Manufacturing method of non-polar ultrahigh pipe
The antibacterial agent is prepared by modifying cyclodextrin carrier, silver salt and thymeol, and the non-polar ultra-high pipe material is prepared by co-extruding ultra-high molecular weight polyethylene and low-density polyethylene, which solves the complex process and inhibition of the existing technology. The problems of poor bacterial effect and insufficient mechanical properties have achieved efficient antibacterial and mechanical properties improvement.
Patent Information
- Application Number
- CN202411451366.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-17
- Publication Date
- 2025-01-10
AI Technical Summary
The production process of existing ultra-high pipe materials is complex, with average antibacterial effect, poor mechanical properties, and high cost of traditional antibacterial agents, which affects the performance of the material.
The modified cyclodextrin carrier, silver salt and thymeol were used to prepare antibacterial agents, and non-polar ultra-high pipes were prepared through the extrusion mechanism. Ultra-high molecular weight polyethylene and low-density polyethylene were co-extruded to form composite pipes, and passed through the vehicle. Cut out the outer wall to improve antibacterial and mechanical properties.
The antibacterial and mechanical properties of the pipe are significantly improved, with the antibacterial rate reaching more than 99%, the oxygen permeability is reduced to 0.04cc/m2·day, the mechanical properties are improved by more than 30%, and the production is simple and the cost is low.
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of pipe preparation, and in particular to a non-polar ultra-high pipe and a manufacturing method thereof. Background Art
[0002] Polyethylene ultra-high pipe is a high molecular thermoplastic material with excellent comprehensive performance. It is widely used in household water supply pipes due to its low cost, strong wear resistance, stable chemical properties, high strength and long-term use. Ultra-high molecular weight polyethylene pipe is made of ultra-high molecular weight polyethylene as the main raw material. In addition to inheriting the excellent properties of the raw materials, it also has the characteristics of light weight, easy installation and construction, and strong low temperature resistance. It is widely used in daily life and home decoration, especially for water supply and floor heating pipe installation.
[0003] As people's quality of life continues to improve, the requirements for home decoration materials are also getting higher and higher. Antibacterial barrier pipes, as a new type of pipe product that can maintain the health of the water quality of the pipe system and isolate oxygen, have been selling better and better in recent years. The preparation of oxygen-barrier pipes on the market is mostly through multi-layer co-extrusion of polyethylene and ethylene-vinyl alcohol copolymer. The high crystallinity and other properties of ethylene-vinyl alcohol copolymer are used to block the entry of oxygen to achieve the effect of oxygen barrier and antibacterial, but this method is complicated and has high production costs. The antibacterial effect of traditional antibacterial pipes is achieved by adding inorganic nano-silver antibacterial agents containing Ag+, but the combination of inorganic nano-silver antibacterial agents and polymer materials will affect the antibacterial ability of the pipes, and the cost is relatively high. Summary of the invention
[0004] In order to solve the above problems, the present application provides a non-polar ultra-high temperature material and a manufacturing method thereof, which solves the problems of complex production process, general antibacterial effect and poor mechanical properties of existing ultra-high temperature materials.
[0005] The purpose of the present invention can be achieved through the following technical solutions:
[0006] A non-polar ultra-high-pressure material comprises the following components: 60-80 parts of ultra-high molecular weight polyethylene, 30-50 parts of low-density polyethylene, 10-20 parts of masterbatch, and 4-8 parts of antibacterial agent; wherein the antibacterial agent is prepared from modified cyclodextrin carrier, silver salt and thymol as main components.
[0007] Optionally, the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 1.5-2.8 million. Within this molecular weight range, the tensile strength, impact strength, hydrostatic pressure, wear resistance, processability and other comprehensive properties of the ultra-high molecular weight polyethylene pipe can reach the best, thereby improving the mechanical properties of the pipe.
[0008] Optionally, the antibacterial agent is prepared by the following method:
[0009] (1) reacting silver nitrate solution and sodium potassium tartrate in an alkaline solution for 1.2-2.5 hours; then adding reducing agent formaldehyde to react for 1.5-2.5 hours;
[0010] (2) mixing cyclodextrin and maltodextrin, adding 40° C.-120° C. water and stirring for 1-2 hours to obtain a modified cyclodextrin carrier;
[0011] (3) adding the product obtained in step (1) to the modified cyclodextrin carrier prepared in step (2), adding ethanol and thymol to carry out a mixed reaction for 0.6-1.5 hours to obtain an antibacterial agent.
[0012] Optionally, in step (1), the mass ratio of the silver nitrate solution to potassium sodium tartrate is 20-30:1; the reaction temperature of the alkaline solution is 28-42°C; the pH of the alkaline solution can be adjusted using aqueous ammonia, sodium hydroxide solution or a mixture thereof.
[0013] Optionally, the mass ratio of the cyclodextrin to maltodextrin in step (2) is 1:2-2:1; maltodextrin and cyclodextrin have similar molecular structures, and the two are combined to form a complex, and after the cyclodextrin is included, the two form an inclusion micelle structure, which increases the solubility and saturation concentration of the cyclodextrin itself, thereby increasing the inclusion amount of the cyclodextrin carrier for the antibacterial factor.
[0014] Optionally, the mass ratio of the product, modified cyclodextrin carrier, ethanol and thymol in step (3) is 4-6:1:1.5-2. Thymol is a natural plant antimicrobial extracted from oregano oil, and also has antifungal and antiparasitic effects, as well as antiseptic effects.
[0015] On the other hand, the present invention provides a method for preparing the above-mentioned non-polar ultrahigh temperature material, comprising the following steps:
[0016] (1) Ultra-high molecular weight polyethylene material, masterbatch and antibacterial agent are introduced into the die head from the main extruder, and low-density polyethylene material is introduced into the die head from the auxiliary extruder. The two materials are combined at the die head and extruded into a composite pipe by the die head. The ultra-high molecular weight polyethylene material forms the inner wall layer of the composite pipe, and the low-density polyethylene material forms the outer wall layer of the composite pipe;
[0017] (2) The outer wall layer of the composite pipe in step (1) is removed by turning to obtain the antibacterial super-high pipe.
[0018] Optionally, the extruder barrel temperature is 120°C-230°C; the barrel of the extruder main machine is a segmented heating barrel; the first segment heating temperature of the barrel is 120-150°C, the second segment heating temperature of the barrel is 150-190°C, and the third segment heating temperature of the barrel is 190-230°C.
[0019] Compared with the prior art, the present invention has the following beneficial effects:
[0020] The present application discloses a non-polar UHV high temperature pipe, in which an independently developed antibacterial agent is innovatively added to the non-polar UHV high temperature pipe, thereby improving the antibacterial performance of the non-polar UHV high temperature pipe, and the number of viable bacteria can be as low as 15 CFU / cm2 or less. The antibacterial agent prepared by the present invention is a composite antibacterial agent containing silver and thymol, and the organic-inorganic composite antibacterial agent prepared by compounding the natural organic antibacterial agent of thymol and loading the modified cyclodextrin carrier can significantly improve the antibacterial property of the antibacterial agent, and the cyclodextrin coating structure can further enhance the barrier effect and mechanical properties of the pipe. DETAILED DESCRIPTION
[0021] The technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.
[0022] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.
[0023] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the prior art can be used. If no manufacturer is specified for the reagents and other instruments used, they are all conventional reagent products that can be obtained commercially. The specific implementation contents of the present invention are as follows:
[0024] In a first aspect, an embodiment of the present invention provides a non-polar ultra-high temperature material, which comprises the following components: 60-80 parts of ultra-high molecular weight polyethylene, 30-50 parts of low-density polyethylene, 10-20 parts of masterbatch, and 4-8 parts of antibacterial agent.
[0025] It should be pointed out that in actual use, corresponding substances can be added according to actual needs to achieve the expected technical effect.
[0026] The non-polar ultra-high pipe provided by the embodiment of the present invention ensures the excellent performance of ultra-high molecular weight polyethylene pipes, and utilizes the lubricity of low-density polyethylene to improve the defects such as surface quality and mechanical strength reduction caused by melt fracture. At the same time, the self-developed antibacterial agent is added in the pipe preparation process, and the cyclodextrin loaded with Ag+ and thymol can not only make the pipe have antibacterial properties, but also the unique bundling effect of the modified cyclodextrin can make the antibacterial factors dispersed evenly, which can increase the impact resistance and antibacterial properties of the pipe products.
[0027] In a second aspect, an embodiment of the present invention provides a method for preparing the non-polar ultrahigh temperature material according to the first aspect, comprising the following steps:
[0028] Step 1, ultra-high molecular weight polyethylene material, masterbatch and antibacterial agent are introduced into the die head from the main extruder, and low-density polyethylene material is introduced into the die head from the auxiliary extruder, the two materials are combined at the die head, and are extruded into a composite pipe by the die head, wherein the ultra-high molecular weight polyethylene material forms the inner wall layer of the composite pipe, and the low-density polyethylene material forms the outer wall layer of the composite pipe;
[0029] Step 2, removing the outer wall layer of the composite pipe in step (1) by turning to obtain the antibacterial super-high pipe.
[0030] Among them, the temperature of the extruder barrel is 120℃-230℃; the barrel of the extruder main machine is a segmented heating barrel; the heating temperature of the first section of the barrel is 120-150℃, the heating temperature of the second section of the barrel is 150-190℃, and the heating temperature of the third section of the barrel is 190-230℃.
[0031] The non-polar ultra-high temperature material provided in this embodiment has a simple preparation method and can be mass-produced. At the same time, the raw materials used are all relatively cheap, non-toxic or extremely low-toxic, so the biosafety is very high during mass production or actual use.
[0032] In order to enable those skilled in the art to better understand the present invention, the antibacterial ultra-high temperature material and the preparation method thereof provided by the present invention are described below through a number of specific embodiments.
[0033] Example 1
[0034] A method for preparing a non-polar ultra-high temperature material is prepared by the following steps:
[0035] (1) Preparation of an antibacterial agent: 1) Add silver nitrate solution and potassium sodium tartrate in a mass ratio of 25:1 to an alkaline solution, and react at a reaction temperature of 35°C for 2 hours; then add a reducing agent, formaldehyde, and react for 2 hours; 2) Mix cyclodextrin and maltodextrin in a mass ratio of 1:1, add 80°C water and stir for 1.5 hours to obtain a modified cyclodextrin carrier; 3) Add the product obtained in step 1) to the modified cyclodextrin carrier prepared in step 2), add ethanol and thymol in a mass ratio of 5:1:1 to the product, the modified cyclodextrin carrier, ethanol, and thymol, and mix for 1.2 hours to obtain an antibacterial agent;
[0036] (2) Weighing 70 parts of ultra-high molecular weight polyethylene, 40 parts of low-density polyethylene, 15 parts of masterbatch, and 6 parts of antibacterial agent respectively; the ultra-high molecular weight polyethylene material, the masterbatch and the antibacterial agent are introduced into the die head from the main extruder, and the low-density polyethylene material is introduced into the die head from the auxiliary extruder, and the two materials are combined at the die head and extruded into a composite pipe by the die head, wherein the ultra-high molecular weight polyethylene material forms the inner wall layer of the composite pipe, and the low-density polyethylene material forms the outer wall layer of the composite pipe;
[0037] (3) The outer wall layer of the composite pipe in step (2) is removed by turning to obtain the antibacterial super-high pipe.
[0038] Example 2
[0039] A method for preparing a non-polar ultra-high temperature material is prepared by the following steps:
[0040] (1) Preparation of an antibacterial agent: 1) Add silver nitrate solution and potassium sodium tartrate in a mass ratio of 20:1 to an alkaline solution, and react at a reaction temperature of 28°C for 2.5 hours; then add a reducing agent, formaldehyde, and react for 1.5 hours; 2) Mix cyclodextrin and maltodextrin in a mass ratio of 1:2, add 40°C water and stir for 2 hours to obtain a modified cyclodextrin carrier; 3) Add the product obtained in step 1) to the modified cyclodextrin carrier prepared in step 2), add ethanol and thymol in a mass ratio of 4:1:1.5 to the product, the modified cyclodextrin carrier, ethanol, and thymol, and mix and react for 0.6 hours to obtain an antibacterial agent;
[0041] (2) Weighing 60 parts of ultra-high molecular weight polyethylene, 30 parts of low-density polyethylene, 10 parts of masterbatch, and 4 parts of antibacterial agent respectively; introducing the ultra-high molecular weight polyethylene material, masterbatch, and antibacterial agent from the main extruder into the die head, and introducing the low-density polyethylene material from the auxiliary extruder into the die head, the two materials merge at the die head, and are extruded into a composite pipe by the die head, wherein the ultra-high molecular weight polyethylene material forms the inner wall layer of the composite pipe, and the low-density polyethylene material forms the outer wall layer of the composite pipe;
[0042] (3) The outer wall layer of the composite pipe in step (2) is removed by turning to obtain the antibacterial super-high pipe.
[0043] Example 3
[0044] A method for preparing a non-polar ultra-high temperature material is prepared by the following steps:
[0045] (1) Preparation of an antibacterial agent: 1) Add silver nitrate solution and potassium sodium tartrate in a mass ratio of 30:1 to an alkaline solution, and react at a reaction temperature of 42°C for 1.2 hours; then add a reducing agent, formaldehyde, and react for 1.5 hours; 2) Mix cyclodextrin and maltodextrin in a mass ratio of 2:1, add 120°C water and stir for 1 hour to obtain a modified cyclodextrin carrier; 3) Add the product obtained in step 1) to the modified cyclodextrin carrier prepared in step 2), add ethanol and thymol in a mass ratio of 6:1:2 to the product, modified cyclodextrin carrier, ethanol, and thymol, and mix and react for 1.5 hours to obtain an antibacterial agent;
[0046] (2) Weighing 60-80 parts of ultra-high molecular weight polyethylene, 30-50 parts of low-density polyethylene, 10-20 parts of masterbatch, and 4-8 parts of antibacterial agent respectively; introducing the ultra-high molecular weight polyethylene material, masterbatch and antibacterial agent into the die head from the main extruder, and introducing the low-density polyethylene material into the die head from the auxiliary extruder, the two materials merge at the die head, and are extruded into a composite pipe by the die head, wherein the ultra-high molecular weight polyethylene material forms the inner wall layer of the composite pipe, and the low-density polyethylene material forms the outer wall layer of the composite pipe;
[0047] (3) The outer wall layer of the composite pipe in step (2) is removed by turning to obtain the antibacterial super-high pipe.
[0048] Comparative Example 1
[0049] Compared with Example 1, thymol was not added, and the remaining steps were the same.
[0050] Comparative Example 2
[0051] Compared with Example 1, nanosilver is used instead of the antibacterial agent, step (1) is omitted, and the remaining steps are the same.
[0052] Comparative Example 3
[0053] Compared with Example 1, step (1) lacks the preparation of modified cyclodextrin carrier, and no modified cyclodextrin carrier is added, and the remaining steps are the same.
[0054] The non-polar ultra-high temperature materials prepared in Examples 1-3 and Comparative Example 1 were subjected to oxygen permeability tests according to the standard of GB / T19789-2005 to detect the oxygen barrier effect; 7CFU / mLDE Staphylococcus aureus and Escherichia coli were smeared on the surface of the pipes of Examples 1-3 and Comparative Examples 1-3, and covered with a layer of sterile PE film. After standing for 1 hour, the pipes were rinsed with phosphate buffer, and the rinse solution was smeared in the culture medium and cultured for 24 hours. The number of colonies was counted and the antibacterial rate was calculated; the tensile strength of the ultra-high tubes of Examples 1-3 and Comparative Examples 1-3 was tested according to the standard of GB / T1040-2006, and the test results are as follows
[0055] As shown in Table 1.
[0056] Performance Testing Escherichia coli antibacterial rate % Staphylococcus aureus antibacterial rate % Tensile strength MPa <![CDATA[Oxygen Permeability cc / m 2 ·day]]> Example 1 99.56 99.36 27.6 0.02 Example 2 99.53 99.29 26.3 0.03 Example 3 99.47 99.32 25.8 0.04 Comparative Example 1 84.63 82.58 18.3 2.1 Comparative Example 2 79.43 78.27 19.2 1.7 Comparative Example 3 87.56 85.49 17.1 1.6
[0057] From the above data, it can be seen that the non-polar ultra-high pipes prepared in various embodiments of the present invention have antibacterial performance and antibacterial durability, with an antibacterial rate of more than 99% and antibacterial durability. It can also improve the mechanical strength and oxygen barrier properties of the pipe, with the mechanical properties being increased by more than 30% and the oxygen permeability being as low as 0.04cc / m 2 ·Day or less.
[0058] The above is a detailed introduction to a non-polar ultra-high temperature material and a preparation method thereof provided by the present invention. Specific examples are used herein to illustrate the principle and implementation mode of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. At the same time, for a person skilled in the art, according to the idea of the present invention, there will be changes in the specific implementation mode and application scope. In summary, the content of this specification should not be understood as a limitation on the present invention.
Claims
1. A non-polar ultra-high temperature material, characterized in that: The invention comprises the following components: 60-80 parts of ultra-high molecular weight polyethylene, 30-50 parts of low-density polyethylene, 10-20 parts of masterbatch and 4-8 parts of antibacterial agent; wherein the antibacterial agent is prepared from modified cyclodextrin carrier, silver salt and thymol as main components.
2. The non-polar ultra-high temperature material according to claim 1, characterized in that: The molecular weight of the ultra-high molecular weight polyethylene is 1.5 million to 2.8 million.
3. The non-polar ultra-high temperature material according to claim 1, characterized in that: The antibacterial agent is prepared by the following method: (1) reacting silver nitrate solution and sodium potassium tartrate in an alkaline solution for 1.2-2.5 hours; then adding reducing agent formaldehyde to react for 1.5-2.5 hours; (2) mixing cyclodextrin and maltodextrin, adding 40° C.-120° C. water and stirring for 1-2 hours to obtain a modified cyclodextrin carrier; (3) adding the product obtained in step (1) to the modified cyclodextrin carrier prepared in step (2), adding ethanol and thymol to carry out a mixed reaction for 0.6-1.5 hours to obtain an antibacterial agent.
4. The non-polar ultra-high temperature material according to claim 3, characterized in that: The mass ratio of the silver nitrate solution to potassium sodium tartrate in step (1) is 20-30:
1.
5. The non-polar ultra-high temperature material according to claim 3, characterized in that: The reaction temperature of the alkaline solution in step (1) is 28-42°C.
6. The non-polar ultra-high temperature material according to claim 3, characterized in that: The mass ratio of the cyclodextrin to maltodextrin in step (2) is 1:2-2:
1.
7. The non-polar ultra-high temperature material according to claim 3, characterized in that: The mass ratio of the product, the modified cyclodextrin carrier, ethanol and thymol in step (3) is 4-6:1:1.5-2.
8. A method for manufacturing the non-polar ultra-high temperature material according to claim 1, characterized in that: The steps include: (1) Ultra-high molecular weight polyethylene material, masterbatch and antibacterial agent are introduced into the die head from the main extruder, and low-density polyethylene material is introduced into the die head from the auxiliary extruder. The two materials are combined at the die head and extruded into a composite pipe by the die head. The ultra-high molecular weight polyethylene material forms the inner wall layer of the composite pipe, and the low-density polyethylene material forms the outer wall layer of the composite pipe; (2) The outer wall layer of the composite pipe in step (1) is removed by turning to obtain the antibacterial super-high pipe.
9. The method for manufacturing non-polar ultra-high temperature materials according to claim 6, characterized in that: The screw barrel temperature of the extruder is 120°C-230°C.