A method for modifying and reinforcing hdpe pipes with zn o-tcs

Abstract

The application discloses a method for modifying and reinforcing HDPE pipe material by ZnO-TCS, and belongs to the field of polymer composite material processing. The method comprises the following steps: melting and mixing high-density polyethylene and ZnO-TCS antibacterial agent, crushing, drying and injection molding to obtain reinforced HDPE composite antibacterial pipe material. The method has the advantages of simple preparation process and low cost, and the obtained reinforced HDPE composite antibacterial pipe material has the characteristics of excellent antibacterial performance and high strength, can be widely used in the fields of living and industrial water conveying pipes, and has remarkable economic value and social benefits.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of polymer composite processing, and particularly relates to a method for modifying and reinforcing HDPE pipe material by ZnO-TCS. BACKGROUND

[0002] High-density polyethylene is a kind of thermoplastic resin with high crystallinity and non-polarity, which has good heat resistance and cold resistance, and good chemical stability and good mechanical strength, and is widely used in the fields of film, pipe, various hollow products, injection molded products, fibers and the like. However, high-density polyethylene as pipe material needs to have stronger antibacterial performance and mechanical performance under specific working conditions. In order to further make polyethylene pipe material more widely used in life and production, and improve the antibacterial performance and mechanical performance of polyethylene pipe material, it is required that the antibacterial agent has good compatibility and dispersibility with the base body.

[0003] Plastic antibacterial agent is a kind of chemical substance that can inhibit or kill bacteria. According to the different chemical components, plastic antibacterial agent can be divided into four categories: inorganic antibacterial agent, organic antibacterial agent, natural antibacterial agent and composite antibacterial agent. Inorganic antibacterial agent mainly includes metal ions and metal oxides of silver, copper, zinc and the like, as well as some nanomaterials, among which, silver-based or zinc-based antibacterial agent is widely used. Organic antibacterial agent is a chemical synthetic substance, and common ones are quaternary ammonium salts, such as cetyltrimethylammonium bromide (CTAB) and cetyltrimethylammonium chloride (CTAC), which play a role by destroying the structure of bacterial cell membrane. Natural antibacterial agent, such as chitosan, is a deacetylation product of chitin, which has stable properties and great development potential. Composite antibacterial agent combines the advantages of inorganic and organic antibacterial agents, and improves the antibacterial effect and application range. Plastic antibacterial agent has a wide range of application fields, including automobiles, household appliances, medical treatment, pipe materials and the like. The development and application of antibacterial plastic have important significance for improving the living environment of human beings.

[0004] Zinc oxide antibacterial agent is a material with multiple antibacterial mechanisms. Under light conditions, especially under ultraviolet light irradiation, zinc oxide can produce highly active photo-generated electrons and holes. These photo-generated holes can excite oxygen in the air to become active oxygen, which has strong chemical activity and can react with various microorganisms to kill bacteria. The zinc ion dissolution mechanism is also an important part of the antibacterial effect of zinc oxide. Zinc oxide slowly releases zinc ions in aqueous medium, and these zinc ions combine with the cell membrane of bacteria to destroy the structure of membrane proteins, making them lose activity and achieving the purpose of killing bacteria. In addition, the generation of active oxygen is related to light. Based on the semiconductor properties of zinc oxide, the generation of free electrons and electron holes under the action of light leads to the generation of active oxygen groups, which makes the active oxygen antibacterial effect of zinc oxide and the photocatalytic antibacterial effect interrelated.

[0005] Triclosan is a broad-spectrum antibacterial agent, its antibacterial principle is mainly through inhibiting the synthesis of fatty acids to play a role. Triclosan has killing and inhibiting effect 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, and medical device disinfectant, wound disinfectant, etc. SUMMARY

[0006] The existing high-density polyethylene pipe formed by injection molding has the problems of poor strength and no antibacterial ability, therefore, the application provides a method for modifying and reinforcing ZnO-TCS HDPE pipe, which combines zinc oxide and triclosan as an antibacterial agent, so that the obtained pipe can not only have the stability of zinc oxide inorganic antibacterial agent and the excellent antibacterial performance of triclosan, but also can improve the strength of the polyethylene pipe.

[0007] To achieve the above purpose, the application adopts the following technical scheme:

[0008] A preparation method of ZnO-TCS reinforced HDPE composite antibacterial pipe, which is prepared by melt mixing, crushing, drying and injection molding of high-density polyethylene and ZnO-TCS antibacterial agent.

[0009] Further, the amount of ZnO-TCS antibacterial agent is 1% to 2% of the mass of high-density polyethylene.

[0010] Further, the model of the high-density polyethylene is 5000S, and the density is 0.941 to 0.960 g / cm³.

[0011] Further, the preparation method of the ZnO-TCS antibacterial agent comprises the following steps:

[0012] (1) accurately weigh 1g of zinc oxide, add it to 60ml of ethanol solution with a volume concentration of 99%, then add 20ml of pure water and 1ml of silane coupling agent KH570, stir at 60℃ and 600r / min in a water bath until completely dissolved, then slowly add glacial acetic acid to adjust the pH value to 4, react for 2h, and finally centrifuge, freeze-dry to obtain ZnO-KH570 powder;

[0013] (2) accurately take 1g of triclosan (TCS) powder, add to 80ml of pure water, heat to 60℃ and stir until completely dissolved, then slowly add 0.7ml of methacrylic anhydride to it, then add 0.3g of 4-dimethylaminopyridine (DMAP) powder, finally add 1M NaOH solution to adjust the pH value to about 9, react at 60℃, 600r / min oil bath for 6h, after the reaction is completed, centrifugal washing, freeze-drying, to obtain TCS-MA powder;

[0014] (3) accurately take 0.5g of TCS-MA powder, add to 40ml of 99% volume concentration of ethanol solution, then add 1g of prepared ZnO-KH570 powder, pass nitrogen for 30min, then add 0.5g of azobis isobutylimidazole hydrochloride (AIBI) powder, react at 55℃, 600r / min oil bath for 10h, finally centrifugal washing, freeze-drying, to obtain the ZnO-TCS antibacterial agent.

[0015] Further, the melt mixing is mixed in a torque rheometer at 200℃, 100r / min for 9~10min.

[0016] Further, the injection molding is punched in a micro injection molding machine at 220℃, pressure 0.3~0.5Mpa for 10s, holding pressure for 5s.

[0017] The beneficial effects of the application are:

[0018] (1) The antibacterial effect of zinc oxide needs light environment, and the antibacterial effect is poor in the absence of light. The application prepares ZnO-TCS antibacterial agent by grafting organic antibacterial agent triclosan onto inorganic antibacterial agent zinc oxide, and in the process, the carbon-carbon double bond on TCS-MA and the carbon-carbon double bond on ZnO-KH570 are polymerized to become high-stability carbon-carbon single bond, which can make the obtained antibacterial agent have high stability and high temperature resistance of inorganic antibacterial agent, and on the other hand, the obtained antibacterial agent still has excellent antibacterial effect in the absence of light. In addition, since the antibacterial agent is modified with zinc oxide as the matrix, it can act as an island structure in polyethylene, greatly improving the strength of the composite material.

[0019] (2) In the preparation process of the ZnO-TCS antibacterial agent, KH570 is grafted on zinc oxide, so that a double bond is introduced; meanwhile, based on the characteristics that triclosan has an independent phenolic hydroxyl group and methyl methacrylate has high esterification reactivity, triclosan and methyl methacrylate are subjected to esterification reaction, so that triclosan is grafted with a double bond, and finally the ZnO-TCS antibacterial agent obtained through the polymerization reaction of the carbon-carbon double bond can have high stability of zinc oxide and broad-spectrum antibacterial properties of triclosan, and can effectively kill and inhibit various gram-positive bacteria, gram-negative bacteria, molds, yeasts and viruses.

[0020] (3) Since the pipe material is difficult to process, the antibacterial modification of the common polyolefin compound is mostly used in the film and coating field. The processing technology for preparing the reinforced high-density polyethylene pipe material is simple, and only needs to be formed by a simple hot processing method, so that the process is simple and fast, and the raw materials are cheap and easy to obtain.

[0021] (4) The reinforced high-density polyethylene pipe material prepared by the application has good antibacterial performance, the antibacterial effect can reach 99%, and the mechanical properties are excellent, the tensile strength is 31.4 MPa ~ 34.8 MPa, the bending strength is 18.5 MPa ~ 19.6 MPa, the impact strength is 107.4 KJ / m 2 ~ 110.4 KJ / m 2 , the elongation at break is 665% ~ 720%, and can be widely used in the fields of life and industrial water pipeline, and has significant economic value and social benefits. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The infrared absorption spectrum of the ZnO-KH570 and ZnO-TCS antibacterial agent prepared in Example 1.

[0023] Figure 2 The infrared absorption spectrum of the TCS-MA prepared in Example 1.

[0024] Figure 3 The cross-sectional morphology of the reinforced modified high-density polyethylene composite antibacterial pipe material prepared in Example 1.

[0025] Figure 4 The cross-sectional morphology of the polyethylene composite material prepared in Comparative Example 1. DETAILED DESCRIPTION

[0026] A ZnO-TCS reinforced HDPE composite antibacterial pipe material, the preparation thereof comprises the following steps:

[0027] (1) Accurately take 1g of zinc oxide and add it to 60ml of 99% volume concentration ethanol solution, then add 20ml of pure water and 1ml of KH570, stir at 60℃, 600r / min in water bath until completely dissolved, then slowly add glacial acetic acid to adjust the pH value to 4, react for 2h, and finally centrifugal wash, freeze-drying to obtain ZnO-KH570 powder;

[0028] (2) Accurately take 1g of triclosan powder and add it to 80ml of pure water, heat to 60℃ and stir until completely dissolved, then slowly add 0.7ml of methacrylic anhydride to it, then add 0.3g of DMAP powder, finally add 1M NaOH solution to adjust the pH value to 9, react at 60℃, 600r / min in oil bath for 6h, after the reaction is completed, centrifugal wash, freeze-drying to obtain TCS-MA powder;

[0029] (3) Accurately take 0.5g of TCS-MA powder and add it to 40ml of 99% volume concentration ethanol solution, then add 1g of prepared ZnO-KH570 powder, pass nitrogen for 30min, then add 0.5g of AIBI powder, react at 55℃, 600r / min in oil bath for 10h, and finally centrifugal wash, freeze-drying to obtain ZnO-TCS antibacterial agent;

[0030] (4) Add high-density polyethylene and 1%~2% of ZnO-TCS antibacterial agent by mass to a torque rheometer, mix at 200℃, 100r / min for 9~10min, then crush, dry in a vacuum drying oven overnight, and then add to a micro injection molding machine, stamp at 220℃, pressure 0.3~0.5Mpa for 10s, and hold for 5s to prepare enhanced HDPE composite antibacterial pipe material.

[0031] In order to make the content of the application more convenient to understand, the technical solutions of the application will be further described in combination with specific embodiments, but the application is not limited thereto.

[0032] The high-density polyethylene used in the examples is model 5000S, and its density is 0.941~0.960g / cm³.

[0033] Example 1

[0034] The preparation steps of ZnO-TCS enhanced high-density polyethylene composite antibacterial pipe material are as follows:

[0035] (1) Accurately take 1 g of zinc oxide, add it to 60 ml of 99% ethanol solution, then add 20 ml of pure water and 1 ml of KH570, stir at 60°C, 600 r / min water bath until completely dissolved, then slowly add glacial acetic acid to adjust the pH to 4, react for 2h, and finally centrifuge, freeze-dry to obtain ZnO-KH570 powder;

[0036] (2) Accurately take 1 g of triclosan powder, add it to 80 ml of pure water, heat to 60°C and stir until completely dissolved, then slowly add 0.7 ml of methacrylic anhydride to it, then add 0.3 g of DMAP powder, finally add 1M NaOH solution to adjust the pH to about 9, react at 60°C, 600 r / min oil bath for 6h, after the reaction is completed, centrifuge, freeze-dry to obtain TCS-MA powder;

[0037] (3) Accurately take 0.5 g of prepared TCS-MA powder, add it to 40 ml of 99% ethanol solution, then add 1 g of prepared ZnO-KH570 powder, pass nitrogen for 30 min, then add 0.5 g of AIBI powder, react at 55°C, 600 r / min oil bath for 10h, and finally centrifuge, freeze-dry to obtain ZnO-TCS antibacterial agent;

[0038] (4) Put 100 parts by weight of high-density polyethylene and 1.5 parts by weight of prepared ZnO-TCS antibacterial agent into a torque rheometer, mix at 200°C, 100 r / min for 9 min, crush, and then put into a 60°C drying oven to dry overnight, then add the obtained powder to a micro injection molding machine, set the mold temperature to 55°C, and punch at 220°C, 0.4Mpa for 10s, hold for 5s, to obtain ZnO-TCS enhanced high-density polyethylene composite antibacterial pipe material.

[0039] Figure 1 The infrared absorption spectrum of the ZnO-KH570 and ZnO-TCS antibacterial agents prepared in this embodiment is shown in the figure. As shown in the figure, the infrared absorption spectrum of ZnO-KH570 has absorption peaks at 1171 cm -1 and 1635 cm -1 corresponding to Si-O bond and carbon-carbon double bond, respectively. Compared with ZnO, it can be seen that silane coupling agent is successfully grafted on ZnO and carbon-carbon double bond is introduced. By comparing ZnO-KH570 and ZnO-TCS, it can be found that the absorption peak of carbon-carbon double bond in ZnO-TCS disappears, which indicates that the polymerization of carbon-carbon double bond into carbon-carbon single bond is caused by polymerization. At the same time, ZnO-TCS has absorption peaks at 1475 cm -1 and 1748 cm -1The absorption peaks of benzene ring and ester group appeared respectively, since ZnO-KH570 itself does not have benzene ring and ester group, thus indicating that zinc oxide is successfully grafted with triclosan.

[0040] Figure 2 The infrared absorption spectrum of TCS-MA prepared in this example is shown in the figure. As shown in the figure, the absorption peak of TCS-MA at 750 cm -1 corresponds to the stretching vibration absorption peak of C-Cl, which indicates that the antibacterial functional group is not damaged in the process of grafting methacrylic anhydride with triclosan; the corresponding hydroxyl stretching vibration absorption peak of triclosan at 3310 cm -1 disappears, while the stretching vibration absorption peak of methyl appears at 2930 cm -1 , indicating that the grafting is successful; the absorption peaks at 1635 cm -1 and 1748 cm -1 correspond to carbon-carbon double bond and carbon-oxygen bond respectively, indicating that TCS-MA successfully grafts carbon-carbon double bond through esterification reaction.

[0041] Figure 3 The fracture morphology of the enhanced modified high-density polyethylene composite antibacterial pipe prepared in this example is shown in the figure. As shown in the figure, a large number of filamentous morphology and granular substances appear in the material fracture, indicating that the addition of antibacterial agent can enhance the high-density polyethylene material.

[0042] Example 2

[0043] The preparation steps of ZnO-TCS enhanced high-density polyethylene composite antibacterial pipe are as follows:

[0044] (1) Accurately weigh 1 g of zinc oxide, add it into 60 ml of 99% ethanol solution, then add 20 ml of pure water and 1 ml of KH570, stir until completely dissolved under the condition of 60°C and 600 r / min water bath, then slowly add glacial acetic acid to adjust the pH to 4, react for 2 h, finally centrifuge, freeze-dry to obtain ZnO-KH570 powder;

[0045] (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat to 60°C and stir until completely dissolved, then slowly add 0.7 ml of methacrylic anhydride to it, then add 0.3 g of DMAP powder, finally add 1M NaOH solution to adjust the pH to about 9, react for 6 h under the condition of 60°C and 600 r / min oil bath, after the reaction is completed, centrifuge, freeze-dry to obtain TCS-MA powder;

[0046] (3) Accurately take 0.5 g of the prepared TCS-MA powder into 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 at 55°C and 600 r / min in an oil bath for 10 h, and finally centrifuge, wash, freeze-dry to obtain the ZnO-TCS antibacterial agent;

[0047] (4) Put 100 parts by weight of high-density polyethylene and 1 part by weight of the prepared ZnO-TCS antibacterial agent into a torque rheometer, mix at 200°C and 100 r / min for 9 min, crush, put into a 60°C drying oven and dry overnight, then add the obtained powder to a micro injection molding machine, set the mold temperature to 55°C, and punch at 220°C, 0.4 MPa pressure for 10 s, and hold for 5 s to obtain the ZnO-TCS enhanced high-density polyethylene composite antibacterial pipe material.

[0048] Example 3

[0049] The preparation steps of the ZnO-TCS enhanced high-density polyethylene composite antibacterial pipe material are as follows:

[0050] (1) Accurately take 1 g of zinc oxide, add it into 60 ml of 99% ethanol solution, then add 20 ml of pure water and 1 ml of KH570, stir until completely dissolved at 60°C and 600 r / min in a water bath, then slowly add glacial acetic acid to adjust the pH to 4, react for 2 h, and finally centrifuge, wash, and freeze-dry to obtain the ZnO-KH570 powder;

[0051] (2) Accurately take 1 g of triclosan powder, add it to 80 ml of pure water, heat to 60°C and stir until completely dissolved, then slowly add 0.7 ml of methacrylic anhydride to it, then add 0.3 g of DMAP powder, finally add 1 M NaOH solution to adjust the pH to about 9, react at 60°C and 600 r / min in an oil bath for 6 h, after the reaction is completed, centrifuge, wash, and freeze-dry to obtain the TCS-MA powder;

[0052] (3) Accurately take 0.5 g of the prepared TCS-MA powder into 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 at 55°C and 600 r / min in an oil bath for 10 h, and finally centrifuge, wash, freeze-dry to obtain the ZnO-TCS antibacterial agent;

[0053] (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℃ and 100r / min for 9min, and then put into a 60℃ drying box for drying overnight. The obtained powder was added into a micro injection molding machine, the mold temperature was set to 55℃, and the pipe material was punched at 220℃ and 0.4Mpa for 10s with 5s of pressure maintaining to obtain a ZnO-TCS enhanced high density polyethylene composite antibacterial pipe material.

[0054] Comparative Example 1

[0055] The preparation steps of the high density polyethylene pipe material were as follows:

[0056] 100 parts by weight of high density polyethylene were put into a torque rheometer, mixed at 200℃ and 100r / min for 9min, and then put into a 60℃ drying box for drying overnight. The obtained powder was added into a micro injection molding machine, the mold temperature was set to 55℃, and the pipe material was punched at 220℃ and 0.4Mpa for 10s with 5s of pressure maintaining to obtain a high density polyethylene pipe material.

[0057] Figure 4 The fracture surface morphology of the high density polyethylene pipe material prepared in this comparative example was shown in the figure. It can be seen from the figure that the fracture surface has no obvious wire drawing state and particulate matter.

[0058] Comparative Example 2

[0059] The preparation steps of the ZnO modified high density polyethylene composite pipe material were as follows:

[0060] 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℃ and 100r / min for 9min, and then put into a 60℃ drying box for drying overnight. The obtained powder was added into a micro injection molding machine, the mold temperature was set to 55℃, and the pipe material was punched at 220℃ and 0.4Mpa for 10s with 5s of pressure maintaining to obtain a ZnO modified high density polyethylene composite pipe material.

[0061] Comparative Example 3

[0062] The preparation steps of the TSC modified high density polyethylene composite pipe material were as follows:

[0063] 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℃ and 100r / min for 9min, and then put into a 60℃ drying box for drying overnight. The obtained powder was added into a micro injection molding machine, the mold temperature was set to 55℃, and the pipe material was punched at 220℃ and 0.4Mpa for 10s with 5s of pressure maintaining to obtain a TCS modified high density polyethylene composite pipe material.

[0064] Comparative Example 4

[0065] The preparation steps of the ZnO-KH570 modified high-density polyethylene composite pipe are as follows:

[0066] (1) 1 g of zinc oxide was accurately weighed and added into 60 ml of 99% ethanol solution, followed by adding 20 ml of pure water and 1 ml of KH570. The solution was stirred at 60°C and 600 r / min in a water bath until completely dissolved. Then, glacial acetic acid was slowly added to the solution to adjust the pH to 4, and the reaction was carried out for 2 h. Finally, the ZnO-KH570 powder was obtained by centrifugal washing and freeze-drying.

[0067] (2) 100 parts by weight of high-density polyethylene and 1.5 parts by weight of ZnO-KH570 powder were put into a torque rheometer and mixed at 200°C and 100 r / min for 9 min. After crushing, the powder was placed in a 60°C drying oven overnight. Then, the obtained powder was added into a micro injection molding machine, the mold temperature was set to 55°C, and the pipe was punched at 220°C and 0.4 MPa for 10 s with 5 s of pressure holding to obtain the ZnO-KH570 modified high-density polyethylene composite pipe.

[0068] Comparative Example 5

[0069] The preparation steps of the ZnO / TCS composite modified high-density polyethylene composite pipe are as follows:

[0070] 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 and mixed at 200°C and 100 r / min for 9 min. After crushing, the powder was placed in a 60°C drying oven overnight. Then, the obtained powder was added into a micro injection molding machine, the mold temperature was set to 55°C, and the pipe was punched at 220°C and 0.4 MPa for 10 s with 5 s of pressure holding to obtain the ZnO / TCS composite modified high-density polyethylene composite pipe.

[0071] The finished products prepared in the examples and comparative examples were tested for antibacterial performance 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; and 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.

[0072] Table 1 Performance test results

[0073]

[0074] As can be seen from the results in Table 1, compared with the pipe obtained in the comparative example, the antibacterial performance and strength of the pipe prepared in the examples are obviously improved, proving that the prepared enhanced high-density polyethylene composite pipe has excellent antibacterial performance, and the mechanical performance thereof can be improved. The enhanced high-density polyethylene composite antibacterial pipe prepared in Example 1 has the most excellent antibacterial performance and excellent mechanical performance.

[0075] The above merely describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the present application should be included in the scope of the present application.

Claims

1. A method of manufacturing a ZnO-TCS modified reinforced HDPE pipe, characterized by: The enhanced HDPE composite antibacterial pipe material is prepared by melt mixing, crushing, drying and injection molding of high density polyethylene and ZnO-TCS antibacterial agent. The preparation method of the ZnO-TCS antibacterial agent comprises the following steps: (1) 1g of zinc oxide is accurately weighed and added into 60ml of ethanol solution with a volume concentration of 99%, then 20ml of pure water and 1ml of KH570 are added, and stirring is carried out at 60°C and 600r / min in a water bath until complete dissolution, then glacial acetic acid is slowly added into the solution to adjust the pH value to 4, and reaction is carried out for 2h, finally centrifugal washing, freeze-drying are carried out to obtain ZnO-KH570 powder; (2) 1g of triclosan powder is accurately weighed and added into 80ml of pure water, heated to 60°C and stirred until complete dissolution, then 0.7ml of methacrylic anhydride is slowly added dropwise, then 0.3g of DMAP powder is added, finally 1M of NaOH solution is added to adjust the pH value to 9, and reaction is carried out at 60°C and 600r / min in an oil bath for 6h, after reaction, centrifugal washing, freeze-drying are carried out to obtain TCS-MA powder; (3) 0.5g of TCS-MA powder is accurately weighed and added into 40ml of ethanol solution with a volume concentration of 99%, then 1g of prepared ZnO-KH570 powder is added, nitrogen is passed for 30min, then 0.5g of AIBI powder is added, and reaction is carried out at 55°C and 600r / min in an oil bath for 10h, finally centrifugal washing, freeze-drying are carried out to obtain the ZnO-TCS antibacterial agent.

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

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

4. The method of modifying ZnO-TCS reinforced HDPE pipe as claimed in claim 1, wherein: The melt mixing is carried out in a torque rheometer at 200°C and 100r / min for 9-10min.

5. The method of manufacturing ZnO-TCS modified reinforced HDPE pipe as claimed in claim 1 wherein: The injection molding is carried out in a micro injection molding machine at 220°C and a pressure of 0.3-0.5Mpa for 10s and pressure maintaining for 5s.

6. The enhanced HDPE composite antibacterial pipe material prepared by the method of claim 1.

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