A kind of antibacterial and anti-scaling functional tube
By blending copper powder particles with polyolefin resin and combining it with fiber-reinforced POM materials, new antibacterial pipes are prepared, which solves the problem of contamination caused by microbial growth in traditional pipes and achieves safe and healthy antibacterial effects and high pressure resistance. .
Patent Information
- Application Number
- CN201910031542.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2019-01-14
- Publication Date
- 2025-01-21
- Estimated Expiration
- 2039-01-14
AI Technical Summary
Traditional water supply pipelines are contaminated by drinking water due to microorganisms. Existing antibacterial pipes such as nano-silver pipes have safety hazards, and safe and healthy antibacterial pipes are needed.
Copper powder particles and polyolefin resin are blended and compounded as the antibacterial layer material, combined with fiber-reinforced POM material as the reinforcing layer, and a new antibacterial pipeline is prepared through a multi-layer co-extrusion process.
It achieves the antibacterial and anti-scaling effect in the pipeline, improves the pressure resistance of the pipe, and the copper material used is safe and reliable, avoiding the potential health risks of nanosilver.
Smart Images
Figure CN111434966B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of pipe production, in particular to a pipe with antibacterial and anti-scaling functions. Background Art
[0002] During the use of traditional water supply pipes, the growth and spread of harmful bacteria, mold and other microorganisms will cause secondary pollution of drinking water, which will harm people's health. Giving pipes antibacterial function can effectively inhibit the growth of harmful bacteria in pipes, thereby ensuring the health and safety of drinking water. In recent years, the antibacterial pipes mainly promote nano-silver antibacterial pipes. Nano-silver has a good antibacterial effect, but its safety has been questioned by researchers at home and abroad. Studies have shown that silver ions have strong oxidizing properties, and excessive accumulation of silver ions entering the human body can also cause symptoms such as edema of internal organs. The strong permeability of nanoparticles not only provides effectiveness for the use of drugs, but also poses a potential threat to human health. Therefore, it is a very meaningful topic to develop a pipe with certain antibacterial function and safety and health. Copper is the earliest metal material discovered and used by humans. Thousands of years of use have certified its safety and reliability, and copper ions are an indispensable element for humans, and the antibacterial properties of copper materials have long been certified. In the "Classification Catalog of Water-Related Products", it is clearly stated that it is one of the materials used for water transmission and distribution. Therefore, the application of copper materials to water pipes has certain development value.
[0003] In the market, copper-containing pipes are mainly copper pipes and copper-plastic composite pipes. However, the cost of copper pipes is high, and water leakage is prone to occur at their joints; while copper-plastic composite pipes are copper pipes lined inside plastic pipes. Although the cost is slightly reduced, there is still a risk of delamination at the copper-plastic interface. Therefore, a new copper-containing pipe product is developed. Therefore, we propose to use copper powder particles and polyolefin resins as antibacterial layer materials to prepare new antibacterial pipes as an iterative upgrade of antibacterial pipe development.
[0004] In addition, in order to further improve the pressure resistance of the pipe and distinguish it from the traditional metal material reinforced composite pipe, the utility model also introduces a fiber-reinforced modified material of the high-strength engineering plastic POM as a reinforcement layer. Through multi-layer co-extrusion, the production process is simple, and the modified material can be better combined with the matrix resin, thereby ensuring that the new pipe has stable pressure resistance. Summary of the invention
[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a tube with antibacterial and anti-scaling functions.
[0006] The objective of the present invention is achieved through the following technical solutions:
[0007] An antibacterial and anti-scaling functional tube, the inner layer of the tube is a modified polyolefin material with antibacterial and anti-scaling functions, the second layer is a hot melt adhesive, the third layer is a fiber-reinforced POM material, the fourth layer is a hot melt adhesive layer, and the fifth layer is a polyolefin material; wherein:
[0008] The introduction of micro-nano copper powder or copper-loaded montmorillonite into the inner layer resin can achieve the effect of antibacterial and anti-scaling; at the same time, the introduction of fiber-reinforced polyoxymethylene material into the middle layer improves the strength of the overall pipe and further realizes the higher pressure resistance of the pipe.
[0009] The base resin material of the inner layer of the pipe is one of PPR, PE, PERT and PB, and an antibacterial and anti-scaling modified material is added.
[0010] The antibacterial and anti-scaling modified material of the inner layer of the pipe is one of micro-nano copper powder, copper-loaded montmorillonite or copper-loaded montmorillonite hybrid material. The particle size of the micro-nano copper powder is 100-800nm, and the mass fraction of the micro-nano copper powder in the inner layer of the pipe is 0.1-1%;
[0011] The copper ion content of the copper-loaded montmorillonite is 50-100 mg / g, the particle size is 500 nanometers to 1 micron, and the mass fraction of the copper-loaded montmorillonite in the inner layer of the pipe is 0.5-5%.
[0012] The copper-loaded montmorillonite hybrid material has a particle size of 500 nanometers to 1 micron, and the mass fraction of the copper-loaded montmorillonite hybrid material in the inner layer of the pipe is 0.5 to 5%.
[0013] The preparation method of copper-loaded montmorillonite hybrid material comprises the following specific steps:
[0014] First, montmorillonite is added to a solution of copper sulfate pentahydrate, stirred by microwave, reacted at 40-60°C for 6h, centrifuged until the montmorillonite is completely precipitated, then washed with deionized water, and part of the water is retained to form a suspension to obtain a primary copper-loaded montmorillonite product; then added to an ethanol solution of aminosilane, the pH value is adjusted to 3-5 with glacial acetic acid, and refluxed at 80°C for 6h; after the reaction is completed, it is filtered, washed with deionized water, and water is added to form a copper-loaded organic modified montmorillonite suspension; finally, it is blended with a graphene oxide suspension, ultrasonicated for 1h, and then stirred for 2h, and then precipitated, filtered, and freeze-dried to prepare a copper-loaded montmorillonite hybrid material.
[0015] The mass ratio of montmorillonite to copper sulfate pentahydrate is 1:2;
[0016] The mass fraction of the primary product of copper-carrying montmorillonite in the suspension is 5 to 10%;
[0017] The mass fraction of aminosilane in ethanol is 5%;
[0018] The mass ratio of the suspension of the copper-loaded montmorillonite primary product to the ethanol solution of aminosilane is 5:1;
[0019] The mass fraction of graphene oxide in the graphene oxide suspension is 1 to 5%; the graphene oxide suspension is formed by dissolving graphene oxide in water;
[0020] The mass ratio of the copper-loaded organically modified montmorillonite suspension to the graphene oxide suspension is 3:1;
[0021] Graphene oxide has a unique two-dimensional (2D) honeycomb hydrophobic surface structure and hydrophilic groups, and its edges contain carboxyl (~COOH) and hydroxyl (~OH) groups, which give it excellent antibacterial activity. Graphene oxide can mechanically destroy bacterial films to achieve antibacterial function.
[0022] Copper-loaded montmorillonite hybrid material: a core-shell double-layer structure, the surface layer of which is wrapped with graphene, and the inner layer is a copper-loaded organic modified montmorillonite composite material.
[0023] The third layer of the pipe is a reinforcement layer, which is reinforced with fiber-reinforced POM with a similar processing temperature to improve the overall strength of the pipe. In order to ensure that there is no stratification between the pipe and the matrix resin, hot melt adhesive is used in the second and fourth layers to ensure direct bonding with the matrix resin. The fiber used can be one of glass fiber, basalt fiber, and carbon fiber.
[0024] The proportions of the various layers of the pipe are: inner layer 5-20%; second layer 0-10%; third layer 0-40%; fourth layer 0-10%; fifth layer 25-80%.
[0025] The inner layer and outer layer matrix resin materials of the pipe are one of PPR, PE, PERT and PB.
[0026] Compared with the prior art, the present invention has the following positive effects:
[0027] 1. The use of non-toxic and safe micro-nano copper materials as antibacterial ingredients in domestic pipes makes the new generation of antibacterial and anti-scaling pipe products have excellent hygienic performance, which is an iterative upgrade of the original antibacterial products.
[0028] 2. POM modified materials with a processing temperature close to that of polyolefins are selected as the reinforcement layer. Through co-extrusion, the interaction force between the material and the matrix resin is ensured to ensure that the product is not delaminated; hot-melt connection between pipes and fittings can be achieved, ensuring that the pipeline product construction is convenient, stable and reliable.
[0029] 3. Antibacterial materials can be prepared into masterbatches or directly blended and extruded; POM reinforced materials can be made into modified pellets for direct production; the entire production process can use the original extrusion equipment, the process operation is simple, and industrial production can be realized. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 This is a schematic diagram of an antibacterial and anti-scaling functional tube;
[0031] In the accompanying drawings: 1 inner layer of the pipe, 2 second layer, 3 third layer, 4 fourth layer, 5 fifth layer. DETAILED DESCRIPTION
[0032] The following provides a specific implementation of an antibacterial and anti-scaling functional tube of the present invention.
[0033] Example 1
[0034] An antibacterial and anti-scaling functional pipe, the inner layer of the pipe is a micro-nano copper powder modified HDPE pipe, the third layer is a glass fiber reinforced POM material, the two are bonded by hot melt adhesive, and the outermost layer is a HDPE substrate. Among them:
[0035] In the inner layer of the pipe, the particle size of the added micro-nano copper powder is 500nm. 10% of the modified masterbatch is first prepared, and then blended with the HDPE base material at an addition ratio of 8%.
[0036] The third layer of the pipe is glass fiber reinforced POM, in which the fiber content is 25%. The modified material contains 8% of a compatibilizer to ensure the bonding between the fiber and the POM matrix. In order to reduce the crystallization rate of POM, 5% of TPU is appropriately added for adjustment.
[0037] The proportions of the various layers of the pipe are as follows: the inner layer 1 is 10%; the second layer 2 is 10%; the third layer 3 is 40%; the fourth layer 4 is 10%; and the fifth layer 5 is 30%.
[0038] The pipe can be directly extruded through a five-layer co-extrusion device.
[0039] The test indexes of the antibacterial performance of the inner layer material are as follows: Table 1
[0040] Experimental strains Antimicrobial performance value Escherichia coli 6.3 Staphylococcus aureus 6.2
[0041] Example 2
[0042] An antibacterial and anti-scaling functional pipe, the inner layer of the pipe is a modified PPR pipe with copper-loaded montmorillonite, the third layer is a glass fiber reinforced POM material, the two are bonded by hot melt adhesive, and the outermost layer is a PPR substrate. Among them:
[0043] In the inner layer of the pipe, the particle size of the added copper-loaded montmorillonite is 800 nm. 10% of the modified masterbatch is first prepared and then blended with the HDPE base material at a 10% addition ratio.
[0044] The third layer of the pipe is glass fiber reinforced POM, with a fiber content of 25%. The modified material contains 8% of a compatibilizer to ensure the bonding between the fiber and the POM matrix. In order to reduce the crystallization rate of POM, 5% of TPU is appropriately added for adjustment.
[0045] The proportions of the various layers of the pipe are: inner layer 12%; second layer 8%; third layer 32%; fourth layer 8%; fifth layer 40%.
[0046] The pipe can be directly extruded through a five-layer co-extrusion device.
[0047] The test indexes of the antibacterial properties of the inner layer materials are as follows: Table 2
[0048] Experimental strains Antimicrobial performance value Escherichia coli 3.2 Staphylococcus aureus 2.9
[0049] Example 3
[0050] An antibacterial and anti-scaling functional pipe, the inner layer of the pipe is a modified HDPE pipe made of copper-loaded montmorillonite hybrid material, the third layer is a basalt fiber reinforced POM material, the two are bonded by hot melt adhesive, and the outermost layer is a HDPE substrate. Among them:
[0051] In the inner layer of the pipe, the particle size of the added copper-loaded montmorillonite hybrid material is 200 nm. 10% of the modified masterbatch is first prepared, and then blended with the HDPE base material at an addition ratio of 5%.
[0052] The third layer of the pipe is basalt fiber reinforced POM, with a fiber content of 25%. The modified material contains 8% of a compatibilizer to ensure the bonding between the fiber and the POM matrix. In order to reduce the crystallization rate of POM, 5% of TPU is appropriately added for adjustment.
[0053] The proportions of the various layers of the pipe are: inner layer 20%; second layer 10%; third layer 30%; fourth layer 10%; fifth layer 30%.
[0054] The pipe can be directly extruded through a five-layer co-extrusion device.
[0055] The preparation method of copper-loaded montmorillonite hybrid material comprises the following specific steps:
[0056] First, montmorillonite is added to a solution of copper sulfate pentahydrate, stirred by microwave, reacted at 40-60°C for 6h, centrifuged until the montmorillonite is completely precipitated, then washed with deionized water, and part of the water is retained to form a suspension to obtain a primary copper-loaded montmorillonite product; then added to an ethanol solution of aminosilane, the pH value is adjusted to 3-5 with glacial acetic acid, and refluxed at 80°C for 6h; after the reaction is completed, it is filtered, washed with deionized water, and water is added to form a copper-loaded organic modified montmorillonite suspension; finally, it is blended with a graphene oxide suspension, ultrasonicated for 1h, and then stirred for 2h, and then precipitated, filtered, and freeze-dried to prepare a copper-loaded montmorillonite hybrid material.
[0057] The mass ratio of montmorillonite to copper sulfate pentahydrate is 1:2;
[0058] The mass fraction of the primary product of copper-loaded montmorillonite in the suspension is 7%;
[0059] The mass fraction of aminosilane in ethanol is 5%;
[0060] The mass ratio of the suspension of the copper-loaded montmorillonite primary product to the ethanol solution of aminosilane is 5:1;
[0061] The mass fraction of graphene oxide in the graphene oxide suspension is 1 to 5%; the graphene oxide suspension is formed by dissolving graphene oxide in water;
[0062] The mass ratio of the copper-loaded organically modified montmorillonite suspension to the graphene oxide suspension is 3:1;
[0063] The test indexes of the antibacterial properties of the inner layer materials are as follows: Table 3
[0064] Experimental strains Antimicrobial performance value Escherichia coli 5.5 Staphylococcus aureus 5.7
[0065] Example 4
[0066] An antibacterial and anti-scaling functional pipe, the inner layer of the pipe is a modified HDPE pipe made of copper-loaded montmorillonite hybrid material, the third layer is a basalt fiber reinforced POM material, the two are bonded by hot melt adhesive, and the outermost layer is a HDPE substrate. Among them:
[0067] In the inner layer of the pipe, the particle size of the added copper-loaded montmorillonite hybrid material is 200 nm. 10% of the modified masterbatch is first prepared, and then blended with the HDPE base material at an addition ratio of 5%.
[0068] The third layer of the pipe is basalt fiber reinforced POM, with a fiber content of 25%. The modified material contains 8% of a compatibilizer to ensure the bonding between the fiber and the POM matrix. In order to reduce the crystallization rate of POM, 5% of TPU is appropriately added for adjustment.
[0069] The proportions of the various layers of the pipe are: inner layer 20%; second layer 10%; third layer 30%; fourth layer 10%; fifth layer 30%.
[0070] The pipe can be directly extruded through a five-layer co-extrusion device.
[0071] The preparation method of copper-loaded montmorillonite hybrid material comprises the following specific steps:
[0072] First, montmorillonite is added to a solution of copper sulfate pentahydrate, stirred by microwave, reacted at 40-60°C for 6 hours, centrifuged until the montmorillonite is completely precipitated, then washed with deionized water, and part of the water is retained to form a suspension to obtain the primary product of copper-loaded montmorillonite; then added to an ethanol solution of aminosilane, the pH value is adjusted to 3-5 with glacial acetic acid, and refluxed at 80°C for 6 hours; after the reaction is completed, it is filtered, washed with deionized water, and water is added to form a copper-loaded organic modified montmorillonite suspension; then washed with deionized water, filtered, and freeze-dried to prepare a copper-loaded montmorillonite hybrid material.
[0073] The mass ratio of montmorillonite to copper sulfate pentahydrate is 1:2;
[0074] The mass fraction of the primary product of copper-loaded montmorillonite in the suspension is 7%;
[0075] The mass fraction of aminosilane in ethanol is 5%;
[0076] The mass ratio of the suspension of the copper-loaded montmorillonite primary product to the ethanol solution of aminosilane is 5:1;
[0077] The test indexes of the antibacterial properties of the inner layer materials are as follows: Table 4
[0078] Experimental strains Antimicrobial performance value Escherichia coli 4.8 Staphylococcus aureus 5.1
[0079] From the antibacterial performance, compared with Example 3, the antibacterial performance decreased by about 10%, which was mainly due to the synergistic effect of graphene oxide.
[0080] Example 5
[0081] An antibacterial and anti-scaling functional pipe, the inner layer of the pipe is a micro-nano copper powder modified HDPE pipe, and the outermost layer is a HDPE substrate. Among them:
[0082] In the inner layer of the pipe, the particle size of the added micro-nano copper powder is 500nm. 10% of the modified masterbatch is first prepared, and then blended with the HDPE base material at an addition ratio of 8%.
[0083] The ratio between the layers of the pipe is: inner layer 10%; fifth layer 90%.
[0084] The pipe can be directly extruded through a two-layer co-extrusion device.
[0085] The test indexes of the antibacterial performance of the inner layer material are as follows: Table 1
[0086] Experimental strains Antimicrobial performance value Escherichia coli 6.8 Staphylococcus aureus 6.5
[0087] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this technical field can make several improvements and modifications without departing from the concept of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.
Claims
1. An antibacterial and anti-scaling functional tube, the inner layer of the tube is a modified polyolefin material with antibacterial and anti-scaling functions, the second layer is a hot melt adhesive, the third layer is a fiber-reinforced POM material, the fourth layer is a hot melt adhesive layer, and the fifth layer is a polyolefin material; wherein: The copper-loaded montmorillonite hybrid material is introduced into the inner layer resin; The fiber-reinforced polyoxymethylene material is introduced into the middle layer; The preparation method of copper-loaded montmorillonite hybrid material comprises the following specific steps: First, montmorillonite is added to a solution of copper sulfate pentahydrate, stirred by microwave, reacted at 40-60°C for 6h, centrifuged until the montmorillonite is completely precipitated, then washed with deionized water, and part of the water is retained to form a suspension to obtain a copper-loaded montmorillonite primary product; then added to an ethanol solution of aminosilane, the pH value is adjusted to 3-5 with glacial acetic acid, and refluxed at 80°C for 6h; after the reaction is completed, filtered, washed with deionized water, and water is added to form a copper-loaded organic modified montmorillonite suspension; finally, mixed with a graphene oxide suspension, ultrasonicated for 1h, and then stirred for 2h, and then precipitated, filtered, and freeze-dried to prepare a copper-loaded montmorillonite hybrid material; The copper-loaded montmorillonite hybrid material has a particle size of 500 nanometers to 1 micron, and the mass fraction of the copper-loaded montmorillonite hybrid material in the inner layer of the pipe is 0.5 to 5%.
2. The antibacterial and anti-scaling functional tube according to claim 1, characterized in that: The third layer of the pipe is a reinforcement layer, which is made by co-extruding fiber-reinforced POM with a similar processing temperature. Hot melt adhesive is used in the second and fourth layers to ensure the bonding strength with the matrix resin.
3. The antibacterial and anti-scaling functional tube according to claim 1, characterized in that: The mass ratios of the various layers of the pipe are as follows: inner layer 5-20%; second layer 0-10%; third layer 0-40%; fourth layer 0-10%; fifth layer 25-80%.
4. The antibacterial and anti-scaling functional tube according to claim 1, characterized in that: The base resin material of the inner layer of the pipe is one of PPR, PE, PERT and PB, and an antibacterial and anti-scaling modified material is added.
5. The antibacterial and anti-scaling functional tube according to claim 1, characterized in that: The outer layer matrix resin material of the pipe is one of PPR, PE, PERT and PB.
Citation Information
Patent Citations
Antibacterial composite Al-plastic tube
CN1309146A
Bacteriostatic and anti-scaling functional pipe
CN209430893U