Bacteriostatic and scale-inhibiting PE material and preparation method thereof

Abstract

The invention provides a bacteriostatic and scale-inhibiting PE material and a preparation method thereof, and belongs to the technical field of high polymer materials, the preparation method comprises the following preparation steps: dissolving polyethylene in xylene, dissolving, adding perfluorohexylethylene and dicumyl peroxide, reacting, precipitating, washing, and drying to obtain perfluoro modified PE; the preparation method comprises the following steps: dissolving four-arm polyethylene glycol amine in a PBS buffer solution, adding 4-carboxyphenylboronic acid, EDC.HCl and NHS, carrying out a stirring reaction in a dark place, carrying out ultrafiltration and freeze drying to obtain PBA-PEG, dissolving the PBA-PEG in a Tris-HCl buffer solution, adding dopamine hydrochloride, and carrying out mixing, oxidation reaction, dialysis purification and drying to obtain a PBA-DA-PEG compound; the preparation method comprises the following steps: pre-mixing perfluorinated modified PE, mixing with an antioxidant and a compatibilizer, injecting the PBA-DA-PEG compound, continuously mixing, extruding, and carrying out water-cooling pelletizing to obtain the antibacterial and scale-inhibiting PE material. According to the PE material obtained by the invention, the antibacterial performance and the scale inhibition performance of the material can be improved at the same time.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a PE material capable of inhibiting bacteria and scaling and a preparation method thereof. Background Art

[0002] Polyethylene (PE) is non-toxic and odorless, and also boasts excellent properties such as corrosion resistance, low-temperature resistance, wear resistance, impact resistance, low friction coefficient, and food-grade hygiene. It is widely used in various fields and can be formed into pipes through injection molding or extrusion or coated on the inner walls of existing pipes. However, the current use of PE materials in some materials such as drainage pipes and tap water pipes is less than ideal in terms of anti-fouling effect. The inner walls of these pipes require regular cleaning, which is time-consuming and labor-intensive. If cleaning is not carried out in a timely manner, the scale deposits become too thick and tightly bonded to the pipe wall, making it extremely difficult to clean and even clogging the pipe. Furthermore, while current PE materials have good chemical stability, their antibacterial properties are only moderate. In some areas with high hygiene requirements, regular sterilization and disinfection are required, which brings a lot of inconvenience and affects their use.

[0003] Currently, metal antimicrobial agents are added to PE materials to achieve antibacterial effects. While these can improve antibacterial properties, they suffer from poor dispersibility and poor control of extrusion conditions when blended with PE, which can easily affect the overall performance of the PE material. Furthermore, it's difficult to simultaneously improve PE's antibacterial properties and its scale inhibition performance, making it even more difficult to maintain long-term stable scale inhibition performance.

[0004] For example, the patent with publication number CN111609223A discloses a PE high-pressure water supply pipe and its preparation method. The PE high-pressure water supply pipe includes an antibacterial inner pipe made of antibacterial modified PE material and a protective outer pipe made of reinforced modified PE material. The antibacterial modified PE material uses zeolite as a carrier and zinc ions as a bactericide. On the one hand, it has an enhancing effect on the PE material, and on the other hand, it makes the PE material have an antibacterial and sterilizing effect, which can effectively prevent the PE pipe from accumulating a large number of bacteria during long-term operation. Although the zinc metal added in this solution improves the antibacterial performance, the zinc ions, as a bactericide, are prone to side reactions during the melt mixing process. Moreover, the zinc ions on the surface of the material are easily detached and hydrolyzed when exposed to water, making it difficult to achieve long-term antibacterial performance. In addition, the pipe does not have a scale inhibition effect, and the simple addition of a scale inhibitor will cause more side reactions and side effects, affecting the mechanical strength of the pipe.

[0005] Therefore, it is necessary to provide a PE material with antibacterial and anti-scaling properties and a preparation method thereof to solve the problems existing in the above-mentioned prior art. Summary of the Invention

[0006] In view of this, the present invention provides an antibacterial and scale-inhibiting PE material and a preparation method thereof, which can simultaneously improve the antibacterial and scale-inhibiting properties of the material.

[0007] To achieve the above-mentioned object, the specific scheme adopted by the present invention is as follows: a method for preparing an antibacterial and scale-inhibiting PE material, comprising the following preparation steps: S1. Dissolve polyethylene in xylene, heat and stir to dissolve, add perfluorohexylethylene and diisopropylbenzene peroxide to react, cool, pour into anhydrous methanol for precipitation, vacuum filter, wash, and vacuum dry to obtain perfluoro-modified PE; S2. Dissolve four-arm polyethylene glycol amine in PBS buffer, add 4-carboxyphenylboronic acid, EDC·HCl, and NHS, stir in the dark, ultrafilter, and freeze-dry to obtain PBA-PEG. S3. The obtained PBA-PEG was dissolved in Tris-HCl buffer, dopamine hydrochloride was added and mixed, and an oxidation reaction was performed. The mixture was purified by dialysis and freeze-dried to obtain a PBA-DA-PEG complex. S4. Premix the perfluorinated modified PE, mix the obtained premix with an antioxidant and a compatibilizer, inject the PBA-DA-PEG complex, continue mixing, extrude, and pelletize after water cooling to obtain an antibacterial and anti-scaling PE material.

[0008] By modifying polyethylene with perfluorohexylethylene, the mechanical strength of the material is improved while a fluorine atom-rich layer is formed on the PE surface, which reduces the surface energy, gives the material super-hydrophobic properties, and improves the surface smoothness. When scale crystals approach, the high interfacial tension prevents the crystals from coming into close contact with the material, effectively reducing the deposition of scale such as calcium carbonate.

[0009] After activating the carboxyl group of 4-carboxyphenylboronic acid (PBA-COOH) with EDC·HCl (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride) and the catalyst NHS (N-hydroxysuccinimide), it reacts with tetra-arm polyethylene glycol amine (tetra-PEG-NH2) to form an amide bond, resulting in PBA-PEG. Dopamine (DA) is then oxidized to dopamine quinone under alkaline conditions, which then binds to the remaining amino groups of PEG via Michael addition to form PBA-DA-PEG. Unreacted dopamine self-polymerizes to form polydopamine (PDA), resulting in a PBA-DA-PEG complex containing PBA-DA-PEG and PDA. The catechol / quinone groups contained in the PDA in this complex interfere with the microbial membrane structure, destroying the integrity of the cell membrane and improving the antibacterial properties of the material. Furthermore, the PDA adsorbs Ca 2+ / Mg 2+Ions and PBA combine with the hydroxyl groups on the surface of scale crystals to inhibit crystal growth, reduce deposition, and give the material scale inhibition properties, thereby achieving effective antibacterial and scale inhibition properties.

[0010] And PDA in the PBA-DA-PEG complex chelates Ca 2+ / Mg 2+ While the ions achieve scale inhibition, PBA provides dynamic covalent bonds and reversibly combines with o-dihydroxyl groups to achieve self-repair function on the surface of the material, thereby extending the service life of the material and maintaining the scale inhibition performance of the material. In addition, the adhesion of PDA can also enhance the interfacial binding force between PEG and PE, preventing the functional components from falling off, thereby achieving long-lasting and stable antibacterial and scale inhibition performance.

[0011] Preferably, in the step S4, POSS-MoS2 hybrid powder is also added and pre-mixed with perfluorinated modified PE; the POSS-MoS2 hybrid powder is prepared by the following method: MoS2 powder is added to anhydrous N-methylpyrrolidone, ultrasonic treatment is performed, octaisobutyl-POSS is added, ultrasonication is continued, vacuum rotary evaporation is performed, and then vacuum drying is performed to obtain.

[0012] By adding POSS-MoS2 hybrid powder, MoS2 is used to improve smoothness, reduce the crystallization and adhesion of scaling ions on its surface, and improve the scaling problem. However, the compatibility and dispersibility of MoS2 in PE are poor, and adding too much will affect the comprehensive performance of the material. The present invention hybridizes MoS2 with octaisobutyl-POSS, utilizes the POSS cage structure to embed the MoS2 interlayer, inhibits MoS2 stacking, improves the dispersion effect in the material and enhances the compatibility with the organic matrix, and forms physical cross-linking points through hydrophobic interaction between the siloxane cage of POSS and the fluorocarbon chain in the perfluorinated modified PE, thereby improving the binding performance of the material. At the same time, MoS2 nanosheets can also provide rigid support and improve the strength of the material, thereby improving the scale inhibition performance while improving the strength of the material through the POSS-MoS2 hybrid powder.

[0013] Preferably, during the preparation of the POSS-MoS2 hybrid powder, MoS2 powder with a particle size of 1-2 μm is added to anhydrous N-methylpyrrolidone, subjected to ultrasonic treatment at a power of 600 W for 2 h, octaisobutyl-POSS is added, ultrasonic treatment is continued for 1 h, the temperature is raised to 80°C for vacuum rotary evaporation, and then vacuum dried at 60°C for 12 h to obtain.

[0014] Preferably, in the step S4, after the POSS-MoS2 hybrid powder is premixed with the perfluorinated modified PE, the obtained premix, antioxidant 1010 and compatibilizer PE-g-MAH are fed into a twin-screw extruder at a temperature of 170-180°C and a screw speed of 250rpm for mixing for 2-3min, and then the PBA-DA-PEG complex is injected from the side feeding port, the temperature is adjusted to 155-160°C, the screw speed is adjusted to 180rpm, and mixing is carried out for 1-2min. The mixture is extruded and pelletized by water cooling to obtain an antibacterial and scale-inhibiting PE material.

[0015] By adding each functional component one by one and mixing them, the dispersion effect is improved, and the entire mixing process is kept at a relatively low mixing temperature, which is conducive to maintaining the performance of each component and achieving better antibacterial and anti-scaling effects.

[0016] Preferably, in step S1, the temperature is raised to 120°C for stirring and dissolving, perfluorohexylethylene and diisopropylbenzene peroxide are added, and the reaction is carried out at 140°C for 3 hours under nitrogen protection, and then cooled to room temperature. Then, under magnetic stirring at a speed of 300-400 rpm, the reaction system is slowly poured into anhydrous methanol for precipitation, vacuum filtered, and the precipitate is washed with methanol 3 times and vacuum dried at 60°C for 12 hours to obtain perfluoro-modified PE.

[0017] The above method is safer and more economical. Using methanol as a poor solvent for PE ensures complete precipitation of the modified PE, reduces product loss, and has a strong ability to dissolve impurities, unreacted monomers, and initiators, effectively removing impurities while being volatile and leaving no residue.

[0018] Preferably, in step S2, four-arm polyethylene glycol amine is dissolved in PBS buffer at a pH of 7.4, 4-carboxyphenylboronic acid, EDC·HCl and NHS are added, and the mixture is stirred in the dark under nitrogen protection for 24 hours, ultrafiltered, and freeze-dried to obtain PBA-PEG.

[0019] Preferably, in step S3, PBA-PEG is dissolved in a 10 mM Tris-HCl buffer solution with a pH of 8.5, dopamine hydrochloride is added and mixed, and air is introduced to carry out an oxidation reaction for 12 hours, dialyzed and purified with a molecular weight cutoff of 3.5 kDa, and freeze-dried to obtain a PBA-DA-PEG complex.

[0020] Preferably, the antioxidant is antioxidant 1010; and the compatibilizer is PE-g-MAH.

[0021] The present invention also provides a PE material for antibacterial and anti-scaling, comprising the following components in parts by mass: 80-90 parts of perfluorinated modified PE, 0.3-0.5 parts of antioxidant, 3-5 parts of compatibilizer, and 5-8 parts of PBA-DA-PEG complex.

[0022] Preferably, the PBA-DA-PEG complex comprises the following raw materials in parts by mass: 10-15 parts of four-arm polyethylene glycol amine, 1-1.5 parts of 4-carboxyphenylboronic acid, 1.5-2 parts of EDC·HCl, 0.8-1 part of NHS and 3-5 parts of dopamine hydrochloride.

[0023] By adopting the above-mentioned proportions, the final PE material can better improve the material's scale inhibition and antibacterial properties while maintaining the good mechanical properties of the PE material. It can be used in water pipes and heat exchanger fins in high-hardness water environments, as well as other material scenarios that require certain antibacterial and scale inhibition properties. It can also be made into the inner wall coating of pipes, and has great market prospects.

[0024] The above technical solution of the present invention includes at least the following beneficial effects: 1. Polyethylene is modified by perfluorohexylethylene to improve the mechanical strength of the material while forming a fluorine atom-enriched layer on the PE surface, giving the material super-hydrophobic properties, improving surface smoothness, and effectively reducing the deposition of scale such as calcium carbonate.

[0025] 2. Through the catechol / quinone groups contained in PDA in the PBA-DA-PEG complex, the microbial membrane structure is disturbed, the integrity of the cell membrane is destroyed, the antibacterial properties of the material are improved, and the Ca adsorption 2+ / Mg 2+ Ions and PBA combine with the hydroxyl groups on the surface of scale crystals to inhibit crystal growth, reduce deposition, and give the material scale inhibition properties, thereby achieving effective antibacterial and scale inhibition properties.

[0026] 3. The PBA in the PBA-DA-PEG complex provides a dynamic covalent bond, which reversibly combines with the o-dihydroxy group to achieve the self-repair function of the material surface, thereby extending the service life of the material and maintaining the scale inhibition performance of the material. In addition, the adhesion of PDA can also enhance the interfacial binding force between PEG and PE, preventing the functional components from falling off, thereby achieving long-lasting and stable antibacterial and scale inhibition performance. DETAILED DESCRIPTION

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. The described embodiments are only part of the embodiments of the present invention. All other embodiments obtained by ordinary technicians in this field based on the described embodiments of the present invention are within the scope of protection of the present invention.

[0028] Example 1 100 g of polyethylene (PE) was dissolved in 300 mL of xylene solvent, heated to 120 ° C and stirred to dissolve, 15 g of perfluorohexylethylene and 0.15 g of diisopropylbenzene peroxide (DCP) were added, and the mixture was reacted at 140 ° C for 3 h under nitrogen protection. After cooling to room temperature, the reaction system was slowly poured into 800 ml of anhydrous methanol under magnetic stirring at a speed of 300 rpm to precipitate. The precipitate was vacuum filtered and washed with methanol 3 times to remove adsorbed impurities. The precipitate was vacuum dried at 60 ° C for 12 h to obtain perfluorinated modified PE particles.

[0029] Ten grams of tetra-PEG-NH2 were dissolved in 500 mL of PBS buffer (pH 7.4). Then, 1 g of 4-carboxyphenylboronic acid (PBA-COOH), 1.5 EDC·HCl (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride), and 0.8 g of NHS (N-hydroxysuccinimide) catalyst were added sequentially. The mixture was stirred under nitrogen and protected from light for 24 h. After completion of the reaction, unreacted material was removed by ultrafiltration and freeze-dried to obtain PBA-PEG. The mixture was then dissolved in 500 mL of 10 mM Tris-HCl buffer (pH 8.5). 3 g of dopamine hydrochloride (DA) was added, mixed, and oxidized by bubbling air for 12 h. When the reaction solution gradually changed from colorless to brown, it was dialyzed to a molecular weight cutoff of 3.5 kDa and freeze-dried to obtain the PBA-DA-PEG complex.

[0030] 10 g of MoS2 powder with a particle size of 1-2 μm was added to 500 mL of anhydrous N-methylpyrrolidone (NMP) and ultrasonically treated at a power of 600 W for 2 h to peel off into few-layer MoS2 nanosheets. 5 g of octaisobutyl-POSS was added and ultrasonication was continued for 1 h to make the octaisobutyl-POSS evenly dispersed and inserted into the MoS2 layers. The temperature was raised to 80 ° C and vacuum rotary evaporation was performed to remove NMP, and then vacuum dried at 60 ° C for 12 h to obtain POSS-MoS2 hybrid powder.

[0031] After premixing 80g of perfluorinated modified PE particles and 3g of POSS-MoS2 hybrid powder, the obtained premix was fed into a twin-screw extruder with 0.3g of antioxidant 1010 and 3g of PE-g-MAH (maleic anhydride grafted PE) at a temperature of 170°C and a screw speed of 250rpm for mixing for 3 minutes. Then, 5g of PBA-DA-PEG complex was injected from the side feed port, the temperature was adjusted to 155°C, the screw speed was adjusted to 180rpm, and mixing was carried out for 2 minutes. The mixture was extruded and pelletized after water cooling to obtain antibacterial and anti-scale PE material particles.

[0032] Example 2 100 g of polyethylene (PE) was dissolved in 300 mL of xylene solvent, heated to 120 ° C and stirred to dissolve, 15 g of perfluorohexylethylene and 0.15 g of diisopropylbenzene peroxide (DCP) were added, and the mixture was reacted at 140 ° C for 3 h under nitrogen protection. After cooling to room temperature, the reaction system was slowly poured into 800 ml of anhydrous methanol under magnetic stirring at a speed of 400 rpm to precipitate. The precipitate was vacuum filtered and washed with methanol 3 times to remove adsorbed impurities. The precipitate was vacuum dried at 60 ° C for 12 h to obtain perfluorinated modified PE particles.

[0033] 15 g of tetra-PEG-NH2 was dissolved in 800 mL of PBS buffer (pH 7.4). 1.5 g of 4-carboxyphenylboronic acid (PBA-COOH), 2 g of EDC·HCl (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride), and 1 g of NHS (N-hydroxysuccinimide) catalyst were added sequentially. The mixture was stirred under nitrogen and protected from light for 24 h. After completion of the reaction, unreacted material was removed by ultrafiltration and freeze-dried to obtain PBA-PEG. The mixture was then dissolved in 600 mL of 10 mM Tris-HCl buffer (pH 8.5). 5 g of dopamine hydrochloride (DA) was added, mixed, and oxidized by bubbling air for 12 h. When the reaction solution gradually changed from colorless to brown, it was dialyzed to a molecular weight cutoff of 3.5 kDa and freeze-dried to obtain the PBA-DA-PEG complex.

[0034] 10 g of MoS2 powder with a particle size of 1-2 μm was added to 500 mL of anhydrous N-methylpyrrolidone (NMP) and ultrasonically treated at a power of 600 W for 2 h to peel off into few-layer MoS2 nanosheets. 5 g of octaisobutyl-POSS was added and ultrasonication was continued for 1 h to make the octaisobutyl-POSS evenly dispersed and inserted into the MoS2 layers. The temperature was raised to 80 ° C and vacuum rotary evaporation was performed to remove NMP, and then vacuum dried at 60 ° C for 12 h to obtain POSS-MoS2 hybrid powder.

[0035] After premixing 90g of perfluorinated modified PE particles and 5g of POSS-MoS2 hybrid powder, the obtained premix was fed into a twin-screw extruder with 0.5g of antioxidant 1010 and 5g of PE-g-MAH (maleic anhydride grafted PE) at a temperature of 180°C and a screw speed of 250rpm for mixing for 2 minutes. Then, 8g of PBA-DA-PEG complex was injected from the side feed port, the temperature was adjusted to 160°C, the screw speed was adjusted to 180rpm, and mixing was carried out for 1 minute. The mixture was extruded and pelletized after water cooling to obtain antibacterial and anti-scaling PE material particles.

[0036] Example 3 100 g of polyethylene (PE) was dissolved in 300 mL of xylene solvent, heated to 120 ° C and stirred to dissolve, 15 g of perfluorohexylethylene and 0.15 g of diisopropylbenzene peroxide (DCP) were added, and the mixture was reacted at 140 ° C for 3 h under nitrogen protection. After cooling to room temperature, the reaction system was slowly poured into 800 ml of anhydrous methanol under magnetic stirring at a speed of 350 rpm to precipitate. The precipitate was vacuum filtered and washed with methanol 3 times to remove adsorbed impurities. The precipitate was vacuum dried at 60 ° C for 12 h to obtain perfluorinated modified PE particles.

[0037] 12 g of tetra-PEG-NH2 was dissolved in 600 mL of PBS buffer (pH 7.4). 1.2 g of 4-carboxyphenylboronic acid (PBA-COOH), 1.6 g of EDC·HCl (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride), and 1 g of NHS (N-hydroxysuccinimide) catalyst were added sequentially. The mixture was stirred under nitrogen and protected from light for 24 h. After the reaction, unreacted material was removed by ultrafiltration and freeze-dried to obtain PBA-PEG. The mixture was then dissolved in 550 mL of 10 mM Tris-HCl buffer (pH 8.5). 4 g of dopamine hydrochloride (DA) was added, mixed, and oxidized by bubbling air for 12 h. When the reaction solution gradually changed from colorless to brown, it was dialyzed to a molecular weight cutoff of 3.5 kDa and freeze-dried to obtain the PBA-DA-PEG complex.

[0038] 10 g of MoS2 powder with a particle size of 1-2 μm was added to 500 mL of anhydrous N-methylpyrrolidone (NMP) and ultrasonically treated at a power of 600 W for 2 h to peel off into few-layer MoS2 nanosheets. 5 g of octaisobutyl-POSS was added and ultrasonication was continued for 1 h to make the octaisobutyl-POSS evenly dispersed and inserted into the MoS2 layers. The temperature was raised to 80 ° C and vacuum rotary evaporation was performed to remove NMP, and then vacuum dried at 60 ° C for 12 h to obtain POSS-MoS2 hybrid powder.

[0039] After premixing 85g of perfluorinated modified PE particles and 4g of POSS-MoS2 hybrid powder, the obtained premix was fed into a twin-screw extruder with 0.4g of antioxidant 1010 and 4g of PE-g-MAH (maleic anhydride grafted PE) at a temperature of 175°C and a screw speed of 250rpm for mixing for 2.5min. Then, 6g of PBA-DA-PEG complex was injected from the side feed port, the temperature was adjusted to 160°C, the screw speed was adjusted to 180rpm, and mixing was carried out for 1.5min. The mixture was extruded and pelletized after water cooling to obtain antibacterial and anti-scale PE material particles.

[0040] Example 4 100 g of polyethylene (PE) was dissolved in 300 mL of xylene solvent, heated to 120 ° C and stirred to dissolve, 15 g of perfluorohexylethylene and 0.15 g of diisopropylbenzene peroxide (DCP) were added, and the mixture was reacted at 140 ° C for 3 h under nitrogen protection. After cooling to room temperature, the reaction system was slowly poured into 800 ml of anhydrous methanol under magnetic stirring at a speed of 350 rpm to precipitate. The precipitate was vacuum filtered and washed with methanol 3 times to remove adsorbed impurities. The precipitate was vacuum dried at 60 ° C for 12 h to obtain perfluorinated modified PE particles.

[0041] Ten grams of tetra-PEG-NH2 were dissolved in 600 mL of PBS buffer (pH 7.4). Then, 1.0 g of 4-carboxyphenylboronic acid (PBA-COOH), 1.5 g of EDC·HCl (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride), and 0.8 g of NHS (N-hydroxysuccinimide) catalyst were added sequentially. The mixture was stirred under nitrogen and protected from light for 24 h. After the reaction, unreacted material was removed by ultrafiltration and freeze-dried to obtain PBA-PEG. The mixture was then dissolved in 550 mL of 10 mM Tris-HCl buffer (pH 8.5). 3 g of dopamine hydrochloride (DA) was added, mixed, and oxidized by bubbling air for 12 h. When the reaction solution gradually changed from colorless to brown, it was dialyzed to a molecular weight cutoff of 3.5 kDa and freeze-dried to obtain the PBA-DA-PEG complex.

[0042] 10 g of MoS2 powder with a particle size of 1-2 μm was added to 500 mL of anhydrous N-methylpyrrolidone (NMP) and ultrasonically treated at a power of 600 W for 2 h to peel off into few-layer MoS2 nanosheets. 5 g of octaisobutyl-POSS was added and ultrasonication was continued for 1 h to make the octaisobutyl-POSS evenly dispersed and inserted into the MoS2 layers. The temperature was raised to 80 ° C and vacuum rotary evaporation was performed to remove NMP, and then vacuum dried at 60 ° C for 12 h to obtain POSS-MoS2 hybrid powder.

[0043] After premixing 80g of perfluorinated modified PE particles and 3g of POSS-MoS2 hybrid powder, the obtained premix was fed into a twin-screw extruder with 0.5g of antioxidant 1010 and 4g of PE-g-MAH (maleic anhydride grafted PE) at a temperature of 175°C and a screw speed of 250rpm for mixing for 2.5min. Then, 6g of PBA-DA-PEG complex was injected from the side feed port, the temperature was adjusted to 160°C, the screw speed was adjusted to 180rpm, and mixing was carried out for 1.5min. The mixture was extruded and pelletized after water cooling to obtain antibacterial and anti-scale PE material particles.

[0044] Example 5 100 g of polyethylene (PE) was dissolved in 300 mL of xylene solvent, heated to 120 ° C and stirred to dissolve, 15 g of perfluorohexylethylene and 0.15 g of diisopropylbenzene peroxide (DCP) were added, and the mixture was reacted at 140 ° C for 3 h under nitrogen protection. After cooling to room temperature, the reaction system was slowly poured into 800 ml of anhydrous methanol under magnetic stirring at a speed of 350 rpm to precipitate. The precipitate was vacuum filtered and washed with methanol 3 times to remove adsorbed impurities. The precipitate was vacuum dried at 60 ° C for 12 h to obtain perfluorinated modified PE particles.

[0045] 12 g of tetra-PEG-NH2 was dissolved in 600 mL of PBS buffer (pH 7.4). 1.2 g of 4-carboxyphenylboronic acid (PBA-COOH), 1.6 g of EDC·HCl (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride), and 1 g of NHS (N-hydroxysuccinimide) catalyst were added sequentially. The mixture was stirred under nitrogen and protected from light for 24 h. After the reaction, unreacted material was removed by ultrafiltration and freeze-dried to obtain PBA-PEG. The mixture was then dissolved in 550 mL of 10 mM Tris-HCl buffer (pH 8.5). 4 g of dopamine hydrochloride (DA) was added, mixed, and oxidized by bubbling air for 12 h. When the reaction solution gradually changed from colorless to brown, it was dialyzed to a molecular weight cutoff of 3.5 kDa and freeze-dried to obtain the PBA-DA-PEG complex.

[0046] 10 g of MoS2 powder with a particle size of 1-2 μm was added to 500 mL of anhydrous N-methylpyrrolidone (NMP) and ultrasonically treated at a power of 600 W for 2 h to peel off into few-layer MoS2 nanosheets. 5 g of octaisobutyl-POSS was added and ultrasonication was continued for 1 h to make the octaisobutyl-POSS evenly dispersed and inserted into the MoS2 layers. The temperature was raised to 80 ° C and vacuum rotary evaporation was performed to remove NMP, and then vacuum dried at 60 ° C for 12 h to obtain POSS-MoS2 hybrid powder.

[0047] After premixing 85g of perfluorinated modified PE particles and 4g of POSS-MoS2 hybrid powder, the obtained premix was fed into a twin-screw extruder with 0.5g of antioxidant 1010 and 4g of PE-g-MAH (maleic anhydride grafted PE) at a temperature of 175°C and a screw speed of 250rpm for mixing for 2 minutes. Then, 6g of PBA-DA-PEG complex was injected from the side feed port, the temperature was adjusted to 160°C, the screw speed was adjusted to 180rpm, and mixing was carried out for 1.5 minutes. The mixture was extruded and pelletized after water cooling to obtain antibacterial and anti-scaling PE material particles.

[0048] The present invention also provides the following comparative examples and conducts relevant comparative tests.

[0049] Comparative Example 1 Compared with Example 5, the only difference is that perfluorinated modified PE is not prepared, but conventional polyethylene is used instead. The other preparation steps and materials used are the same, and finally antibacterial and scale-inhibiting PE material particles are prepared.

[0050] Comparative Example 2 Compared with Example 5, the only difference is that the PBA-DA-PEG complex is not prepared, and the other preparation steps and materials used are the same, and finally the antibacterial and anti-scaling PE material particles are prepared.

[0051] Comparative Example 3 Compared with Example 5, the only difference is that MoS2 hybrid powder is not prepared, and MoS2 hybrid powder is used instead of MoS2 hybrid powder. The other preparation steps and materials used are the same, and finally antibacterial and scale-inhibiting PE material particles are prepared.

[0052] Performance testing (I) The PE material particles obtained in Examples 1-5 and Comparative Examples 1-3 were injection molded to form a 10 cm × 10 cm × 0.2 cm flat plate, and the following tests were performed: with reference to the standard GB / T 31402-2023, the plates were disinfected with ethanol and then rinsed with sterile water, and Escherichia coli (ATCC 8739) and Staphylococcus aureus (ATCC 6538) were inoculated respectively for antibacterial performance test. The test results are summarized in Table 1 below; a water contact angle test was performed using a JC2000D2G contact angle tester, and the test results are summarized in Table 1 below; a tensile strength test was performed with reference to the standard GB / T 1040.2-2022, and the test results are summarized in Table 1 below.

[0053] Table 1 As can be seen from the test results in Table 1 above, the PE material particles obtained in Examples 1-5 of the present invention have good antibacterial properties and ultra-high hydrophobicity, and can maintain good tensile strength. Compared with Example 5, Comparative Example 1 does not use perfluorohexylethylene to modify PE, and the water contact angle decreases significantly, the hydrophobicity decreases, and the tensile strength also decreases significantly; while Comparative Example 2 does not prepare a PBA-DA-PEG complex, the antibacterial property is poor, and the material cannot meet the antibacterial requirements; and the MoS2 of Comparative Example 3 is not hybridized, and the antibacterial effect also decreases slightly, and the contact angle and tensile strength also decrease. This is mainly due to the hybridized MoS2, which not only improves the dispersion effect, but also helps to improve the antibacterial effect through POSS adsorption, while improving the strength and hydrophobicity of the material.

[0054] (II) The PE material particles obtained in Examples 1-5 and Comparative Examples 1-3 were injection molded into pipes and the following tests were performed: 2+ Under the condition of concentration of 150mg / L (calculated as CaCO3), the inhibition rate of calcium carbonate deposition was tested. The test results are summarized in Table 2 below. Accelerated scaling experiment was also carried out. 2+ Under the condition of concentration of 150 mg / L (calculated as CaCO3), the scale inhibition performance was tested for a long term stability after 30 days of circulation. The calcium carbonate deposition inhibition rate after 30 days was tested. The test results are summarized in Table 2 below.

[0055] Table 2 From the test results in Table 2 above, it can be seen that the PE material particles obtained in Examples 1-5 of the present invention can achieve a good calcium carbonate deposition inhibition rate, all of which are greater than 84.5%, and have good scale inhibition performance. Moreover, after 30 days of heating cycle, the deposition inhibition rate does not decrease much and can still be maintained at above 78.2%, indicating that the antibacterial and scale-inhibiting PE material obtained by the present invention can maintain long-term and stable scale inhibition performance. Compared with Example 5, the inhibition rate of Comparative Example 1 is slightly lower, mainly because perfluorohexylethylene is not used to modify PE, the hydrophobicity is reduced, the surface smoothness becomes lower, and there is a little precipitation adsorption, but after 30 days of heating cycle, the deposition inhibition rate does not decrease too much; while Comparative Example 2 does not prepare PBA-DA-PEG composite, the scale inhibition performance is the worst, and the scale inhibition requirements cannot be met, and after 30 days of heating cycle, the deposition inhibition rate decreases significantly, indicating that the PBA-DA-PEG composite plays a key role in self-repair and maintaining the stability of scale inhibition performance; and the scale inhibition performance of Comparative Example 3 also decreases slightly, indicating that the POSS-MoS2 hybrid powder can better improve the surface smoothness and more effectively reduce scale deposition.

[0056] The above are preferred embodiments of the present invention. For ordinary technicians in this technical field, several improvements and modifications made without departing from the principles of the present invention should also be considered as the scope of protection of the present invention.

Claims

1. A method for preparing a PE material with antibacterial and anti-scaling properties, characterized by: The method comprises the following preparation steps: S1. Dissolve polyethylene in xylene, heat and stir to dissolve, add perfluorohexylethylene and diisopropylbenzene peroxide to react, cool, pour into anhydrous methanol for precipitation, vacuum filter, wash, and vacuum dry to obtain perfluoro-modified PE; S2. Dissolve four-arm polyethylene glycol amine in PBS buffer, add 4-carboxyphenylboronic acid, EDC·HCl, and NHS, stir in the dark, ultrafilter, and freeze-dry to obtain PBA-PEG. S3. The obtained PBA-PEG was dissolved in Tris-HCl buffer, dopamine hydrochloride was added and mixed, and an oxidation reaction was performed. The mixture was purified by dialysis and freeze-dried to obtain a PBA-DA-PEG complex. S4. The POSS-MoS2 hybrid powder is premixed with perfluorinated modified PE, the obtained premix is ​​mixed with an antioxidant and a compatibilizer, and the PBA-DA-PEG complex is injected. The premix is ​​further mixed, extruded, and pelletized by water cooling to obtain an antibacterial and anti-scaling PE material.

2. The method for preparing a bacteriostatic and scale-inhibiting PE material according to claim 1, characterized in that: The POSS-MoS2 hybrid powder is prepared by the following method: adding MoS2 powder to anhydrous N-methylpyrrolidone, performing ultrasonic treatment, adding octaisobutyl-POSS, continuing ultrasonication, performing vacuum rotary evaporation, and then vacuum drying to obtain.

3. The method for preparing a bacteriostatic and scale-inhibiting PE material according to claim 2, characterized in that: During the preparation process of the POSS-MoS2 hybrid powder, MoS2 powder with a particle size of 1-2 μm is added to anhydrous N-methylpyrrolidone, ultrasonically treated at a power of 600 W for 2 hours, octaisobutyl-POSS is added, ultrasonication is continued for 1 hour, the temperature is raised to 80°C for vacuum rotary evaporation, and then vacuum dried at 60°C for 12 hours to obtain.

4. The method for preparing a bacteriostatic and scale-inhibiting PE material according to claim 2, characterized in that: In the step S4, after the POSS-MoS2 hybrid powder is premixed with the perfluorinated modified PE, the obtained premix is ​​fed into a twin-screw extruder with an antioxidant and a compatibilizer at a temperature of 170-180°C and a screw speed of 250 rpm for mixing for 2-3 minutes, and then the PBA-DA-PEG complex is injected from the side feeding port, the temperature is adjusted to 155-160°C, the screw speed is adjusted to 180 rpm, and mixing is carried out for 1-2 minutes. The mixture is extruded and pelletized after water cooling to obtain an antibacterial and scale-inhibiting PE material.

5. The method for preparing a bacteriostatic and scale-inhibiting PE material according to claim 1, characterized in that: In step S1, the temperature is raised to 120° C. for stirring and dissolving, perfluorohexylethylene and diisopropylbenzene peroxide are added, and the reaction is carried out at 140° C. for 3 hours under nitrogen protection. The reaction is cooled to room temperature, and then the reaction system is slowly poured into anhydrous methanol for precipitation under magnetic stirring at a speed of 300-400 rpm. The reaction is vacuum filtered, and the precipitate is washed with methanol three times and vacuum dried at 60° C. for 12 hours to obtain perfluoro-modified PE.

6. The method for preparing a bacteriostatic and scale-inhibiting PE material according to claim 1, characterized in that: In step S2, four-arm polyethylene glycol amine is dissolved in PBS buffer at a pH of 7.4, 4-carboxyphenylboronic acid, EDC·HCl and NHS are added, and the mixture is stirred in the dark under nitrogen protection for 24 hours, ultrafiltered and freeze-dried to obtain PBA-PEG.

7. The method for preparing a bacteriostatic and scale-inhibiting PE material according to claim 1, characterized in that: In step S3, PBA-PEG is dissolved in a 10 mM Tris-HCl buffer solution with a pH of 8.5, dopamine hydrochloride is added and mixed, and air is introduced to carry out an oxidation reaction for 12 hours, followed by purification by dialysis with a molecular weight cutoff of 3.5 kDa, and freeze-drying to obtain a PBA-DA-PEG complex.

8. The method for preparing a bacteriostatic and scale-inhibiting PE material according to claim 1, characterized in that: The antioxidant is antioxidant 1010; the compatibilizer is PE-g-MAH.

9. A PE material with antibacterial and anti-scaling properties, characterized by: The antibacterial and scale-inhibiting PE material is prepared by the preparation method of any one of claims 1 to 8, and comprises the following components in parts by mass: 80-90 parts of perfluorinated modified PE, 0.3-0.5 parts of antioxidant, 3-5 parts of compatibilizer, and 5-8 parts of PBA-DA-PEG complex.

10. The antibacterial and anti-scaling PE material according to claim 9, characterized in that: The PBA-DA-PEG complex comprises the following raw materials in parts by mass: 10-15 parts of four-arm polyethylene glycol amine, 1-1.5 parts of 4-carboxylphenylboronic acid, 1.5-2 parts of EDC·HCl, 0.8-1 part of NHS and 3-5 parts of dopamine hydrochloride.

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