Method for modifying and reinforcing HDPE pipe through ZnO-TCS

Abstract

The invention discloses a method for modifying and reinforcing an HDPE pipe through ZnO-TCS, and belongs to the field of polymer composite material processing. The preparation method comprises the following steps: melting and mixing high-density polyethylene and a ZnO-TCS antibacterial agent, crushing, drying, and carrying out injection molding to prepare the enhanced HDPE composite antibacterial pipe. The preparation process is simple, the cost is low, and the obtained enhanced HDPE composite antibacterial pipe has the characteristics of excellent antibacterial performance, high strength and the like, can be widely applied to the field of domestic and industrial water delivery pipelines, and has remarkable economic value and social benefit.

Description

Technical Field

[0001] The invention belongs to the field of polymer composite material processing, and in particular relates to a method for ZnO-TCS modified and reinforced HDPE pipe. Background Art

[0002] High-density polyethylene is a highly crystalline, non-polar thermoplastic resin with good heat resistance and cold resistance, good chemical stability and good mechanical strength. It is widely used in films, pipes, various hollow products, injection molded products, fibers and other material fields. However, high-density polyethylene as a pipe must have stronger antibacterial and mechanical properties under specific working conditions. In order to further make polyethylene pipes more widely used in life and production, and to improve the antibacterial and mechanical properties of polyethylene pipes, it is required that the antibacterial agent has good enough compatibility and dispersibility with the matrix.

[0003] Antimicrobial agents for plastics are a class of chemical substances that can inhibit or kill bacteria. According to their different chemical compositions, antimicrobial agents for plastics can be divided into four categories: inorganic antimicrobial agents, organic antimicrobial agents, natural antimicrobial agents, and composite antimicrobial agents. Inorganic antimicrobial agents mainly include metal ions and metal oxides such as silver, copper, and zinc, as well as some nanomaterials. Among them, silver or zinc antimicrobial agents are widely used. Organic antimicrobial agents are chemically synthesized substances. Common ones include quaternary ammonium salts, such as hexadecyltrimethylammonium bromide (CTAB) and hexadecyltrimethylammonium chloride (CTAC), which work by destroying the bacterial cell membrane structure. Natural antimicrobial agents, such as chitosan, are deacetylated products of chitin, with stable properties and great development potential. Composite antimicrobial agents combine the advantages of inorganic and organic antimicrobial agents to improve the antimicrobial effect and application range. Antimicrobial agents for plastics have a wide range of applications, including automobiles, household appliances, medical treatment, pipes, etc. The development and application of antimicrobial plastics are of great significance to improving the living environment of human beings.

[0004] Zinc oxide antimicrobial agent is a material with multiple antimicrobial mechanisms. Zinc oxide can generate highly active photogenerated electrons and holes under light conditions, especially ultraviolet light. These photogenerated holes can excite oxygen in the air to become active oxygen, have extremely strong chemical activity, and can undergo oxidation reactions with a variety of microorganisms, thereby killing bacteria. The zinc ion dissolution mechanism is also an important part of the antibacterial effect of zinc oxide. Zinc oxide will slowly release zinc ions in an aqueous medium. These zinc ions bind to the bacterial cell membrane, destroy the structure of membrane proteins, and make them inactive, achieving the purpose of sterilization. In addition, the generation of active oxygen is related to light. Based on the semiconductor properties of zinc oxide, light will lead to the generation of free electrons and electron holes, and then generate active oxygen groups, which connects the active oxygen antibacterial of zinc oxide with the photocatalytic antibacterial effect.

[0005] Triclosan is a broad-spectrum antibacterial agent, and its antibacterial principle is mainly to inhibit bacterial fatty acid synthesis. Triclosan has killing and inhibitory effects on a variety of Gram-positive bacteria, Gram-negative bacteria, fungi and viruses, so its application field is very wide, including toothpaste, soap, facial cleanser, hand sanitizer and other personal care products, as well as medical device disinfectants, wound disinfectants, etc. Summary of the invention

[0006] The existing high-density polyethylene pipes obtained by injection molding have the problems of poor strength and no antibacterial ability. To this end, the present invention provides a method for ZnO-TCS modified and reinforced HDPE pipes, which combines zinc oxide with triclosan as antibacterial agents so that the obtained pipes can not only take into account the stability of the zinc oxide inorganic antibacterial agent and the excellent antibacterial properties of triclosan, but also can simultaneously achieve the improvement of the strength of the polyethylene pipe.

[0007] To achieve the above object, the present invention adopts the following technical solution: A method for preparing a ZnO-TCS enhanced HDPE composite antibacterial pipe comprises the steps of melt-mixing, crushing, drying and injection molding high-density polyethylene and a ZnO-TCS antibacterial agent to obtain the enhanced HDPE composite antibacterial pipe.

[0008] Furthermore, the dosage of the ZnO-TCS antibacterial agent is 1% to 2% of the mass of the high-density polyethylene.

[0009] Furthermore, the model of the high-density polyethylene is 5000S, and its density is 0.941~0.960 g / cm³.

[0010] Furthermore, the preparation method of the ZnO-TCS antibacterial agent comprises the following steps: (1) Accurately weigh 1g zinc oxide and add it to 60ml ethanol solution with a volume concentration of 99%, then add 20ml pure water and 1ml silane coupling agent KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH value to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan (TCS) powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly add 0.7 ml of methacrylic anhydride, then add 0.3 g of 4-dimethylaminopyridine (DMAP) powder, and finally add 1 M NaOH solution to adjust the pH value to about 9. React for 6 h in an oil bath at 60°C and 600 r / min. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, pass nitrogen for 30 min, then add 0.5 g of azobisisobutylimidazoline hydrochloride (AIBI) powder, react under oil bath conditions of 55°C and 600 r / min for 10 h, and finally centrifuge, wash, and freeze-dry to obtain the ZnO-TCS antibacterial agent.

[0011] Furthermore, the melt mixing is carried out in a torque rheometer at 200° C. and 100 r / min for 9 to 10 min.

[0012] Furthermore, the injection molding is performed in a micro injection molding machine at 220° C. and a pressure of 0.3-0.5 MPa for 10 seconds and holding the pressure for 5 seconds.

[0013] The beneficial effects of the present invention are: (1) The antibacterial effect of zinc oxide requires a light environment, and the antibacterial effect is poor in the absence of light. The present invention prepares the ZnO-TCS antibacterial agent by grafting the organic antibacterial agent triclosan onto the inorganic antibacterial agent zinc oxide. In the process, the carbon-carbon double bond on TCS-MA is polymerized with the carbon-carbon double bond of ZnO-KH570 to form a highly stable carbon-carbon single bond. On the one hand, this allows the obtained antibacterial agent to have the high stability and high temperature resistance of the inorganic antibacterial agent, and on the other hand, it allows the obtained antibacterial agent to still have excellent antibacterial effects in the absence of light. In addition, since the antibacterial agent is obtained by modifying zinc oxide as a matrix, it can act as a sea island structure in polyethylene, which greatly improves the strength of the composite material.

[0014] (2) In the process of preparing the ZnO-TCS antibacterial agent of the present invention, KH570 is grafted onto zinc oxide to insert a double bond. At the same time, based on the characteristics of triclosan having independent phenolic hydroxyl groups and methacrylic anhydride having high esterification reaction ability, triclosan and methacrylic anhydride are subjected to an esterification reaction to graft a double bond onto triclosan. Finally, the ZnO-TCS antibacterial agent obtained by the polymerization reaction of carbon-carbon double bonds can take into account the high stability of zinc oxide and the broad-spectrum antibacterial properties of triclosan, and can effectively kill and inhibit a variety of Gram-positive bacteria, Gram-negative bacteria, molds, yeasts and viruses.

[0015] (3) Due to the difficulty in processing pipes, the antibacterial modification of common polyolefin compounds on the market is mostly seen in the field of films and coatings. The processing technology for preparing the enhanced high-density polyethylene pipe of the present invention is simple, and only requires simple thermal processing to form. The process is simple and fast, and the raw materials are cheap and easy to obtain.

[0016] (4) The reinforced high-density polyethylene pipe prepared by the present invention has good antibacterial properties, and its antibacterial effect can reach 99%. It also has excellent mechanical properties, with a tensile strength of 31.4MPa~34.8MPa, a bending strength of 18.5MPa~19.6MPa, and an impact strength of 107.4 KJ / m 2 ~110.4 KJ / m 2 The elongation at break is 665% ~ 720%, which can be widely used in the fields of domestic and industrial water pipelines, and has significant economic value and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The infrared absorption spectra of ZnO-KH570 and ZnO-TCS antibacterial agents prepared in Example 1 are shown in FIG.

[0018] Figure 2 This is the infrared absorption spectrum of TCS-MA prepared in Example 1.

[0019] Figure 3 This is a cross-sectional morphology of the enhanced modified high-density polyethylene composite antibacterial pipe prepared in Example 1.

[0020] Figure 4 This is a cross-sectional morphology diagram of the polyethylene composite material prepared in Comparative Example 1. DETAILED DESCRIPTION

[0021] A ZnO-TCS enhanced HDPE composite antibacterial pipe, the preparation of which comprises the following steps: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH value to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly add 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH value to 9. React for 6 h in an oil bath at 60°C and 600 r / min. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, flow nitrogen for 30 min, then add 0.5 g of AIBI powder, react for 10 h in an oil bath at 55 °C and 600 r / min, and finally centrifuge and wash, and freeze-dry to obtain the ZnO-TCS antibacterial agent; (4) High-density polyethylene and 1% to 2% ZnO-TCS antibacterial agent by weight were added to a torque rheometer and mixed at 200°C and 100 r / min for 9 to 10 min. After that, the mixture was crushed and dried in a vacuum drying oven overnight. It was then added to a micro injection molding machine and pressed at 220°C and a pressure of 0.3 to 0.5 MPa for 10 seconds and maintained at pressure for 5 seconds to obtain a reinforced HDPE composite antibacterial pipe.

[0022] In order to make the contents of the present invention easier to understand, the technical solution of the present invention is further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0023] The model of high-density polyethylene used in the embodiment is 5000S, and its density is 0.941-0.960 g / cm³.

[0024] Example 1 The preparation steps of ZnO-TCS enhanced high-density polyethylene composite antibacterial pipe are as follows: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly drop 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH to about 9. React at 60°C, 600 r / min oil bath conditions for 6 h. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of the prepared TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, flow nitrogen for 30 min, then add 0.5 g of AIBI powder, react under oil bath conditions of 55 °C and 600 r / min for 10 h, finally centrifuge and wash, and freeze-dry to obtain ZnO-TCS antibacterial agent; (4) 100 parts by weight of high-density polyethylene and 1.5 parts by weight of the prepared ZnO-TCS antibacterial agent were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed and dried in a 60°C drying oven overnight, and then added to a micro injection molding machine. The mold temperature was set to 55°C, and stamped at 220°C and a pressure of 0.4 MPa for 10 s, and the pressure was maintained for 5 s to obtain a ZnO-TCS-reinforced high-density polyethylene composite antibacterial pipe.

[0025] Figure 1 The infrared absorption spectra of ZnO-KH570 and ZnO-TCS antibacterial agents prepared in this embodiment are shown in the figure. -1 and 1635 cm -1 The absorption peaks of the carbon-carbon double bond and the Si-O bond correspond to the absorption peaks of the carbon-carbon double bond. By comparing ZnO, it can be seen that the silane coupling agent was successfully grafted onto ZnO and a carbon-carbon double bond was introduced. By comparing ZnO-KH570 and ZnO-TCS, it can be found that the absorption peak of the carbon-carbon double bond in ZnO-TCS disappeared, indicating that the polymerization reaction caused the carbon-carbon double bond to polymerize into a carbon-carbon single bond. At the same time, the absorption peak of ZnO-TCS at 1475 cm -1 and 1748 cm -1 The absorption peaks of benzene ring and ester group appear at the bottom of the graphite layer. Since ZnO-KH570 itself does not have benzene ring and ester group, it shows that zinc oxide has been successfully grafted with triclosan.

[0026] Figure 2 The infrared absorption spectrum of TCS-MA prepared in this example is shown in the figure. -1 The absorption peak of triclosan corresponds to the stretching vibration absorption peak of C-Cl, which indicates that the antibacterial functional group is not damaged during the grafting of triclosan with methacrylic anhydride; triclosan has an absorption peak of 3310 cm -1 The corresponding hydroxyl stretching vibration absorption peak at 2930 cm -1 The stretching vibration absorption peak of methyl group appeared at 1635 cm -1 and 1748 cm -1 The corresponding absorption peaks are carbon-carbon double bond and carbon-oxygen bond, respectively, indicating that TCS-MA has been successfully grafted with carbon-carbon double bond through esterification reaction.

[0027] Figure 3 This is a cross-sectional morphology diagram of the enhanced modified high-density polyethylene composite antibacterial pipe prepared in this embodiment. As shown in the figure, a large number of wire drawing morphologies and granular substances appear on the cross section of the material, indicating that the addition of antibacterial agents can enhance the high-density polyethylene material.

[0028] Example 2 The preparation steps of ZnO-TCS enhanced high-density polyethylene composite antibacterial pipe are as follows: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly drop 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH to about 9. React at 60°C, 600 r / min oil bath conditions for 6 h. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of the prepared TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, flow nitrogen for 30 min, then add 0.5 g of AIBI powder, react under oil bath conditions of 55 °C and 600 r / min for 10 h, finally centrifuge and wash, and freeze-dry to obtain ZnO-TCS antibacterial agent; (4) 100 parts by weight of high-density polyethylene and 1 part by weight of the prepared ZnO-TCS antibacterial agent were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed and dried in a 60°C drying oven overnight, and then added to a micro injection molding machine. The mold temperature was set to 55°C, and punched at 220°C and a pressure of 0.4 MPa for 10 s, and the pressure was maintained for 5 s to obtain a ZnO-TCS-enhanced high-density polyethylene composite antibacterial pipe.

[0029] Example 3 The preparation steps of ZnO-TCS enhanced high-density polyethylene composite antibacterial pipe are as follows: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly drop 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH to about 9. React at 60°C, 600 r / min oil bath conditions for 6 h. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of the prepared TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, flow nitrogen for 30 min, then add 0.5 g of AIBI powder, react under oil bath conditions of 55 °C and 600 r / min for 10 h, finally centrifuge and wash, and freeze-dry to obtain ZnO-TCS antibacterial agent; (4) 100 parts by weight of high-density polyethylene and 2 parts by weight of the prepared ZnO-TCS antibacterial agent were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed and dried in a 60°C drying oven overnight, and then added to a micro injection molding machine. The mold temperature was set to 55°C, and punched at 220°C and a pressure of 0.4 MPa for 10 s, and the pressure was maintained for 5 s to obtain a ZnO-TCS-reinforced high-density polyethylene composite antibacterial pipe.

[0030] Comparative Example 1 The preparation steps of high-density polyethylene pipe are as follows: 100 parts by weight of high-density polyethylene were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 minutes, crushed and dried in a 60°C drying oven overnight, and then the obtained powder was added to a micro injection molding machine, the mold temperature was set to 55°C, and punched at 220°C and a pressure of 0.4 MPa for 10 seconds, and the pressure was maintained for 5 seconds to obtain a high-density polyethylene pipe.

[0031] Figure 4 This is a cross-sectional morphology diagram of the high-density polyethylene pipe prepared in this comparative example. As can be seen from the figure, there is no obvious wire drawing state and particles in its cross section.

[0032] Comparative Example 2 The preparation steps of ZnO modified high-density polyethylene composite pipe are as follows: 100 parts by weight of high-density polyethylene and 1.5 parts by weight of ZnO were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 minutes, crushed and dried in a 60°C drying oven overnight, and then added to a micro injection molding machine. The mold temperature was set to 55°C, and punched at 220°C and a pressure of 0.4 MPa for 10 seconds, and the pressure was maintained for 5 seconds to obtain a ZnO-modified high-density polyethylene composite pipe.

[0033] Comparative Example 3 The preparation steps of TSC modified high-density polyethylene composite pipe are as follows: 100 parts by weight of high-density polyethylene and 1.5 parts by weight of TCS were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 minutes, crushed and dried in a 60°C drying oven overnight, and then the obtained powder was added to a micro injection molding machine, the mold temperature was set to 55°C, and punched at 220°C and a pressure of 0.4 MPa for 10 seconds, and the pressure was maintained for 5 seconds to obtain a TCS-modified high-density polyethylene composite pipe.

[0034] Comparative Example 4 The preparation steps of ZnO-KH570 modified high-density polyethylene composite pipe are as follows: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) 100 parts by weight of high-density polyethylene and 1.5 parts by weight of ZnO-KH570 powder were placed in a torque rheometer and mixed at 200°C and 100 r / min for 9 min. After being crushed, the powder was placed in a 60°C drying oven and dried overnight. The resulting powder was then added to a micro injection molding machine, the mold temperature was set to 55°C, and the machine was punched at 220°C and a pressure of 0.4 MPa for 10 s and maintained at pressure for 5 s to obtain a ZnO-KH570-modified high-density polyethylene composite pipe.

[0035] Comparative Example 5 The preparation steps of ZnO / TCS composite modified high-density polyethylene composite pipe are as follows: 100 parts by weight of high-density polyethylene, 1 part by weight of ZnO, and 0.5 parts by weight of TCS were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 minutes, crushed and dried in a 60°C drying oven overnight, and then added to a micro injection molding machine. The mold temperature was set to 55°C, and punched at 220°C and a pressure of 0.4 MPa for 10 seconds, and the pressure was maintained for 5 seconds to obtain a ZnO / TCS composite-modified high-density polyethylene composite pipe.

[0036] The finished products obtained in the embodiments and comparative examples were tested for antibacterial properties according to GB / T 20944.3-2008; the bending strength was tested according to the test method of GB / T9341-2008; the impact strength was tested according to the test method of ISO179-1:2000; the tensile strength and elongation at break were tested according to the test method of GB / T 1040.2-2006. The results are shown in Table 1.

[0037] Table 1 Performance test results

[0038] From the results in Table 1, it can be seen that compared with the pipe obtained in the comparative example, the antibacterial performance and strength of the pipe prepared in the embodiment are significantly improved, proving that the prepared enhanced high-density polyethylene composite pipe has excellent antibacterial performance and can achieve improved mechanical properties. Among them, the enhanced high-density polyethylene composite antibacterial pipe prepared in Example 1 has the best antibacterial performance and excellent mechanical properties.

[0039] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. A method for ZnO-TCS modified and reinforced HDPE pipe, characterized in that: The high-density polyethylene and the ZnO-TCS antibacterial agent are melt-mixed, crushed, dried and injection-molded to obtain a reinforced HDPE composite antibacterial pipe.

2. The method for ZnO-TCS modified and reinforced HDPE pipe according to claim 1, characterized in that: The model of the high-density polyethylene is 5000S, and its density is 0.941~0.960 g / cm³.

3. The method for ZnO-TCS modified and reinforced HDPE pipe according to claim 1, characterized in that: The dosage of the ZnO-TCS antibacterial agent is 1% to 2% of the mass of the high-density polyethylene.

4. The method for ZnO-TCS modified and reinforced HDPE pipe according to claim 1 or 3, characterized in that: The preparation method of the ZnO-TCS antibacterial agent comprises the following steps: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH value to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly add 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH value to 9. React for 6 h in an oil bath at 60°C and 600 r / min. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, pass nitrogen for 30 min, then add 0.5 g of AIBI powder, react for 10 h in an oil bath at 55°C and 600 r / min, and finally centrifuge, wash, and freeze-dry to obtain the ZnO-TCS antibacterial agent.

5. The method for ZnO-TCS modified and reinforced HDPE pipe according to claim 1, characterized in that: The melt mixing is carried out in a torque rheometer at 200° C. and 100 r / min for 9 to 10 min.

6. The method for ZnO-TCS modified and reinforced HDPE pipe according to claim 1, characterized in that: The injection molding is carried out in a micro injection molding machine at 220° C. and a pressure of 0.3-0.5 MPa for 10 seconds and holding the pressure for 5 seconds.

7. A reinforced HDPE composite antibacterial pipe prepared by the method as claimed in claim 1.

Images