Preparation method of hydrophilic anti-fouling HDPE composite antibacterial pipe material

Abstract

The application discloses a preparation method of hydrophilic anti-fouling HDPE composite antibacterial pipe material and belongs to the field of polymer composite material processing. The composite antibacterial pipe material is prepared from high-density polyethylene, ethylene-vinyl alcohol copolymer, EVA-g-MAH compatilizer, ZnO-TCS antibacterial agent and Span 40 as raw materials through melt mixing, crushing, drying and injection molding. The application has the advantages of simple preparation process and low cost, and the obtained composite antibacterial pipe material has the characteristics of excellent antibacterial performance and high strength and can be widely applied to the fields of living and industrial water conveying pipes and the like, and has remarkable economic value and social benefits.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of polymer composite processing, and particularly relates to a preparation method of a hydrophilic and anti-fouling HDPE composite antibacterial pipe. 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 mechanical strength, and is widely used in the fields of film, pipe, various hollow products, injection molded products, fibers and the like. However, in order to meet the requirements of specific working conditions, the high-density polyethylene pipe needs to have stronger anti-fouling and antibacterial properties and mechanical properties. In order to further make the polyethylene pipe more widely used in life and production, and to improve the antibacterial and hydrophilic properties of the polyethylene pipe, the antibacterial agent and the hydrophilic agent need to have good compatibility and dispersibility with the base body.

[0003] Zinc oxide antibacterial agent is a material with multiple antibacterial mechanisms. Under light conditions, especially under ultraviolet light, zinc oxide can generate high-activity 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 can slowly release zinc ions in aqueous media, and these zinc ions can combine with bacterial cell membranes 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 will further produce active oxygen groups, which makes the active oxygen antibacterial effect of zinc oxide and the photocatalytic antibacterial effect interrelated.

[0004] Triclosan is a broad-spectrum antibacterial agent, and its antibacterial principle is mainly to inhibit the synthesis of bacterial fatty acids. Triclosan has killing and inhibiting effects on various gram-positive bacteria, gram-negative bacteria, fungi and viruses, so its application fields are very wide, including personal care products such as toothpaste, soap, facial cleanser, hand sanitizer, and medical device disinfectant, wound disinfectant, etc.

[0005] Span 40, also known as sorbitan palmitate, is a non-ionic surfactant with emulsifying, thickening and dispersing properties. It is a light yellow granular solid at room temperature, and the melting point is about 46-47℃. Its hydrophilicity mainly comes from the multiple hydroxyl structures in the molecule, which can form hydrogen bonds with water molecules to provide certain hydrophilicity. At the same time, its molecular structure also contains a long hydrophobic fatty acid chain, so it also has good compatibility with plastics. SUMMARY

[0006] In view of the problems of poor strength and no antibacterial ability of the pipe material obtained by injection molding of the existing high-density polyethylene, the application provides a preparation method of a hydrophilic and stain-resistant HDPE composite antibacterial pipe material, which adds ZnO-TCS antibacterial agent, on the one hand, by combining zinc oxide and triclosan, the stability of the inorganic antibacterial agent zinc oxide and the excellent antibacterial performance of triclosan can be taken into account, and the nano-scale island structure of zinc oxide can be formed to enhance the mechanical properties of the pipe material; on the other hand, since span 40 contains a large number of hydroxyl groups and relatively suitable hydrophobic chains, the hydrophilicity of the material can be ensured, and the compatibility with the polyethylene material can also be taken into account, so that the hydrophilic ability and the strength of the polyethylene pipe material can be improved at the same time.

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

[0008] A hydrophilic and stain-resistant HDPE composite antibacterial pipe material is prepared by using high-density polyethylene, ethylene-vinyl alcohol copolymer, EVA-g-MAH compatibilizer, ZnO-TCS antibacterial agent and span 40 as raw materials through melt mixing, crushing, drying and injection molding.

[0009] Among them, each raw material is 100 parts by weight of high-density polyethylene, 4 parts of ethylene-vinyl alcohol copolymer, 2 parts of EVA-g-MAH compatibilizer, 1-2 parts by weight of ZnO-TCS antibacterial agent and 2.5-3.5 parts of span 40.

[0010] Further, the model of the high-density polyethylene is 5000S, and the density is 0.941-0.960 g / cm 3 .

[0011] Further, the model of the ethylene-vinyl alcohol copolymer is EW-3801.

[0012] Further, the model of the EVA-g-MAH compatibilizer is Bynel 39E660.

[0013] Further, the preparation method of the ZnO-TCS antibacterial agent comprises the following steps:

[0014] (1) 1g of zinc oxide is accurately weighed and added to 60ml of ethanol solution with a volume concentration of 99%, then 20ml of pure water and 1ml of silane coupling agent KH570 are added, and stirring is carried out under the condition of a water bath at 60℃ and 600r / min until complete dissolution, then ice acetic acid is slowly added to the solution to adjust the pH value to 4, and the reaction is carried out for 2h, finally the ZnO-KH570 powder is obtained by centrifugal washing and freeze-drying;

[0015] (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;

[0016] (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.

[0017] Further, the melt mixing is mixed in a torque rheometer at 200℃, 100r / min for 9~10min.

[0018] 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.

[0019] The beneficial effects of the application are:

[0020] (1) The antibacterial effect of zinc oxide requires 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 of TCS-MA and the carbon-carbon double bond of 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.

[0021] (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 independent phenolic hydroxyl 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 characteristics of triclosan, and can effectively kill and inhibit various gram-positive bacteria, gram-negative bacteria, molds, yeasts and viruses.

[0022] (3) Ethylene-vinyl alcohol copolymer is an olefin thermoplastic plastic, which has the advantages of high strength, high thermal stability, high barrier property and excellent hydrophilic property. The ethylene-vinyl alcohol copolymer is added to the polyethylene in the application, so that the problems of poor barrier property and poor hydrophilic property of the polyethylene can be solved. At the same time, the high-temperature melt blending process is adopted in the application, so that the ethylene-vinyl alcohol copolymer can be uniformly dispersed in the polyethylene. In addition, since the crystallization temperature of the ethylene-vinyl alcohol copolymer is different from that of the high-density polyethylene, the island particle structure can be formed in the polyethylene material during the crystallization process, so that the mechanical properties of the material can be further improved.

[0023] (4) The superiority of Span 40 as a hydrophilic agent mainly lies in the following aspects: first, Span 40 has amphiphilicity, which makes it not only have good hydrophilic property, but also have good compatibility with polyethylene material. In addition, the carbon chain length of Span 40 is 16 carbon atoms, which not only ensures its hydrophilic property in the form of small molecules, but also ensures its high-temperature stability in the plastic processing process.

[0024] (5) The preparation process of the application is simple and low in cost, the obtained composite antibacterial pipe material has excellent antibacterial performance and high strength, 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

[0025] Figure 1 The infrared absorption spectrum of ZnO-KH570 and ZnO-TCS prepared in Example 1.

[0026] Figure 2 The infrared absorption spectrum of TCS-MA prepared in Example 1.

[0027] Figure 3 The cross-sectional morphology diagram of the composite antibacterial pipe material prepared in Example 1.

[0028] Figure 4 The cross-sectional morphology diagram of the high-density polyethylene pipe material prepared in Comparative Example 1. DETAILED DESCRIPTION

[0029] A hydrophilic anti-fouling HDPE composite antibacterial pipe material, the preparation comprising the following steps:

[0030] (1) accurately take 1g of zinc oxide, add to 60ml volume concentration of 99% ethanol solution, then add 20ml pure water and 1ml KH570, stirring at 60℃, 600r / min water bath conditions until completely dissolved, then slowly add glacial acetic acid to adjust the pH value to 4, after 2h, finally centrifugal washing, freeze drying, to obtain ZnO-KH570 powder;

[0031] (2) accurately take 1g of triclosan powder, add to 80ml of pure water, heated to 60℃ and stirred until completely dissolved, then slowly drop 0.7ml of methacrylic anhydride into it, then add 0.3g of DMAP powder, finally add 1M NaOH solution to adjust the pH value to about 9, under the condition of 60℃, 600r / min oil bath, reaction for 6h, after the reaction, centrifugal washing, freeze drying, to obtain TCS-MA powder;

[0032] (3) accurately take 0.5g of TCS-MA powder prepared in step (2), add to 40ml volume concentration of 99% ethanol solution, then add 1g of ZnO-KH570 powder prepared in step (1), nitrogen for 30min, then add 0.5g of AIBI powder, under the condition of 55℃, 600r / min oil bath, reaction for 10h, finally centrifugal washing, freeze drying, to obtain ZnO-TCS antibacterial agent;

[0033] (4) according to the weight part, 100 parts of high density polyethylene, 4 parts of ethylene-vinyl alcohol copolymer, 2 parts of EVA-g-MAH compatibilizer, 1~2 parts of ZnO-TCS antibacterial agent, 2.5~3.5 parts of Span 40 are added into torque rheometer, mixed at 200℃, 100r / min for 9~10min, then crushed, dried in vacuum drying oven overnight, then added into a micro injection molding machine, punched at 220℃, pressure 0.3~0.5Mpa for 10s, holding for 5s.

[0034] In order to make the content of the application more convenient to understand, the technical solutions of the application are further described below in combination with specific embodiments, but the application is not limited thereto.

[0035] The high density polyethylene used in the examples is model 5000S, with a density of 0.941~0.960 g / cm 3 . The ethylene-vinyl alcohol copolymer used is model EW-3801. The EVA-g-MAH compatibilizer used is model Bynel 39E660.

[0036] Example 1

[0037] The preparation steps of the hydrophilic and stain-resistant HDPE composite antibacterial pipe material are as follows:

[0038] (1) Accurately take 1 g of zinc oxide and 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 and 600 r / min in a water bath until completely dissolved, then slowly add glacial acetic acid to adjust the pH to 4, react for 2 h, and finally centrifuge, freeze-dry to obtain ZnO-KH570 powder;

[0039] (2) Accurately take 1 g of triclosan powder and 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, and finally add 1M 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, freeze-dry to obtain TCS-MA powder;

[0040] (3) Accurately take 0.5 g of prepared TCS-MA powder and 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 and 600 r / min in an oil bath for 10 h, and finally centrifuge, freeze-dry to obtain ZnO-TCS powder;

[0041] (4) According to the weight parts, 100 parts of high-density polyethylene, 1.5 parts of ZnO-TCS antibacterial agent, 3 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer, and 4 parts of ethylene-vinyl alcohol copolymer are put into a torque rheometer and mixed at 200°C and 100 r / min for 9 min, then crushed and placed in a 60°C drying oven overnight, then the obtained powder is added to a micro injection molding machine, the mold temperature is set to 55°C, and the pipe material is obtained by stamping at 220°C and 0.4Mpa for 10 s and holding for 5 s.

[0042] Figure 1 The infrared absorption spectra of ZnO-KH570 and ZnO-TCS prepared in this example are 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 -1corresponding to Si-O bond and carbon-carbon double bond, respectively, it can be seen from the comparison of ZnO 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 disappears in ZnO-TCS, which indicates that the polymerization reaction causes the carbon-carbon double bond to polymerize into carbon-carbon single bond. At the same time, ZnO-TCS appears absorption peaks of benzene ring and ester group at 1475 cm -1 and 1748 cm -1 , respectively, since ZnO-KH570 itself does not have benzene ring and ester group, which indicates that zinc oxide is successfully grafted with triclosan.

[0043] 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 on triclosan; the corresponding hydroxyl stretching vibration absorption peak of triclosan at 3310 cm -1 disappears, and the stretching vibration absorption peak of methyl appears at 2930 cm -1 , which indicates that the grafting is successful; the absorption peaks of carbon-carbon double bond and carbon-oxygen bond at 1635 cm -1 and 1748 cm -1 , respectively, indicate that TCS-MA successfully grafts carbon-carbon double bond through esterification reaction.

[0044] Figure 3 The cross-sectional morphology of the composite antibacterial pipe material 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 cross-section, which indicates that the toughness of the composite material is enhanced and the overall dispersibility of ZnO-TCS is excellent.

[0045] Example 2

[0046] The preparation steps of the hydrophilic and stain-resistant HDPE composite antibacterial pipe material are as follows:

[0047] (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 water bath and 600 r / min, then slowly add glacial acetic acid to adjust the pH to 4, react for 2 h, and finally centrifuge, freeze-dry to obtain ZnO-KH570 powder;

[0048] (2) Accurately weigh 1 g of triclosan powder and 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, followed by the addition of 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 6 h. After the reaction is completed, centrifugal washing, freeze-drying to obtain TCS-MA powder;

[0049] (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, pass nitrogen for 30 min, and then add 0.5 g of AIBI powder. React at 55°C, 600 r / min oil bath for 10 h. Finally, centrifugal washing, freeze-drying to obtain ZnO-TCS powder;

[0050] (4) According to the weight parts, 100 parts of high-density polyethylene, 1 part of ZnO-TCS antibacterial agent, 3.5 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer, and 4 parts of ethylene-vinyl alcohol copolymer are put into a torque rheometer and mixed at 200°C, 100 r / min for 9 min. After crushing, it is placed in a drying oven at 60°C overnight. Then the obtained powder is added to a micro injection molding machine, the mold temperature is set to 55°C, and the pressure is 0.4 MPa. The hydrophilic and anti-fouling HDPE composite antibacterial pipe material is obtained by stamping for 10 s and holding for 5 s at 220°C.

[0051] Example 3

[0052] The preparation steps of the hydrophilic and anti-fouling HDPE composite antibacterial pipe material are as follows:

[0053] (1) Accurately weigh 1 g of zinc oxide and 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 the solution to adjust the pH to 4, and react for 2 h. Finally, centrifugal washing, freeze-drying to obtain ZnO-KH570 powder;

[0054] (2) Accurately weigh 1 g of triclosan powder and 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, followed by the addition of 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 6 h. After the reaction is completed, centrifugal washing, freeze-drying to obtain TCS-MA powder;

[0055] (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 ZnO-TCS powder;

[0056] (4) According to weight parts, 100 parts of high-density polyethylene, 2 parts of ZnO-TCS antibacterial agent, 2.5 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer, and 4 parts of ethylene-vinyl alcohol copolymer are put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed, and then put into a drying box at 60°C overnight, then the obtained powder is added into a micro injection molding machine, the mold temperature is set to 55°C, and the obtained hydrophilic and anti-fouling HDPE composite antibacterial pipe material is obtained by stamping at 220°C and 0.4 MPa pressure for 10 s and holding for 5 s.

[0057] Comparative Example 1

[0058] The preparation steps of the high-density polyethylene pipe material are as follows:

[0059] 100 parts by weight of high-density polyethylene are put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed, and then put into a drying box at 60°C overnight, then the obtained powder is added into a micro injection molding machine, the mold temperature is set to 55°C, and the high-density polyethylene pipe material is obtained by stamping at 220°C and 0.4 MPa pressure for 10 s and holding for 5 s.

[0060] Figure 4 The fracture surface morphology of the high-density polyethylene pipe material prepared in this comparative example is shown in the figure. As can be seen from the figure, the fracture surface has no obvious wire drawing state and particulate matter.

[0061] Comparative Example 2

[0062] The preparation steps of the HDPE composite pipe material are as follows:

[0063] According to weight parts, 100 parts of high-density polyethylene, 3 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer, and 4 parts of ethylene-vinyl alcohol copolymer are put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed, and then put into a drying box at 60°C overnight, then the obtained powder is added into a micro injection molding machine, the mold temperature is set to 55°C, and the HDPE composite pipe material is obtained by stamping at 220°C and 0.4 MPa pressure for 10 s and holding for 5 s.

[0064] Comparative Example 3

[0065] The preparation steps of the HDPE composite antibacterial pipe are as follows:

[0066] (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 and 600 r / min in a water bath until completely dissolved, then slowly add glacial acetic acid to adjust the pH to 4, react for 2 h, and finally centrifuge, freeze-dry to obtain ZnO-KH570 powder;

[0067] (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, and finally add 1M 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, freeze-dry to obtain TCS-MA powder;

[0068] (3) Accurately take 0.5 g of the prepared TCS-MA powder, 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 at 55°C and 600 r / min in an oil bath for 10 h, and finally centrifuge, freeze-dry to obtain ZnO-TCS powder;

[0069] (4) According to the weight parts, 100 parts of high-density polyethylene, 1.5 parts of ZnO-TCS antibacterial agent, 3 parts of Span 40 and 4 parts of ethylene-vinyl alcohol copolymer are put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed, and then put into a drying box at 60°C and dried overnight, then the obtained powder is added to a micro injection molding machine, the mold temperature is set to 55°C, and the obtained HDPE composite antibacterial pipe is obtained by stamping at 220°C and a pressure of 0.4 MPa for 10 s and holding for 5 s.

[0070] Comparative Example 4

[0071] The preparation steps of the HDPE composite antibacterial pipe are as follows:

[0072] (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 and 600 r / min in a water bath until completely dissolved, then slowly add glacial acetic acid to adjust the pH to 4, react for 2 h, and finally centrifuge, freeze-dry to obtain ZnO-KH570 powder;

[0073] (2) Accurately take 1 g of triclosan powder and 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, followed by the addition of 0.3 g of DMAP powder, and finally add 1M NaOH solution to adjust the pH to about 9. React at 60°C, 600 r / min oil bath for 6 h. After the reaction is completed, centrifugal washing, freeze-drying, and TCS-MA powder are obtained;

[0074] (3) Accurately take 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, pass nitrogen for 30 min, and then add 0.5 g of AIBI powder. React at 55°C, 600 r / min oil bath for 10 h. Finally, centrifugal washing, freeze-drying, and ZnO-TCS powder are obtained;

[0075] (4) According to the weight parts, 100 parts of high-density polyethylene, 1.5 parts of ZnO-TCS antibacterial agent, 2 parts of EVA-g-MAH compatibilizer, and 4 parts of ethylene-vinyl alcohol copolymer are put into a torque rheometer and mixed at 200°C, 100 r / min for 9 min. After crushing, it is placed in a 60°C drying oven overnight. Then the obtained powder is added to a micro injection molding machine, the mold temperature is set to 55°C, and the HDPE composite antibacterial pipe material is obtained by stamping at 220°C, 0.4Mpa pressure for 10 s and holding for 5 s.

[0076] Comparative Example 5

[0077] The preparation steps of the hydrophilic and stain-resistant HDPE composite antibacterial pipe material are as follows:

[0078] According to the weight parts, 100 parts of high-density polyethylene, 1.5 parts of ZnO antibacterial agent, 3 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer, and 4 parts of ethylene-vinyl alcohol copolymer are put into a torque rheometer and mixed at 200°C, 100 r / min for 9 min. After crushing, it is placed in a 60°C drying oven overnight. Then the obtained powder is added to a micro injection molding machine, the mold temperature is set to 55°C, and the HDPE composite antibacterial pipe material is obtained by stamping at 220°C, 0.4Mpa pressure for 10 s and holding for 5 s.

[0079] Comparative Example 6

[0080] The preparation steps of the HDPE composite antibacterial pipe material are as follows:

[0081] The 100 parts of high density polyethylene, 1.5 parts of TCS antibacterial agent, 3 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200℃, 100r / min for 9min, crushed, dried in a drying oven at 60℃ overnight, then the obtained powder was added into a micro injection molding machine, the mold temperature was set to 55℃, and the HDPE composite antibacterial pipe material was obtained by stamping at 220℃, pressure 0.4Mpa for 10s, holding for 5s.

[0082] Comparative Example 7

[0083] The preparation steps of the HDPE composite antibacterial pipe material are as follows:

[0084] The 100 parts of high density polyethylene, 1 part of ZnO, 0.5 part of TCS, 3 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200℃, 100r / min for 9min, crushed, dried in a drying oven at 60℃ overnight, then the obtained powder was added into a micro injection molding machine, the mold temperature was set to 55℃, and the HDPE composite antibacterial pipe material was obtained by stamping at 220℃, pressure 0.4Mpa for 10s, holding for 5s.

[0085] The finished products prepared in the examples and comparative examples were tested for antibacterial performance according to GB / T 20944.3-2008, water contact angle according to GB / T 30693-2014, bending strength according to the test method of GB / T 9341-2008, impact strength according to the test method of ISO 179-1:2000, and tensile strength and elongation at break according to the test method of GB / T 1040.2-2006. The results are shown in Table 1.

[0086] Table 1 Performance test results

[0087]

[0088] As can be seen from the results in Table 1, compared with the material obtained in the comparative examples, the antibacterial performance and strength of the material prepared in the examples are greatly improved, which proves that the prepared HDPE composite pipe material has excellent antibacterial performance, and its mechanical properties can be improved. The HDPE composite antibacterial pipe material prepared in Example 1 has the most excellent hydrophilic and anti-fouling properties and mechanical properties.

[0089] The above only describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the patent application of the present application shall be included in the scope of the present application.

Claims

1. A method for preparing a hydrophilic, stain resistant, HDPE composite antibacterial pipe material, characterized by: The hydrophilic anti-fouling HDPE composite antibacterial pipe material is prepared by melt mixing, crushing, drying and injection molding with high-density polyethylene, ethylene-vinyl alcohol copolymer, EVA-g-MAH compatibilizer, ZnO-TCS antibacterial agent and Span 40 as raw materials. The preparation method of the ZnO-TCS antibacterial agent comprises the following steps: (1) 1 g of zinc oxide is accurately weighed and added into 60 ml of ethanol solution with a volume concentration of 99%, followed by adding 20 ml of pure water and 1 ml of KH570, stirring at 60°C and 600 r / min in a water bath until completely dissolved, then slowly adding glacial acetic acid into the solution to adjust the pH value to 4, and reacting for 2 h, finally centrifuging, washing and freeze-drying to obtain ZnO-KH570 powder; (2) 1 g of triclosan powder is accurately weighed and added into 80 ml of pure water, heated to 60°C and stirred until completely dissolved, then slowly adding 0.7 ml of methacrylic anhydride into the solution, followed by adding 0.3 g of DMAP powder, finally adding 1M NaOH solution to adjust the pH value to 9, and reacting for 6 h at 60°C and 600 r / min in an oil bath, after the reaction, centrifuging, washing and freeze-drying to obtain TCS-MA powder; (3) 0.5 g of TCS-MA powder is accurately weighed and added into 40 ml of ethanol solution with a volume concentration of 99%, followed by adding 1 g of prepared ZnO-KH570 powder, passing nitrogen for 30 min, then adding 0.5 g of AIBI powder, and reacting for 10 h at 55°C and 600 r / min in an oil bath, finally centrifuging, washing and freeze-drying to obtain the ZnO-TCS antibacterial agent.

2. The process for the preparation of hydrophilic anti-fouling HDPE composite antibacterial pipe as claimed in claim 1, wherein: The raw materials are as follows in terms of weight parts: high-density polyethylene 100 parts, ethylene-vinyl alcohol copolymer 4 parts, EVA-g-MAH compatibilizer 2 parts, ZnO-TCS antibacterial agent 1-2 parts by weight, and Span 40 2.5-3.5 parts.

3. The process for the preparation of hydrophilic anti-fouling HDPE composite antibacterial pipe as claimed in claim 1 or 2, wherein: The high density polyethylene is of the type 5000S, having a density of 0.941 to 0.960 g / cm 3 .

4. The process for the preparation of hydrophilic anti-fouling HDPE composite antibacterial pipe as claimed in claim 1 or 2, wherein the process comprises of: The ethylene-vinyl alcohol copolymer is of model EW-3801.

5. The process for the preparation of hydrophilic anti-fouling HDPE composite antibacterial pipe as claimed in claim 1 or 2 wherein the process further comprises of: The EVA-g-MAH compatibilizer is of model Bynel 39E660.

6. The process for the preparation of hydrophilic anti-fouling HDPE composite antibacterial pipe as claimed in claim 1, wherein: The melt mixing is carried out in a torque rheometer at 200°C and 100 r / min for 9-10 min.

7. The process for the preparation of hydrophilic anti-fouling HDPE composite antibacterial 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 0.3-0.5 MPa for 10 s and a holding pressure of 5 s.

8. A hydrophilic anti-fouling HDPE composite antibacterial pipe material prepared by the method of claim 1.

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