High-antibacterial durable PPR material and preparation method thereof

Abstract

The invention discloses a high-antibacterial durability PPR material and a preparation method thereof, and relates to the field of plastic materials, the high-antibacterial durability PPR material comprises an antibacterial agent A, an antibacterial agent B, polypropylene random copolymer, a silane coupling agent and an antioxidant; the antibacterial agent A is prepared from the following raw materials: low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth; the antibacterial agent B is prepared from the following raw materials: high-density polyethylene, hemicellulose, zinc oxide, a 3wt% acetic acid aqueous solution and leucite. According to the high-antibacterial durability PPR material provided by the technical scheme, the antibacterial agent A, the antibacterial agent B, the polypropylene random copolymer, the silane coupling agent and the antioxidant are included, the antibacterial agent A is prepared from the low-density polyethylene, the carbon nanotubes, the silver carbonate, the ethyl alcohol and the tragacanth, and the antioxidant is prepared from the low-density polyethylene, the carbon nanotubes, the silver carbonate, the ethyl alcohol and the tragacanth; the antibacterial agent B is prepared from high-density polyethylene, hemicellulose, zinc oxide, a 3wt% acetic acid aqueous solution and leucite, and the antibacterial agent B has excellent antibacterial performance and mechanical performance and meets the requirement for hygienic performance.

Description

Technical Field

[0001] The present invention relates to the field of plastic materials, and in particular to a highly antibacterial and durable PPR material and a preparation method thereof. Background Art

[0002] PPR plastic pipes are made of non-toxic, pressure-resistant, and lightweight random copolymer polypropylene materials. It is mainly used in industrial and civil building hot and cold water pipe systems, heating systems, drinking water systems, etc. The inner wall of the PPR pipe is smooth, has a long service life, and excellent corrosion resistance. In our daily life, tap water and direct drinking water will eventually pass through the PPR water supply pipe and enter the normal use process of the user. Since the PPR water supply pipe is not easily replaced after installation, it is easy to breed a large number of bacteria and algae on the inner pipe wall after a period of use, which will affect the performance of the pipe, shorten the service life of the pipe, and increase the maintenance cost; even these bacteria and algae will enter the human body with the water flow, thereby affecting people's health. Therefore, the use of antibacterial PPR water supply pipes with long-term bactericidal effects has become increasingly important. CN109253321A discloses an antibacterial self-cleaning PPR pipe, but its antibacterial performance is not excellent enough, there is a problem of silver precipitation, and the mechanical properties are poor.

[0003] In summary, after extensive searching by the applicant, it is found that at least the existing PPR materials in this field have insufficient antibacterial properties, silver precipitation problems, and poor mechanical properties. Therefore, it is necessary to develop or improve a highly antibacterial and durable PPR material and its preparation method. Summary of the invention

[0004] Based on this, in order to solve the problems that the existing PPR materials have insufficient antibacterial properties, especially antibacterial durability, silver precipitation does not meet the requirements of hygienic performance, and the mechanical properties are poor, the present invention provides a high antibacterial and durable PPR material and a preparation method thereof, and the specific technical scheme is as follows: A highly antibacterial and durable PPR material, comprising an antibacterial agent A, an antibacterial agent B, random copolymer polypropylene, a silane coupling agent and an antioxidant; The raw materials for preparing the antibacterial agent A include low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth gum; The raw materials for preparing the antibacterial agent B include high-density polyethylene, hemicellulose, zinc oxide, 3 wt % acetic acid aqueous solution and leucite.

[0005] Furthermore, the preparation method of the antibacterial agent A comprises the following steps: The carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 80-120 kH for 1.2-1.8 hours, and then the tragacanth gum is added, and then sealed, the temperature is raised to 110-120° C., and the reaction is carried out for 5-6 hours at a stirring speed of 1200-1300 r / min, and then the temperature is lowered to room temperature, and then the seal is opened, and then the mixture is placed in a drying oven, dried at 90-100° C., and then added to a twin-screw extruder, and then the low-density polyethylene is added to the twin-screw extruder, and then mixed and extruded to obtain the antibacterial agent A.

[0006] Furthermore, the preparation method of the antibacterial agent B comprises the following steps: The hemicellulose and zinc oxide are added to a 3wt% acetic acid aqueous solution, stirred at a speed of 800-900r / min for 0.8-1.2h, then the white garnet is added, and then sealed, ultrasonicated at a frequency of 80-120kH for 1.1-1.5h, and then heated to 100-110°C, reacted at a stirring speed of 1000-1100r / min for 3.3-3.7h, and then cooled to room temperature, and then opened the seal, and then placed in a drying oven, dried at 70-80°C, and then added to a twin-screw extruder, and then the high-density polyethylene was added to the twin-screw extruder, and then mixed and extruded to obtain the antibacterial agent B.

[0007] Further, the silane coupling agent includes at least one of γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane and vinyltri(β-methoxyethoxy)silane.

[0008] Further, the antioxidant includes at least one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester, tris[2,4-di-tert-butylphenyl]phosphite and bis(2,4-dicumylphenyl)pentaerythritol-diphosphite.

[0009] Further, the high-density polyethylene includes high-density polyethylene resin Hanwha F920A or high-density polyethylene resin Dow AT6900; The low-density polyethylene includes low-density polyethylene Dow Elite 5400G or low-density polyethylene FP120-A.

[0010] Furthermore, the mass ratio of the low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 60-70:3-7:5-15:70-90:5-15.

[0011] Furthermore, the mass ratio of the high-density polyethylene, hemicellulose, zinc oxide, 3 wt % acetic acid aqueous solution and leucite is 60-70:5-15:5-15:60-80:5-15.

[0012] Furthermore, the mass ratio of the antibacterial agent A, the antibacterial agent B, the random copolymer polypropylene, the silane coupling agent and the antioxidant is 1-3:1-3:90-110:0.3-0.7:0.3-0.7.

[0013] The present technical solution also provides a method for preparing a highly antibacterial and durable PPR material, which comprises the following steps: The antibacterial agent A, the antibacterial agent B, the random copolymer polypropylene, the silane coupling agent and the antioxidant are uniformly mixed, and then added into a twin-screw extruder, and mixed and extruded to obtain the highly antibacterial and durable PPR material.

[0014] The highly antibacterial and durable PPR material provided by the above technical solution includes antibacterial agent A, antibacterial agent B, random copolymer polypropylene, silane coupling agent and antioxidant, wherein the raw materials for preparing antibacterial agent A include low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth gum, and the raw materials for preparing antibacterial agent B include high-density polyethylene, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and white garnet. It has excellent antibacterial properties and mechanical properties, and the antibacterial properties are long-lasting and stable. At the same time, it meets the requirements of hygienic performance and has low silver precipitation. Specifically, due to the certain degree of bending of the carbon atoms in the hexagonal arrangement of carbon nanotubes, a spatial topological structure can be formed, and then a helical structure can be formed. Tragacanth gum has rich multifunctional groups, which has both partial helical structure and partial linear structure. In the multi-directional microscopic environment constructed by carbon nanotubes and tragacanth gum, silver is not only more evenly distributed, but also more stable, and can be more durable and effective in antibacterial. Furthermore, it guides the nucleation of low-density polyethylene to form an effective bactericidal microenvironment and induce oxidative stress response; hemicellulose has abundant short side chains, which can effectively molecular water Dispersing zinc oxide, 3wt% acetic acid aqueous solution and white garnet on a flat plate can further affect the nucleation of high-density polyethylene; further, preparing an antibacterial agent A whose raw materials include low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth gum, and preparing an antibacterial agent B whose raw materials include high-density polyethylene, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and white garnet can not only affect the nucleation of random copolymer polypropylene, but also further cross-react with silane coupling agents and antioxidants to produce complex interactive reactions, and finally obtain a highly antibacterial and durable PPR material with excellent antibacterial and mechanical properties. DETAILED DESCRIPTION

[0015] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with its embodiments. It should be understood that the specific implementation methods described herein are only used to explain the present invention and do not limit the protection scope of the present invention.

[0016] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0017] A highly antibacterial and durable PPR material in one embodiment of the present invention comprises an antibacterial agent A, an antibacterial agent B, random copolymer polypropylene, a silane coupling agent and an antioxidant; The raw materials for preparing the antibacterial agent A include low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth gum; The raw materials for preparing the antibacterial agent B include high-density polyethylene, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite.

[0018] In one embodiment, the preparation method of the antibacterial agent A comprises the following steps: The carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 80-120 kH for 1.2-1.8 hours, and then the tragacanth gum is added, and then sealed, the temperature is raised to 110-120° C., and the reaction is carried out for 5-6 hours at a stirring speed of 1200-1300 r / min, and then the temperature is lowered to room temperature, and then the seal is opened, and then the mixture is placed in a drying oven, dried at 90-100° C., and then added to a twin-screw extruder, and then the low-density polyethylene is added to the twin-screw extruder, and then mixed and extruded to obtain the antibacterial agent A.

[0019] In one embodiment, the preparation method of the antibacterial agent B comprises the following steps: The hemicellulose and zinc oxide are added to a 3wt% acetic acid aqueous solution, stirred at a speed of 800-900r / min for 0.8-1.2h, then the white garnet is added, and then sealed, ultrasonicated at a frequency of 80-120kH for 1.1-1.5h, and then heated to 100-110°C, reacted at a stirring speed of 1000-1100r / min for 3.3-3.7h, and then cooled to room temperature, and then opened the seal, and then placed in a drying oven, dried at 70-80°C, and then added to a twin-screw extruder, and then the high-density polyethylene was added to the twin-screw extruder, and then mixed and extruded to obtain the antibacterial agent B.

[0020] In one embodiment, the silane coupling agent includes at least one of γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane and vinyltri(β-methoxyethoxy)silane.

[0021] In one embodiment, the antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris[2,4-di-tert-butylphenyl]phosphite and bis(2,4-dicumylphenyl)pentaerythritol-diphosphite.

[0022] In one embodiment, the high-density polyethylene includes high-density polyethylene resin Hanwha F920A or high-density polyethylene resin Dow AT6900; The low-density polyethylene includes low-density polyethylene Dow Elite 5400G or low-density polyethylene FP120-A.

[0023] In one embodiment, the mass ratio of the low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 60-70:3-7:5-15:70-90:5-15.

[0024] In one of the embodiments, the mass ratio of the high-density polyethylene, hemicellulose, zinc oxide, 3 wt % acetic acid aqueous solution and leucite is 60~70:5~15:5~15:60~80:5~15.

[0025] In one embodiment, the mass ratio of the antibacterial agent A, the antibacterial agent B, the random copolymer polypropylene, the silane coupling agent and the antioxidant is 1~3:1~3:90~110:0.3~0.7:0.3~0.7.

[0026] In one embodiment, the present technical solution provides a method for preparing a highly antibacterial and durable PPR material, which comprises the following steps: The antibacterial agent A, the antibacterial agent B, the random copolymer polypropylene, the silane coupling agent and the antioxidant are uniformly mixed, and then added into a twin-screw extruder, and mixed and extruded to obtain the highly antibacterial and durable PPR material.

[0027] The embodiments of the present invention will be described in detail below with reference to specific examples.

[0028] Embodiment 1: Preparation of antibacterial agent A: carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 100kH for 1.5h, and then tragacanth gum is added, and then sealed, heated to 115°C, reacted at a stirring speed of 1250r / min for 5.5h, and then cooled to room temperature, and then opened the seal, and then put into a drying oven, dried at 95°C, and then added to a twin-screw extruder, and then low-density polyethylene Dow Elite 5400G is added to the twin-screw extruder, and then mixed and extruded to obtain antibacterial agent A, wherein the mass ratio of low-density polyethylene Dow Elite 5400G, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 65:5:10:80:10; Preparation of antibacterial agent B: add hemicellulose and zinc oxide to a 3wt% acetic acid aqueous solution, stir at a speed of 850r / min for 1h, then add leucite, then seal, ultrasonicate at a frequency of 100kH for 1.3h, then heat to 105°C, react at a stirring speed of 1000r / min for 3.5h, then cool to room temperature, then open the seal, then place in a drying oven, dry at 75°C, then add a twin-screw extruder, then add the high-density polyethylene resin Dow AT6900 to the twin-screw extruder, and then mix and extrude to obtain antibacterial agent B, wherein the mass ratio of high-density polyethylene resin Dow AT6900, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite is 65:10:10:70:10; Preparation of PPR material: The above-mentioned antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester are mixed evenly, then added into a twin-screw extruder, and mixed and extruded to obtain a high antibacterial and durable PPR material, wherein the mass ratio of antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester is 2:2:100:0.5:0.5.

[0029] Embodiment 2: Preparation of antibacterial agent A: carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 100kH for 1.5 hours, and then tragacanth gum is added, and then sealed, heated to 115°C, reacted at a stirring speed of 1250r / min for 5.5 hours, and then cooled to room temperature, and then opened the seal, and then put into a drying oven, dried at 95°C, and then added to a twin-screw extruder, and then low-density polyethylene Dow Elite 5400G is added to the twin-screw extruder, and then mixed and extruded to obtain antibacterial agent A, wherein the mass ratio of low-density polyethylene Dow Elite 5400G, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 65:5:10:80:15; Preparation of antibacterial agent B: add hemicellulose and zinc oxide to a 3wt% acetic acid aqueous solution, stir at a speed of 850r / min for 1h, then add leucite, then seal, ultrasonicate at a frequency of 100kH for 1.3h, then heat to 105°C, react at a stirring speed of 1000r / min for 3.5h, then cool to room temperature, then open the seal, then place in a drying oven, dry at 75°C, then add a twin-screw extruder, then add the high-density polyethylene resin Dow AT6900 to the twin-screw extruder, and then mix and extrude to obtain antibacterial agent B, wherein the mass ratio of high-density polyethylene resin Dow AT6900, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite is 65:10:10:70:10; Preparation of PPR material: The above-mentioned antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester are mixed evenly, then added into a twin-screw extruder, and mixed and extruded to obtain a high antibacterial and durable PPR material, wherein the mass ratio of antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester is 2:2:100:0.5:0.5.

[0030] Embodiment 3: Preparation of antibacterial agent A: carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 100kH for 1.5h, and then tragacanth gum is added, and then sealed, heated to 115°C, reacted at a stirring speed of 1250r / min for 5.5h, and then cooled to room temperature, and then opened the seal, and then put into a drying oven, dried at 95°C, and then added to a twin-screw extruder, and then low-density polyethylene Dow Elite 5400G was added to the twin-screw extruder, and then mixed and extruded to obtain antibacterial agent A, wherein the mass ratio of low-density polyethylene Dow Elite 5400G, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 65:5:10:80:5; Preparation of antibacterial agent B: add hemicellulose and zinc oxide to a 3wt% acetic acid aqueous solution, stir at a speed of 850r / min for 1h, then add leucite, then seal, ultrasonicate at a frequency of 100kH for 1.3h, then heat to 105°C, react at a stirring speed of 1000r / min for 3.5h, then cool to room temperature, then open the seal, then place in a drying oven, dry at 75°C, then add a twin-screw extruder, then add the high-density polyethylene resin Dow AT6900 to the twin-screw extruder, and then mix and extrude to obtain antibacterial agent B, wherein the mass ratio of high-density polyethylene resin Dow AT6900, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite is 65:10:10:70:10; Preparation of PPR material: The above-mentioned antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester are mixed evenly, then added into a twin-screw extruder, and mixed and extruded to obtain a high antibacterial and durable PPR material, wherein the mass ratio of antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester is 2:2:100:0.5:0.5.

[0031] Embodiment 4: Preparation of antibacterial agent A: carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 100kH for 1.5h, and then tragacanth gum is added, and then sealed, heated to 115°C, reacted at a stirring speed of 1250r / min for 5.5h, and then cooled to room temperature, and then opened the seal, and then put into a drying oven, dried at 95°C, and then added to a twin-screw extruder, and then low-density polyethylene Dow Elite 5400G is added to the twin-screw extruder, and then mixed and extruded to obtain antibacterial agent A, wherein the mass ratio of low-density polyethylene Dow Elite 5400G, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 65:7:10:80:10; Preparation of antibacterial agent B: add hemicellulose and zinc oxide to a 3wt% acetic acid aqueous solution, stir at a speed of 850r / min for 1h, then add leucite, then seal, ultrasonicate at a frequency of 100kH for 1.3h, then heat to 105°C, react at a stirring speed of 1000r / min for 3.5h, then cool to room temperature, then open the seal, then place in a drying oven, dry at 75°C, then add a twin-screw extruder, then add the high-density polyethylene resin Dow AT6900 to the twin-screw extruder, and then mix and extrude to obtain antibacterial agent B, wherein the mass ratio of high-density polyethylene resin Dow AT6900, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite is 65:10:10:70:10; Preparation of PPR material: The above-mentioned antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester are mixed evenly, then added into a twin-screw extruder, and mixed and extruded to obtain a high antibacterial and durable PPR material, wherein the mass ratio of antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester is 2:2:100:0.5:0.5.

[0032] Embodiment 5: Preparation of antibacterial agent A: carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 100kH for 1.5h, and then tragacanth gum is added, and then sealed, heated to 115°C, reacted at a stirring speed of 1250r / min for 5.5h, and then cooled to room temperature, and then opened the seal, and then put into a drying oven, dried at 95°C, and then added to a twin-screw extruder, and then low-density polyethylene Dow Elite 5400G was added to the twin-screw extruder, and then mixed and extruded to obtain antibacterial agent A, wherein the mass ratio of low-density polyethylene Dow Elite 5400G, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 65:3:10:80:10; Preparation of antibacterial agent B: add hemicellulose and zinc oxide to a 3wt% acetic acid aqueous solution, stir at a speed of 850r / min for 1h, then add leucite, then seal, ultrasonicate at a frequency of 100kH for 1.3h, then heat to 105°C, react at a stirring speed of 1000r / min for 3.5h, then cool to room temperature, then open the seal, then place in a drying oven, dry at 75°C, then add a twin-screw extruder, then add the high-density polyethylene resin Dow AT6900 to the twin-screw extruder, and then mix and extrude to obtain antibacterial agent B, wherein the mass ratio of high-density polyethylene resin Dow AT6900, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite is 65:10:10:70:10; Preparation of PPR material: The above-mentioned antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester are mixed evenly, then added into a twin-screw extruder, and mixed and extruded to obtain a high antibacterial and durable PPR material, wherein the mass ratio of antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester is 2:2:100:0.5:0.5.

[0033] Comparative Example 1: Preparation of antibacterial agent A: carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 100kH for 1.5 hours, and then sealed, heated to 115°C, reacted at a stirring speed of 1250r / min for 5.5 hours, and then cooled to room temperature, and then unsealed, and then placed in a drying oven, dried at 95°C, and then added to a twin-screw extruder, and then low-density polyethylene Dow Elite 5400G was added to the twin-screw extruder, and then mixed and extruded to obtain antibacterial agent A, wherein the mass ratio of low-density polyethylene Dow Elite 5400G, carbon nanotubes, silver carbonate and ethanol is 65:5:10:80; Preparation of antibacterial agent B: add hemicellulose and zinc oxide to a 3wt% acetic acid aqueous solution, stir at a speed of 850r / min for 1h, then add leucite, then seal, ultrasonicate at a frequency of 100kH for 1.3h, then heat to 105°C, react at a stirring speed of 1000r / min for 3.5h, then cool to room temperature, then open the seal, then place in a drying oven, dry at 75°C, then add a twin-screw extruder, then add the high-density polyethylene resin Dow AT6900 to the twin-screw extruder, and then mix and extrude to obtain antibacterial agent B, wherein the mass ratio of high-density polyethylene resin Dow AT6900, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite is 65:10:10:70:10; Preparation of PPR material: The above-mentioned antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester are mixed evenly, then added into a twin-screw extruder, and mixed and extruded to obtain a high antibacterial and durable PPR material, wherein the mass ratio of antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester is 2:2:100:0.5:0.5.

[0034] Comparative Example 2: Preparation of antibacterial agent A: carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 100kH for 1.5h, and then tragacanth gum is added, and then sealed, heated to 115°C, reacted at a stirring speed of 1250r / min for 5.5h, and then cooled to room temperature, and then opened the seal, and then put into a drying oven, dried at 95°C, and then added to a twin-screw extruder, and then low-density polyethylene Dow Elite 5400G is added to the twin-screw extruder, and then mixed and extruded to obtain antibacterial agent A, wherein the mass ratio of low-density polyethylene Dow Elite 5400G, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 65:5:10:80:10; Preparation of antibacterial agent B: cellulose and zinc oxide are added to a 3wt% acetic acid aqueous solution, stirred at a speed of 850r / min for 1h, then white garnet is added, then sealed, ultrasonicated at a frequency of 100kH for 1.3h, then heated to 105°C, reacted at a stirring speed of 1000r / min for 3.5h, then cooled to room temperature, then unsealed, then placed in a drying oven, dried at 75°C, then added to a twin-screw extruder, then the high-density polyethylene resin Dow AT6900 is added to the twin-screw extruder, and then mixed and extruded to obtain antibacterial agent B, wherein the mass ratio of high-density polyethylene resin Dow AT6900, cellulose, zinc oxide, 3wt% acetic acid aqueous solution and white garnet is 65:10:10:70:10; Preparation of PPR material: The above-mentioned antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester are mixed evenly, then added into a twin-screw extruder, and mixed and extruded to obtain a high antibacterial and durable PPR material, wherein the mass ratio of antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester is 2:2:100:0.5:0.5.

[0035] Comparative Example 3: Preparation of antibacterial agent A: silver carbonate is added to ethanol, and then ultrasonicated at a power of 100kH for 1.5h, and then tragacanth gum is added, and then sealed, heated to 115°C, reacted at a stirring speed of 1250r / min for 5.5h, and then cooled to room temperature, and then unsealed, and then placed in a drying oven, dried at 95°C, and then added to a twin-screw extruder, and then low-density polyethylene Dow Elite 5400G was added to the twin-screw extruder, and then mixed and extruded to obtain antibacterial agent A, wherein the mass ratio of low-density polyethylene Dow Elite 5400G, silver carbonate, ethanol and tragacanth gum is 65:10:80:10; Preparation of antibacterial agent B: add hemicellulose and zinc oxide to a 3wt% acetic acid aqueous solution, stir at a speed of 850r / min for 1h, then add leucite, then seal, ultrasonicate at a frequency of 100kH for 1.3h, then heat to 105°C, react at a stirring speed of 1000r / min for 3.5h, then cool to room temperature, then open the seal, then place in a drying oven, dry at 75°C, then add a twin-screw extruder, then add the high-density polyethylene resin Dow AT6900 to the twin-screw extruder, and then mix and extrude to obtain antibacterial agent B, wherein the mass ratio of high-density polyethylene resin Dow AT6900, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite is 65:10:10:70:10; Preparation of PPR material: The above-mentioned antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester are mixed evenly, then added into a twin-screw extruder, and mixed and extruded to obtain a high antibacterial and durable PPR material, wherein the mass ratio of antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester is 2:2:100:0.5:0.5.

[0036] Comparative Example 4: Preparation of antimicrobial agent A: adding carbon nanotubes, silver carbonate, ethanol and tragacanth gum into a twin-screw extruder respectively, and then adding low-density polyethylene Dow Elite 5400G into the twin-screw extruder, and then mixing and extruding to obtain antimicrobial agent A, wherein the mass ratio of low-density polyethylene Dow Elite 5400G, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 65:5:10:80:10; Preparation of antibacterial agent B: add hemicellulose and zinc oxide to a 3wt% acetic acid aqueous solution, stir at a speed of 850r / min for 1h, then add leucite, then seal, ultrasonicate at a frequency of 100kH for 1.3h, then heat to 105°C, react at a stirring speed of 1000r / min for 3.5h, then cool to room temperature, then open the seal, then place in a drying oven, dry at 75°C, then add a twin-screw extruder, then add the high-density polyethylene resin Dow AT6900 to the twin-screw extruder, and then mix and extrude to obtain antibacterial agent B, wherein the mass ratio of high-density polyethylene resin Dow AT6900, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite is 65:10:10:70:10; Preparation of PPR material: The above-mentioned antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester are mixed evenly, then added into a twin-screw extruder, and mixed and extruded to obtain a high antibacterial and durable PPR material, wherein the mass ratio of antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester is 2:2:100:0.5:0.5.

[0037] Comparative Example 5: Preparation of antibacterial agent A: carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 100kH for 1.5h, and then tragacanth gum is added, and then sealed, heated to 115°C, reacted at a stirring speed of 1250r / min for 5.5h, and then cooled to room temperature, and then opened the seal, and then put into a drying oven, dried at 95°C, and then added to a twin-screw extruder, and then low-density polyethylene Dow Elite 5400G is added to the twin-screw extruder, and then mixed and extruded to obtain antibacterial agent A, wherein the mass ratio of low-density polyethylene Dow Elite 5400G, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 65:5:10:80:10; Preparation of antimicrobial agent B: adding hemicellulose, zinc oxide, 3 wt% acetic acid aqueous solution and leucite to a twin-screw extruder respectively, then adding the high-density polyethylene resin Dow AT6900 to the twin-screw extruder, and then mixing and extruding to obtain antimicrobial agent B, wherein the mass ratio of high-density polyethylene resin Dow AT6900, hemicellulose, zinc oxide, 3 wt% acetic acid aqueous solution and leucite is 65:10:10:70:10; Preparation of PPR material: The above-mentioned antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester are mixed evenly, then added into a twin-screw extruder, and mixed and extruded to obtain a high antibacterial and durable PPR material, wherein the mass ratio of antibacterial agent A, antibacterial agent B, random copolymer polypropylene, γ-aminopropyl triethoxysilane and tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester is 2:2:100:0.5:0.5.

[0038] The PPR materials obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were tested for antibacterial properties and durability. The test results are shown in Table 1.

[0039] Hygienic performance test: Test silver precipitation according to standard GB / T17219.

[0040] Antibacterial property: The antibacterial property and durability of PPR materials were tested according to JCT 939-2004 standard.

[0041] Mechanical strength: The tensile modulus test was carried out using a three-point bending tester.

[0042] Table 1:

[0043] As can be seen from Table 1, the highly antibacterial and durable PPR material provided by the present invention includes antibacterial agent A, antibacterial agent B, random copolymer polypropylene, silane coupling agent and antioxidant, wherein the raw materials for preparing antibacterial agent A include low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth gum, and the raw materials for preparing antibacterial agent B include high-density polyethylene, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and white garnet, which has excellent antibacterial properties and mechanical properties, long-lasting and stable antibacterial properties, and meets the requirements of hygienic properties, and the amount of silver precipitation is low. Specifically, the silver precipitation is less than 5PPb, the tensile modulus is as high as 796MPa (inclusive) and above, the antibacterial property of Staphylococcus aureus is as high as 99.9% (inclusive) and above, the antibacterial property of Escherichia coli is as high as 99.9% (inclusive) and above, the antibacterial durability of Staphylococcus aureus is as high as 97.8% (inclusive) and above, and the antibacterial durability of Escherichia coli is as high as 98.3% (inclusive) and above. More specifically, due to the fact that the carbon atoms in the hexagonal arrangement of carbon nanotubes are bent to a certain extent, a spatial topological structure can be formed, and then a helical structure can be formed. Tragacanth gum has rich multifunctional groups, which has both partial helical structure and partial linear structure. In the multi-directional microscopic environment constructed by carbon nanotubes and tragacanth gum, silver is not only more evenly distributed, but also more stable, and can be more durable and effective in antibacterial. Furthermore, it guides the nucleation of low-density polyethylene to form an effective bactericidal microenvironment and induce oxidative stress response; hemicellulose has abundant short side chains, which can effectively molecule Zinc oxide, 3wt% acetic acid aqueous solution and leucite are dispersed horizontally, which further affects the nucleation of high-density polyethylene; further, the preparation of antibacterial agent A whose raw materials include low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth gum, and the preparation of antibacterial agent B whose raw materials include high-density polyethylene, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite can not only affect the nucleation of random copolymer polypropylene, but also further cross-react with silane coupling agents and antioxidants to produce complex interactive reactions, and finally obtain a highly antibacterial and durable PPR material with excellent antibacterial and mechanical properties.

[0044] The tragacanth gum provided by the invention is food grade, non-toxic and edible.

[0045] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0046] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A highly antibacterial and durable PPR material, characterized in that: It includes antibacterial agent A, antibacterial agent B, random copolymer polypropylene, silane coupling agent and antioxidant; The raw materials for preparing the antibacterial agent A include low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth gum; The raw materials for preparing the antibacterial agent B include high-density polyethylene, hemicellulose, zinc oxide, 3 wt % acetic acid aqueous solution and leucite.

2. The highly antibacterial and durable PPR material according to claim 1, characterized in that: The preparation method of the antibacterial agent A comprises the following steps: The carbon nanotubes and silver carbonate are added to ethanol, and then ultrasonicated at a power of 80-120 kH for 1.2-1.8 hours, and then the tragacanth gum is added, and then sealed, the temperature is raised to 110-120° C., and the reaction is carried out for 5-6 hours at a stirring speed of 1200-1300 r / min, and then the temperature is lowered to room temperature, and then the seal is opened, and then the mixture is placed in a drying oven, dried at 90-100° C., and then added to a twin-screw extruder, and then the low-density polyethylene is added to the twin-screw extruder, and then mixed and extruded to obtain the antibacterial agent A.

3. The highly antibacterial and durable PPR material according to claim 1, characterized in that: The preparation method of the antibacterial agent B comprises the following steps: The hemicellulose and zinc oxide are added to a 3wt% acetic acid aqueous solution, stirred at a speed of 800-900r / min for 0.8-1.2h, then the white garnet is added, and then sealed, ultrasonicated at a frequency of 80-120kH for 1.1-1.5h, and then heated to 100-110°C, reacted at a stirring speed of 1000-1100r / min for 3.3-3.7h, and then cooled to room temperature, and then opened the seal, and then placed in a drying oven, dried at 70-80°C, and then added to a twin-screw extruder, and then the high-density polyethylene was added to the twin-screw extruder, and then mixed and extruded to obtain the antibacterial agent B.

4. The highly antibacterial and durable PPR material according to claim 1, characterized in that: The silane coupling agent includes at least one of γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane and vinyltri(β-methoxyethoxy)silane.

5. The highly antibacterial and durable PPR material according to claim 1, characterized in that: The antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris[2,4-di-tert-butylphenyl]phosphite and bis(2,4-dicumylphenyl)pentaerythritol-diphosphite.

6. The highly antibacterial and durable PPR material according to claim 1, characterized in that: The high-density polyethylene includes high-density polyethylene resin Hanwha F920A or high-density polyethylene resin Dow AT6900; The low-density polyethylene includes low-density polyethylene Dow Elite 5400G or low-density polyethylene FP120-A.

7. The highly antibacterial and durable PPR material according to claim 1, characterized in that: The mass ratio of the low-density polyethylene, carbon nanotubes, silver carbonate, ethanol and tragacanth gum is 60-70:3-7:5-15:70-90:5-15.

8. The highly antibacterial and durable PPR material according to claim 1, characterized in that: The mass ratio of the high-density polyethylene, hemicellulose, zinc oxide, 3wt% acetic acid aqueous solution and leucite is 60-70:5-15:5-15:60-80:5-15.

9. The highly antibacterial and durable PPR material according to claim 1, characterized in that: The mass ratio of the antibacterial agent A, the antibacterial agent B, the random copolymer polypropylene, the silane coupling agent and the antioxidant is 1-3:1-3:90-110:0.3-0.7:0.3-0.

7.

10. A method for preparing a highly antibacterial and durable PPR material, characterized in that: The preparation method is used to prepare the highly antibacterial and durable PPR material as claimed in claim 1, and comprises the following steps: The antibacterial agent A, the antibacterial agent B, the random copolymer polypropylene, the silane coupling agent and the antioxidant are uniformly mixed, and then added into a twin-screw extruder, and mixed and extruded to obtain the highly antibacterial and durable PPR material.

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