4) Adding polypropylene resin, antioxidant, and nano-calcium carbonate into a mixer for blending to obtain a mixture, extruding the mixture through a pipe extruder, and then pulling the mixture into a vacuum setting machine through a traction machine for setting to obtain a polymer pipe matrix; spraying the modified coating prepared above on the surface of the polymer pipe matrix, and drying it to obtain an antibacterial self-cleaning pipe.

2. The method for preparing a high-performance antibacterial self-cleaning pipe according to claim 1, characterized in that: In step (1), the concentration of the zinc gluconate solution is 0.3-0.4 g / ml, the concentration of the benzimidazole solution is 1-2 g / ml, and the volume ratio of the zinc gluconate solution to the benzimidazole solution is 1:

1.

3. The method for preparing a high-performance antibacterial self-cleaning pipe according to claim 1, characterized in that: In step (1), the stirring treatment time is 40-50 hours; the centrifugal speed is 5000-10000 rpm, and the time is 5-10 minutes.

4. The method for preparing a high-performance antibacterial self-cleaning pipe according to claim 1, characterized in that: In step (2), the diameter of the basic magnesium sulfate whiskers is 200-500 nm, and the aspect ratio is 50-100; the concentration of the ammonia solution is 25 wt%; and the amount ratio of the basic magnesium sulfate whiskers, zeolite imidazolate framework material, ammonia solution, and 1H,1H,2H,2H-perfluorodecyltriethoxysilane is 0.5 g:(0.5-1) g:(1-2) ml:100 μL.

5. The method for preparing a high-performance antibacterial self-cleaning pipe according to claim 1, characterized in that: In step (2), the stirring treatment time is 5-10 minutes, and the stirring reaction is 1-2 hours.

6. The method for preparing a high-performance antibacterial self-cleaning pipe according to claim 1, characterized in that: In step (3), the epoxy resin is bisphenol A epoxy resin, the curing agent is diethylenetriamine, the diluent is n-butanol, and the leveling agent is leveling agent GLP388.

7. The method for preparing a high-performance antibacterial self-cleaning pipe according to claim 1, characterized in that: In step (3), the amounts of the components used, in parts by weight, are 20-30 parts of epoxy resin, 15-25 parts of curing agent, 10-15 parts of diluent, 1-1.5 parts of leveling agent, and 5-10 parts of modified filler.

8. The method for preparing a high-performance antibacterial self-cleaning pipe according to claim 1, characterized in that: In step (4), the polypropylene resin is selected from at least one of homopolypropylene and copolymer polypropylene; the isotacticity of the homopolypropylene is above 90%; and the antioxidant is antioxidant HP136.

9. The method for preparing a high-performance antibacterial self-cleaning pipe according to claim 1, characterized in that: In step (4), the mass ratio of the polypropylene resin, the antioxidant and the nano-calcium carbonate is 100:(0.2-0.5):(2-5).

10. The method for preparing a high-performance antibacterial self-cleaning pipe according to claim 1, characterized in that: In step (4), the temperature of the blending treatment is 70-80°C and the time is 30-60 minutes; during extrusion, the temperature of each zone of the pipe extruder is 180-200°C.

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