A polyolefin-based long-acting antibacterial agent and its preparation method and application
A polyolefin-based antibacterial agent, modified with polyethylene-grafted maleic anhydride and silver nitrate, addresses the issue of metal ion precipitation and hydrophobicity in polyolefin pipes, ensuring long-lasting antibacterial performance by forming a hydrophobic modified masterbatch for co-extruded tubes.
Patent Information
- Application Number
- CN202310017625.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-01-06
- Publication Date
- 2024-12-10
- Estimated Expiration
- 2043-01-06
AI Technical Summary
Existing polyolefin antibacterial pipes fail to maintain effective antibacterial performance throughout their life cycle due to the precipitation of metal ions, which can also be harmful in excessive amounts, and the antibacterial layer's hydrophobicity is not optimized to prevent water penetration.
A polyolefin-based long-acting antibacterial agent is prepared by modifying zeolite with polyethylene-grafted maleic anhydride and silver nitrate, enhanced with a coupling agent, and combined with a fluorine-containing processing aid to form a hydrophobic modified masterbatch, which is then co-extruded with polyolefin to create a tube with a long-lasting antibacterial effect.
The modified antibacterial agent reduces metal ion precipitation, enhances dispersibility and binding, and improves hydrophobicity, resulting in a polyolefin antibacterial tube with high inner wall smoothness, low adhesion, and sustained antibacterial properties.
Smart Images
Figure BDA0004041117730000161
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of plastics, and particularly relates to a polyolefin-based long-acting antibacterial agent and a preparation method and application thereof. Background Art
[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.
[0003] Nowadays, polyolefin antibacterial pipes are mostly used as household pipes for household water pipes to reduce the growth of bacteria in the pipes so that the water quality can meet the needs of direct drinking. However, it is mostly achieved by the precipitation of antibacterial agents such as metal ions or organic compounds into the water, inhibiting the reproduction of bacteria in the water and killing bacteria. Once all the antibacterial agents contained in the pipe are precipitated, the antibacterial effect will no longer exist. The design service life of the water pipe is more than 30 years, and the antibacterial properties of most antibacterial pipes today can only last for a few years. Since the working principle of metal ion antibacterial agents is that metal ions precipitate and kill microorganisms, this requires that the metal ions reach a concentration that can kill microorganisms in the water within a certain period of time, and at the same time ensure that the metal content can meet the release amount for decades. In order to enhance the antibacterial life of antibacterial pipes in the market, the method of thickening the antibacterial layer is usually adopted. However, since the farther the antibacterial layer is from the inner wall, the slower the rate of metal ion precipitation into the pipe, the antibacterial effect cannot be guaranteed in the later stage, and at the same time, excessive metal ion content will also cause harm to the human body.
[0004] In summary, how to solve the problem that the antibacterial performance of water pipelines cannot be guaranteed in the later stage of their entire life cycle has become an urgent need. Summary of the invention
[0005] In order to solve the shortcomings of the prior art, the purpose of the present invention is to provide a polyolefin-based long-acting antibacterial agent and a preparation method and application thereof, by modifying the antibacterial agent so that it is completely coated with a resin to reduce the precipitation of metal ions, enhance its dispersibility and its binding effect with the matrix to meet the dispersion requirements under high addition conditions; modify the antibacterial layer to enhance the hydrophobicity of the antibacterial layer, weaken the penetration of water into the antibacterial layer, and reduce the precipitation rate of metal ions, so that the antibacterial layer has a lower precipitation amount and a longer precipitation time when it has a higher antibacterial agent content.
[0006] In order to achieve the above object, the technical solution of the present invention is:
[0007] The first aspect of the present invention provides a polyolefin-based long-acting antibacterial agent, which comprises, by weight, 10 parts of zeolite, 0.5-4.5 parts of polyethylene-grafted maleic anhydride, 10-50 parts of 5% silver nitrate solution, and 0.05-0.4 parts of a coupling agent.
[0008] The second aspect of the present invention provides a method for preparing the above-mentioned polyolefin-based long-acting antibacterial agent, comprising the following steps:
[0009] 1) treating the zeolite with ultrasonic waves in a mixed acid, and then subjecting the zeolite to a reflux reaction. After the reaction is completed, the zeolite is washed with deionized water, filtered until the filtrate is neutral, and dried to obtain an oxide zeolite.
[0010] The oxidized zeolite is subjected to ultrasonic treatment in anhydrous ethylenediamine and N,N-dicyclohexylcarboximide, and then refluxed for reaction. After the reaction is completed, the zeolite is washed with anhydrous ethanol, filtered until the filtrate is neutral, and dried to obtain aminated zeolite powder.
[0011] 2) dissolving the polyethylene grafted maleic anhydride in xylene, adding aminated zeolite powder, ultrasonic treatment, and then reflux reaction, washing with anhydrous ethanol and filtering after the reaction, and drying to obtain the polyethylene grafted maleic anhydride modified zeolite powder;
[0012] 3) dissolving polyethylene grafted maleic anhydride modified zeolite powder in a silver nitrate solution, adjusting the pH value, heating in a water bath, stirring in the dark, then centrifuging, washing with distilled water, drying, and then mixing with a coupling agent and anhydrous ethanol mixed solution at a high speed to obtain.
[0013] The third aspect of the present invention provides an antibacterial hydrophobic modified masterbatch, which comprises, by weight: 50 parts of a polyolefin matrix long-acting antibacterial agent, 3 parts of silicone, 3 parts of a fluorine-containing processing aid, 4 parts of an oxidized polyethylene wax, and 40 parts of a linear polyethylene;
[0014] After the raw materials are weighed in proportion, they are kneaded in an internal mixer at 150° C. for 20 minutes, and granulated by single-screw extrusion.
[0015] The fourth aspect of the present invention provides a polyolefin antibacterial tube, wherein the polyolefin antibacterial tube is divided into an outer layer and an antibacterial layer, wherein the outer layer is formulated as 96 parts of polyolefin and 4 parts of masterbatch, and the inner layer is formulated as 80 parts of polyolefin, 16 parts of antibacterial hydrophobic modified masterbatch, and 4 parts of masterbatch;
[0016] The polyolefin antibacterial tube is produced by a co-extrusion process.
[0017] The fifth aspect of the present invention provides the use of the above-mentioned polyolefin-based long-acting antibacterial agent or antibacterial hydrophobic modified masterbatch or polyolefin antibacterial tube.
[0018] The above-mentioned polyolefin-based long-acting antibacterial agent or antibacterial hydrophobic modified masterbatch or polyolefin antibacterial tube is used in the fields of home water supply, building floor heating, food packaging or medical and sanitary equipment.
[0019] The beneficial effects of the present invention are:
[0020] 1. The present invention uses polyethylene grafted maleic anhydride to modify the surface of the antibacterial agent carrier nano zeolite, then replaces the silver ions, and then treats the coupling agent to obtain a polyolefin matrix long-acting antibacterial agent. After polyethylene grafted maleic anhydride is modified and modified with a coupling agent, the zeolite and the polyolefin matrix can ensure an excellent composite effect, and the dispersion performance is greatly improved. The antibacterial agent is modified so that it is completely coated with the resin to reduce the precipitation of metal ions, enhance its dispersibility and the combination with the matrix to meet the dispersion requirements under high addition conditions.
[0021] 2. The present invention uses linear polyethylene as a carrier, adds a fluorine-containing polymer modifier and a modified antibacterial agent, and prepares a high-content antibacterial lubricating masterbatch.
[0022] 3. The present invention uses a co-extrusion process to mix the modified masterbatch with the polyolefin raw material as the inner wall of the pipe and co-extrude it with the conventional polyolefin outer layer to prepare a polyolefin antibacterial tube. The tube has the advantages of high inner wall smoothness, low adhesion, and long-lasting antibacterial properties. The antibacterial layer is modified to enhance the hydrophobicity of the antibacterial layer, weaken the penetration of water into the antibacterial layer, and reduce the precipitation rate of metal ions. Therefore, the antibacterial tube has a low precipitation amount and long-lasting precipitation under the condition of a high antibacterial agent content. DETAILED DESCRIPTION
[0023] It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.
[0024] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.
[0025] In view of the fact that the antibacterial performance of existing polyolefin antibacterial pipes as water pipelines cannot be guaranteed during their entire life cycle, and excessive metal ion content may also cause harm to the human body, the present invention proposes a method for preparing a polyolefin-based long-acting antibacterial agent.
[0026] A typical embodiment of the present invention provides a polyolefin-based long-acting antibacterial agent, which includes, by weight: 10 parts of zeolite, 0.5-4.5 parts of polyethylene-grafted maleic anhydride, 10-50 parts of 5% silver nitrate solution, and 0.05-0.4 parts of a coupling agent.
[0027] In some examples of this implementation mode, the composition includes, by weight: 10 parts of zeolite, 1-3 parts of polyethylene grafted maleic anhydride, 20-40 parts of 5% silver nitrate solution, and 0.1-0.3 parts of coupling agent.
[0028] A typical embodiment of the present invention provides a method for preparing a polyolefin-based long-acting antibacterial agent, comprising the following steps:
[0029] 1) treating the zeolite with ultrasonic waves in a mixed acid, and then subjecting the zeolite to a reflux reaction. After the reaction is completed, the zeolite is washed with deionized water, filtered until the filtrate is neutral, and dried to obtain an oxide zeolite.
[0030] The oxidized zeolite is subjected to ultrasonic treatment in anhydrous ethylenediamine and N,N-dicyclohexylcarboximide, and then refluxed for reaction. After the reaction is completed, the zeolite is washed with anhydrous ethanol, filtered until the filtrate is neutral, and dried to obtain aminated zeolite powder.
[0031] 2) dissolving the polyethylene grafted maleic anhydride in xylene, adding aminated zeolite powder, ultrasonic treatment, and then reflux reaction, washing with anhydrous ethanol and filtering after the reaction, and drying to obtain the polyethylene grafted maleic anhydride modified zeolite powder;
[0032] 3) dissolving polyethylene grafted maleic anhydride modified zeolite powder in a silver nitrate solution, adjusting the pH value, heating in a water bath, stirring in the dark, then centrifuging, washing with distilled water, drying, and then mixing with a coupling agent and anhydrous ethanol mixed solution at a high speed to obtain.
[0033] In step 1) of the present invention, the zeolite is oxidized and amidated, the mixed acid can make the zeolite produce more oxidized groups, the amine compound reacts with the oxidized groups to amidate the oxidized zeolite, the amide groups react with the anhydride groups in the polyethylene grafted maleic anhydride, the grafting rate is higher, and the process is indispensable; in step 2), the polymer grafting and coating surface (polyethylene grafted maleic anhydride is grafted onto the zeolite surface) enhances the embedding property, reduces the wetting effect of water on the zeolite, and works together with the coupling agent to improve dispersion, avoid agglomeration, improve the binding force with the matrix, and avoid freedom; in step 3), the polyethylene grafted maleic anhydride modified zeolite powder is used as a carrier, and silver nitrate and zeolite undergo a replacement reaction to replace silver ions with metal ions on the surface of the zeolite, so as to achieve the purpose of zeolite silver loading, and the silver loading amount obtained at pH 6-8 is higher, which is 5%-10%.
[0034] In some examples of this embodiment, the mixed acid is concentrated H2SO4 and concentrated HNO3, with a volume ratio of 3:1.
[0035] In some examples of this embodiment, the mass ratio of zeolite to mixed acid is 2:3.
[0036] In some examples of this embodiment, in step 1), the zeolite is subjected to ultrasonic treatment for 10 min; the temperature of the reflux reaction is 70° C., and the reflux reaction time is 24 h; the drying time is 12 h, and the drying temperature is 100-120° C.
[0037] In some examples of this embodiment, in step 1), the oxidized zeolite is subjected to ultrasonic treatment for 10 min; the temperature of the reflux reaction is 120° C., and the reflux reaction time is 48 h; the drying time is 12 h, and the drying temperature is 100-120° C.
[0038] In some examples of this embodiment, in step 1), the mass ratio of zeolite oxide to anhydrous ethylenediamine and N,N-dicyclohexylcarboximide is 1:1:1.
[0039] In some examples of this embodiment, in step 2), the mass ratio of polyethylene grafted maleic anhydride to xylene is 0.5-4.5:15.
[0040] In some examples of this embodiment, in step 2), the ultrasonic treatment is performed for 20 min; the temperature of the reflux reaction is 70° C., and the reflux reaction time is 24 h; and the drying temperature is 70-80° C.
[0041] In some examples of this embodiment, in step 3), the pH value is 5-9, preferably 6-8; the water bath heating temperature is 70-80°C; the drying temperature is 105°C, and the drying time is 8h; the stirring temperature is 150°C, and the stirring time is 30min.
[0042] In some examples of this implementation mode, in step 3), the coupling agent is one or both of aminosilane and vinylsilane; and the volume ratio of the coupling agent to the mixed solution of anhydrous ethanol is 1:10.
[0043] The third embodiment of the present invention provides an antibacterial hydrophobic modified masterbatch, which includes, by weight: 50 parts of a polyolefin-based long-acting antibacterial agent, 3 parts of silicone, 3 parts of a fluorine-containing processing aid, 4 parts of an oxidized polyethylene wax, and 40 parts of a linear polyethylene.
[0044] In some examples of this embodiment, the preparation method of the antibacterial hydrophobic modified masterbatch includes: weighing the raw materials in proportion, mixing them in an internal mixer at 150° C. for 20 minutes, and granulating them by single-screw extrusion.
[0045] In some examples of this implementation mode, the fluorine-containing processing aid is the American 3M fluorine-containing processing aid FX-5914; and the single-screw extrusion temperature is 160-180°C.
[0046] The fourth embodiment of the present invention provides a polyolefin antibacterial tube. The polyolefin antibacterial tube is divided into an outer layer and an antibacterial layer. The outer layer formula is 96 parts of polyolefin and 4 parts of masterbatch, and the inner layer formula is 80 parts of polyolefin, 16 parts of antibacterial hydrophobic modified masterbatch, and 4 parts of masterbatch.
[0047] In some examples of this embodiment, the polyolefin antibacterial tube is made by a co-extrusion process.
[0048] The fifth aspect of the present invention provides the use of the above-mentioned polyolefin-based long-acting antibacterial agent or antibacterial hydrophobic modified masterbatch or polyolefin antibacterial tube.
[0049] The above-mentioned polyolefin-based long-acting antibacterial agent or antibacterial hydrophobic modified masterbatch or polyolefin antibacterial tube is used in the fields of home water supply, building floor heating, food packaging or medical and sanitary equipment.
[0050] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.
[0051] Embodiment 1:
[0052] A polyolefin-based long-acting antibacterial agent comprises the following components by weight: 10 parts of zeolite, 1 part of polyethylene-grafted maleic anhydride, 20 parts of 5% silver nitrate solution, and 0.1 part of a coupling agent.
[0053] The preparation method of the above-mentioned olefin-based long-acting antibacterial agent comprises the following steps:
[0054] 1) treating the zeolite in a mixed acid (concentrated H2SO4 and concentrated HNO3, volume ratio 3:1, 15 parts of the mixed acid) by ultrasonic wave for 10 minutes, and then reacting at 70°C for 24 hours. After the reaction, washing with deionized water and filtering several times until the filtrate is neutral, drying it in an oven for 12 hours at a drying temperature of 100-120°C to obtain zeolite oxide; treating the zeolite oxide in anhydrous ethylenediamine and N,N-dicyclohexylcarboximide (10 parts of anhydrous ethylenediamine and 10 parts of N,N-dicyclohexylcarboximide) by ultrasonic wave for 10 minutes, and then reacting in a reflux device at 120°C for 48 hours. After the reaction, washing with anhydrous ethanol and filtering are repeated several times until the filtrate is neutral, and drying it in a vacuum oven for 12 hours at a drying temperature of 100-120°C to obtain aminated zeolite powder;
[0055] 2) dissolving polyethylene grafted maleic anhydride in xylene (15 parts of xylene), adding aminated zeolite powder, ultrasonically treating for 20 minutes, and then reflux reacting at 70°C for 24 hours. After the reaction is completed, washing with anhydrous ethanol and filtering, the sample is dried in a vacuum oven at a drying temperature of 70-80°C to obtain polyethylene grafted maleic anhydride modified zeolite powder;
[0056] 3) The polyethylene grafted maleic anhydride modified zeolite powder was dissolved in a silver nitrate solution, the pH value was adjusted to 6-8, heated in a water bath at 70-80°C, stirred for a certain period of time in the dark, then centrifuged, washed several times with distilled water, then dried at 105°C for 8h, and then mixed with a coupling agent and anhydrous ethanol mixture (volume ratio 1:10) at 150°C with high-speed stirring for 30min to obtain a polyolefin-based long-acting antibacterial agent.
[0057] An antibacterial hydrophobic modified masterbatch
[0058] An antibacterial hydrophobic modified masterbatch comprises, by weight, 50 parts of a polyolefin-based long-acting antibacterial agent, 3 parts of silicone, 3 parts of a fluorine-containing processing aid (US 3M fluorine-containing processing aid FX-5914), 4 parts of oxidized polyethylene wax, and 40 parts of linear polyethylene.
[0059] The preparation method of the above antibacterial hydrophobic modified masterbatch comprises:
[0060] After the raw materials are weighed in proportion, they are kneaded in an internal mixer at 150° C. for 20 minutes, and then granulated by single-screw extrusion at a temperature of 160-180° C. to obtain the antibacterial hydrophobic modified masterbatch.
[0061] A polyolefin antibacterial tube
[0062] The polyolefin antibacterial pipe material is divided into an outer layer and an antibacterial layer. The outer layer formula is 96 parts of polyolefin and 4 parts of masterbatch, and the inner layer formula is 80 parts of polyolefin, 16 parts of the antibacterial hydrophobic modified masterbatch according to claim 6, and 4 parts of masterbatch.
[0063] The polyolefin antibacterial tube is produced by a co-extrusion process.
[0064] Example 2
[0065] A polyolefin-based long-acting antibacterial agent comprises the following components by weight: 10 parts of zeolite, 1 part of polyethylene-grafted maleic anhydride, 30 parts of 5% silver nitrate solution, and 0.1 part of a coupling agent.
[0066] The preparation method of the above-mentioned olefin-based long-acting antibacterial agent comprises the following steps:
[0067] 1) treating the zeolite in a mixed acid (concentrated H2SO4 and concentrated HNO3, volume ratio 3:1, 15 parts of the mixed acid) by ultrasonic wave for 10 minutes, and then reacting at 70°C for 24 hours. After the reaction, washing with deionized water and filtering several times until the filtrate is neutral, drying it in an oven for 12 hours at a drying temperature of 100-120°C to obtain zeolite oxide; treating the zeolite oxide in anhydrous ethylenediamine and N,N-dicyclohexylcarboximide (10 parts of anhydrous ethylenediamine and 10 parts of N,N-dicyclohexylcarboximide) by ultrasonic wave for 10 minutes, and then reacting in a reflux device at 120°C for 48 hours. After the reaction, washing with anhydrous ethanol and filtering are repeated several times until the filtrate is neutral, and drying it in a vacuum oven for 12 hours at a drying temperature of 100-120°C to obtain aminated zeolite powder;
[0068] 2) dissolving polyethylene grafted maleic anhydride in xylene (15 parts of xylene), adding aminated zeolite powder, ultrasonically treating for 20 minutes, and then reflux reacting at 70°C for 24 hours. After the reaction is completed, washing with anhydrous ethanol and filtering, the sample is dried in a vacuum oven at a drying temperature of 70-80°C to obtain polyethylene grafted maleic anhydride modified zeolite powder;
[0069] 3) The polyethylene grafted maleic anhydride modified zeolite powder was dissolved in a silver nitrate solution, the pH value was adjusted to 6-8, heated in a water bath at 70-80°C, stirred for a certain period of time in the dark, then centrifuged, washed several times with distilled water, then dried at 105°C for 8h, and then mixed with a coupling agent and anhydrous ethanol mixture (volume ratio 1:10) at 150°C with high-speed stirring for 30min to obtain a polyolefin-based long-acting antibacterial agent.
[0070] An antibacterial hydrophobic modified masterbatch
[0071] An antibacterial hydrophobic modified masterbatch comprises, by weight, 50 parts of a polyolefin-based long-acting antibacterial agent, 3 parts of silicone, 3 parts of a fluorine-containing processing aid (US 3M fluorine-containing processing aid FX-5914), 4 parts of oxidized polyethylene wax, and 40 parts of linear polyethylene.
[0072] The preparation method of the above antibacterial hydrophobic modified masterbatch comprises:
[0073] After the raw materials are weighed in proportion, they are kneaded in an internal mixer at 150° C. for 20 minutes, and then granulated by single-screw extrusion at a temperature of 160-180° C. to obtain the antibacterial hydrophobic modified masterbatch.
[0074] A polyolefin antibacterial tube
[0075] The polyolefin antibacterial pipe material is divided into an outer layer and an antibacterial layer. The outer layer formula is 96 parts of polyolefin and 4 parts of masterbatch, and the inner layer formula is 80 parts of polyolefin, 16 parts of the antibacterial hydrophobic modified masterbatch according to claim 6, and 4 parts of masterbatch.
[0076] The polyolefin antibacterial tube is produced by a co-extrusion process.
[0077] Example 3
[0078] A polyolefin-based long-acting antibacterial agent comprises the following components by weight: 10 parts of zeolite, 2 parts of polyethylene-grafted maleic anhydride, 20 parts of 5% silver nitrate solution, and 0.1 part of a coupling agent.
[0079] The preparation method of the above-mentioned olefin-based long-acting antibacterial agent comprises the following steps:
[0080] 1) treating the zeolite in a mixed acid (concentrated H2SO4 and concentrated HNO3, volume ratio 3:1, 15 parts of the mixed acid) by ultrasonic wave for 10 minutes, and then reacting at 70°C for 24 hours. After the reaction, washing with deionized water and filtering several times until the filtrate is neutral, drying it in an oven for 12 hours at a drying temperature of 100-120°C to obtain zeolite oxide; treating the zeolite oxide in anhydrous ethylenediamine and N,N-dicyclohexylcarboximide (10 parts of anhydrous ethylenediamine and 10 parts of N,N-dicyclohexylcarboximide) by ultrasonic wave for 10 minutes, and then reacting in a reflux device at 120°C for 48 hours. After the reaction, washing with anhydrous ethanol and filtering are repeated several times until the filtrate is neutral, and drying it in a vacuum oven for 12 hours at a drying temperature of 100-120°C to obtain aminated zeolite powder;
[0081] 2) dissolving polyethylene grafted maleic anhydride in xylene (15 parts of xylene), adding aminated zeolite powder, ultrasonically treating for 20 minutes, and then reflux reacting at 70°C for 24 hours. After the reaction is completed, washing with anhydrous ethanol and filtering, the sample is dried in a vacuum oven at a drying temperature of 70-80°C to obtain polyethylene grafted maleic anhydride modified zeolite powder;
[0082] 3) The polyethylene grafted maleic anhydride modified zeolite powder was dissolved in a silver nitrate solution, the pH value was adjusted to 6-8, heated in a water bath at 70-80°C, stirred for a certain period of time in the dark, then centrifuged, washed several times with distilled water, then dried at 105°C for 8h, and then mixed with a coupling agent and anhydrous ethanol mixture (volume ratio 1:10) at 150°C with high-speed stirring for 30min to obtain a polyolefin-based long-acting antibacterial agent.
[0083] An antibacterial hydrophobic modified masterbatch
[0084] An antibacterial hydrophobic modified masterbatch comprises, by weight, 50 parts of a polyolefin-based long-acting antibacterial agent, 3 parts of silicone, 3 parts of a fluorine-containing processing aid (US 3M fluorine-containing processing aid FX-5914), 4 parts of oxidized polyethylene wax, and 40 parts of linear polyethylene.
[0085] The preparation method of the above antibacterial hydrophobic modified masterbatch comprises:
[0086] After the raw materials are weighed in proportion, they are kneaded in an internal mixer at 150° C. for 20 minutes, and then granulated by single-screw extrusion at a temperature of 160-180° C. to obtain the antibacterial hydrophobic modified masterbatch.
[0087] A polyolefin antibacterial tube
[0088] The polyolefin antibacterial pipe material is divided into an outer layer and an antibacterial layer. The outer layer formula is 96 parts of polyolefin and 4 parts of masterbatch, and the inner layer formula is 80 parts of polyolefin, 16 parts of the antibacterial hydrophobic modified masterbatch according to claim 6, and 4 parts of masterbatch.
[0089] The polyolefin antibacterial tube is produced by a co-extrusion process.
[0090] Example 4
[0091] A polyolefin-based long-acting antibacterial agent comprises the following components by weight: 10 parts of zeolite, 2.5 parts of polyethylene-grafted maleic anhydride, 20 parts of 5% silver nitrate solution, and 0.1 part of a coupling agent.
[0092] The preparation method of the above-mentioned olefin-based long-acting antibacterial agent comprises the following steps:
[0093] 1) treating the zeolite in a mixed acid (concentrated H2SO4 and concentrated HNO3, volume ratio 3:1, 15 parts of the mixed acid) by ultrasonic wave for 10 minutes, and then reacting at 70°C for 24 hours. After the reaction, washing with deionized water and filtering several times until the filtrate is neutral, drying it in an oven for 12 hours at a drying temperature of 100-120°C to obtain zeolite oxide; treating the zeolite oxide in anhydrous ethylenediamine and N,N-dicyclohexylcarboximide (10 parts of anhydrous ethylenediamine and 10 parts of N,N-dicyclohexylcarboximide) by ultrasonic wave for 10 minutes, and then reacting in a reflux device at 120°C for 48 hours. After the reaction, washing with anhydrous ethanol and filtering are repeated several times until the filtrate is neutral, and drying it in a vacuum oven for 12 hours at a drying temperature of 100-120°C to obtain aminated zeolite powder;
[0094] 2) dissolving polyethylene grafted maleic anhydride in xylene (15 parts of xylene), adding aminated zeolite powder, ultrasonically treating for 20 minutes, and then reflux reacting at 70°C for 24 hours. After the reaction is completed, washing with anhydrous ethanol and filtering, the sample is dried in a vacuum oven at a drying temperature of 70-80°C to obtain polyethylene grafted maleic anhydride modified zeolite powder;
[0095] 3) The polyethylene grafted maleic anhydride modified zeolite powder was dissolved in a silver nitrate solution, the pH value was adjusted to 6-8, heated in a water bath at 70-80°C, stirred for a certain period of time in the dark, then centrifuged, washed several times with distilled water, then dried at 105°C for 8h, and then mixed with a coupling agent and anhydrous ethanol mixture (volume ratio 1:10) at 150°C with high-speed stirring for 30min to obtain a polyolefin-based long-acting antibacterial agent.
[0096] An antibacterial hydrophobic modified masterbatch
[0097] An antibacterial hydrophobic modified masterbatch comprises, by weight, 50 parts of a polyolefin-based long-acting antibacterial agent, 3 parts of silicone, 3 parts of a fluorine-containing processing aid (US 3M fluorine-containing processing aid FX-5914), 4 parts of oxidized polyethylene wax, and 40 parts of linear polyethylene.
[0098] The preparation method of the above antibacterial hydrophobic modified masterbatch comprises:
[0099] After the raw materials are weighed in proportion, they are kneaded in an internal mixer at 150° C. for 20 minutes, and then granulated by single-screw extrusion at a temperature of 160-180° C. to obtain the antibacterial hydrophobic modified masterbatch.
[0100] A polyolefin antibacterial tube
[0101] The polyolefin antibacterial pipe material is divided into an outer layer and an antibacterial layer. The outer layer formula is 96 parts of polyolefin and 4 parts of masterbatch, and the inner layer formula is 80 parts of polyolefin, 16 parts of the antibacterial hydrophobic modified masterbatch according to claim 6, and 4 parts of masterbatch.
[0102] The polyolefin antibacterial tube is produced by a co-extrusion process.
[0103] Example 5
[0104] A polyolefin-based long-acting antibacterial agent comprises the following components by weight: 10 parts of zeolite, 3 parts of polyethylene-grafted maleic anhydride, 20 parts of 5% silver nitrate solution, and 0.1 part of a coupling agent.
[0105] The preparation method of the above-mentioned olefin-based long-acting antibacterial agent comprises the following steps:
[0106] 1) treating the zeolite in a mixed acid (concentrated H2SO4 and concentrated HNO3, volume ratio 3:1, 15 parts of the mixed acid) by ultrasonic wave for 10 minutes, and then reacting at 70°C for 24 hours. After the reaction, washing with deionized water and filtering several times until the filtrate is neutral, drying it in an oven for 12 hours at a drying temperature of 100-120°C to obtain zeolite oxide; treating the zeolite oxide in anhydrous ethylenediamine and N,N-dicyclohexylcarboximide (10 parts of anhydrous ethylenediamine and 10 parts of N,N-dicyclohexylcarboximide) by ultrasonic wave for 10 minutes, and then reacting in a reflux device at 120°C for 48 hours. After the reaction, washing with anhydrous ethanol and filtering are repeated several times until the filtrate is neutral, and drying it in a vacuum oven for 12 hours at a drying temperature of 100-120°C to obtain aminated zeolite powder;
[0107] 2) dissolving polyethylene grafted maleic anhydride in xylene (15 parts of xylene), adding aminated zeolite powder, ultrasonically treating for 20 minutes, and then reflux reacting at 70°C for 24 hours. After the reaction is completed, washing with anhydrous ethanol and filtering, the sample is dried in a vacuum oven at a drying temperature of 70-80°C to obtain polyethylene grafted maleic anhydride modified zeolite powder;
[0108] 3) The polyethylene grafted maleic anhydride modified zeolite powder was dissolved in a silver nitrate solution, the pH value was adjusted to 6-8, heated in a water bath at 70-80°C, stirred for a certain period of time in the dark, then centrifuged, washed several times with distilled water, then dried at 105°C for 8h, and then mixed with a coupling agent and anhydrous ethanol mixture (volume ratio 1:10) at 150°C with high-speed stirring for 30min to obtain a polyolefin-based long-acting antibacterial agent.
[0109] An antibacterial hydrophobic modified masterbatch
[0110] An antibacterial hydrophobic modified masterbatch comprises, by weight, 50 parts of a polyolefin-based long-acting antibacterial agent, 3 parts of silicone, 3 parts of a fluorine-containing processing aid (US 3M fluorine-containing processing aid FX-5914), 4 parts of oxidized polyethylene wax, and 40 parts of linear polyethylene.
[0111] The preparation method of the above antibacterial hydrophobic modified masterbatch comprises:
[0112] After the raw materials are weighed in proportion, they are kneaded in an internal mixer at 150° C. for 20 minutes, and then granulated by single-screw extrusion at a temperature of 160-180° C. to obtain the antibacterial hydrophobic modified masterbatch.
[0113] A polyolefin antibacterial tube
[0114] The polyolefin antibacterial pipe material is divided into an outer layer and an antibacterial layer. The outer layer formula is 96 parts of polyolefin and 4 parts of masterbatch, and the inner layer formula is 80 parts of polyolefin, 16 parts of the antibacterial hydrophobic modified masterbatch according to claim 6, and 4 parts of masterbatch.
[0115] The polyolefin antibacterial tube is produced by a co-extrusion process.
[0116] Example 6
[0117] A polyolefin-based long-acting antibacterial agent comprises the following components by weight: 10 parts of zeolite, 1 part of polyethylene-grafted maleic anhydride, 20 parts of 5% silver nitrate solution, and 0.3 parts of a coupling agent.
[0118] The preparation method of the above-mentioned olefin-based long-acting antibacterial agent comprises the following steps:
[0119] 1) treating the zeolite in a mixed acid (concentrated H2SO4 and concentrated HNO3, volume ratio 3:1, 15 parts of the mixed acid) by ultrasonic wave for 10 minutes, and then reacting at 70°C for 24 hours. After the reaction, washing with deionized water and filtering several times until the filtrate is neutral, drying it in an oven for 12 hours at a drying temperature of 100-120°C to obtain zeolite oxide; treating the zeolite oxide in anhydrous ethylenediamine and N,N-dicyclohexylcarboximide (10 parts of anhydrous ethylenediamine and 10 parts of N,N-dicyclohexylcarboximide) by ultrasonic wave for 10 minutes, and then reacting in a reflux device at 120°C for 48 hours. After the reaction, washing with anhydrous ethanol and filtering are repeated several times until the filtrate is neutral, and drying it in a vacuum oven for 12 hours at a drying temperature of 100-120°C to obtain aminated zeolite powder;
[0120] 2) dissolving polyethylene grafted maleic anhydride in xylene (15 parts of xylene), adding aminated zeolite powder, ultrasonically treating for 20 minutes, and then reflux reacting at 70°C for 24 hours. After the reaction is completed, washing with anhydrous ethanol and filtering, the sample is dried in a vacuum oven at a drying temperature of 70-80°C to obtain polyethylene grafted maleic anhydride modified zeolite powder;
[0121] 3) The polyethylene grafted maleic anhydride modified zeolite powder was dissolved in a silver nitrate solution, the pH value was adjusted to 6-8, heated in a water bath at 70-80°C, stirred for a certain period of time in the dark, then centrifuged, washed several times with distilled water, then dried at 105°C for 8h, and then mixed with a coupling agent and anhydrous ethanol mixture (volume ratio 1:10) at 150°C with high-speed stirring for 30min to obtain a polyolefin-based long-acting antibacterial agent.
[0122] An antibacterial hydrophobic modified masterbatch
[0123] An antibacterial hydrophobic modified masterbatch comprises, by weight, 50 parts of a polyolefin-based long-acting antibacterial agent, 3 parts of silicone, 3 parts of a fluorine-containing processing aid (US 3M fluorine-containing processing aid FX-5914), 4 parts of oxidized polyethylene wax, and 40 parts of linear polyethylene.
[0124] The preparation method of the above antibacterial hydrophobic modified masterbatch comprises:
[0125] After the raw materials are weighed in proportion, they are kneaded in an internal mixer at 150° C. for 20 minutes, and then granulated by single-screw extrusion at a temperature of 160-180° C. to obtain the antibacterial hydrophobic modified masterbatch.
[0126] A polyolefin antibacterial tube
[0127] The polyolefin antibacterial pipe material is divided into an outer layer and an antibacterial layer. The outer layer formula is 96 parts of polyolefin and 4 parts of masterbatch, and the inner layer formula is 80 parts of polyolefin, 16 parts of the antibacterial hydrophobic modified masterbatch according to claim 6, and 4 parts of masterbatch.
[0128] The polyolefin antibacterial tube is produced by a co-extrusion process.
[0129] Comparative Example 1
[0130] The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 does not have step (2), that is, the surface of the antimicrobial agent carrier nano zeolite is not modified by polyethylene grafting maleic anhydride. The rest of the process is the same as Example 1.
[0131] Comparative Example 2
[0132] The difference between Comparative Example 2 and Example 1 is that there is no step (3) in Comparative Example 2, that is, the polyethylene grafted maleic anhydride modified zeolite is not treated with a coupling agent. The rest of the process is the same as Example 1.
[0133] Comparative Example 3
[0134] The difference between Comparative Example 4 and Example 1 is that Comparative Example 4 lacks a fluorine-containing processing aid, and the rest of the process is the same as Example 1.
[0135] Antibacterial test
[0136] 1. Antibacterial tube product durability test
[0137] A section of about 10 cm long was cut from the prepared antibacterial tubing, first soaked in 80°C water for 100 hours, taken out and rinsed, then soaked in 20°C water for 24 hours, and the mass m1 of silver ions in the soaking solution was tested; then the section was soaked in 80°C water for 1000 hours, taken out and rinsed, then soaked in 20°C water for 24 hours, and the mass m2 of silver ions in the soaking solution was tested.
[0138] Note: Silver ion content test method
[0139] Direct titration method: In an acidic medium, use ammonium thiocyanate (NH4SCN) standard solution to directly titrate the silver-containing solution. After silver thiocyanate (AgSCN) is completely precipitated, a slightly excess of SCN - with Fe 3+The reaction generates red complex ions, indicating that the titration endpoint has been reached. The acidic medium uses dilute nitric acid to adjust the hydrogen ion concentration to 0.1-1 mol / L, and the concentration of the ammonium thiocyanate (NH4SCN) standard solution is 0.015 mol / L.
[0140] 2. Antibacterial performance test of antibacterial composite layer of antibacterial tube
[0141] According to the test method in standard QB / T 2591-2003, the sample is immersed in 80℃ water for 1000 hours before testing, and the test antibacterial level is not lower than the level II requirement.
[0142] The durability test and antibacterial performance of the antibacterial tubes prepared in various embodiments and comparative examples are shown in Table 1.
[0143] Table 1 Durability test and antibacterial performance of antibacterial tubes prepared in various embodiments and comparative examples
[0144]
[0145] As can be seen from the above table, by using polyethylene grafted maleic anhydride to modify the surface of the antibacterial agent carrier nano zeolite, then replacing silver ions, and then treating with a coupling agent, a polyolefin matrix long-acting antibacterial agent is obtained. The antibacterial grade of the prepared polyolefin antibacterial tube meets the requirements of Class II, and the difference in the tested silver ions does not exceed 20% (Examples 1-6). By respectively testing and analyzing the durability of the zeolite, it is found that: first, polyethylene grafted maleic anhydride is grafted onto the zeolite surface to enhance the embedding of silver ions (Example and Comparative Example 1), polyethylene grafted maleic anhydride affects the precipitation rate of silver ions, and the more polyethylene grafted maleic anhydride, the slower the precipitation rate of silver ions (Examples 3-5); second, silver nitrate affects the silver loading of zeolite, and the higher the silver loading, the faster the precipitation rate (Examples 1 and 2), and the coupling agent prevents the precipitation of silver ions to a certain extent (Examples 1 and 6). It can be shown that the present invention modifies the antibacterial agent so that it is completely coated with the resin, which reduces the precipitation of metal ions, enhances its dispersibility and the binding effect with the matrix to meet the dispersion requirements under high addition conditions, and under high antibacterial agent content, the precipitation amount is low and the precipitation is long-lasting, effectively improving the antibacterial life.
[0146] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. An antibacterial hydrophobic modified masterbatch, characterized in that: Calculated by mass, it includes: 50 parts of polyolefin-based long-acting antibacterial agent, 3 parts of silicone, 3 parts of fluorine-containing processing aid, 4 parts of oxidized polyethylene wax, and 40 parts of linear polyethylene; The fluorine-containing processing aid is the American 3M fluorine-containing processing aid FX-5914; After weighing the raw materials according to the proportion, they were mixed in an internal mixer at 150°C for 20 minutes, and granulated by single-screw extrusion; The polyolefin-based long-acting antibacterial agent comprises, by weight: 10 parts of zeolite, 0.5-4.5 parts of polyethylene-grafted maleic anhydride, 10-50 parts of 5% silver nitrate solution, and 0.05-0.4 parts of a coupling agent; The preparation method of the polyolefin-based long-acting antibacterial agent comprises the following steps: 1) treating the zeolite with ultrasonic waves in a mixed acid, and then reflux reacting the zeolite. After the reaction is completed, washing the zeolite with deionized water, filtering the filtrate until the filtrate is neutral, and drying the zeolite oxide. The oxidized zeolite is subjected to ultrasonic treatment in anhydrous ethylenediamine and N,N-dicyclohexylcarboximide, and then refluxed for reaction. After the reaction is completed, the zeolite is washed with anhydrous ethanol, filtered until the filtrate is neutral, and dried to obtain aminated zeolite powder. 2) dissolving polyethylene grafted maleic anhydride in xylene, adding aminated zeolite powder, ultrasonic treatment, and then reflux reaction, washing and filtering with anhydrous ethanol after the reaction, and drying to obtain polyethylene grafted maleic anhydride modified zeolite powder; 3) Dissolve the polyethylene grafted maleic anhydride modified zeolite powder in a silver nitrate solution, adjust the pH value, heat in a water bath, stir in the dark, then centrifuge, wash with distilled water, dry, and then stir with a coupling agent and anhydrous ethanol mixture at a high speed to obtain the product.
2. The antibacterial hydrophobic modified masterbatch according to claim 1, characterized in that: The single screw extrusion temperature is 160-180°C.
3. The antibacterial hydrophobic modified masterbatch according to claim 1, characterized in that: The polyolefin-based long-acting antibacterial agent comprises: 10 parts of zeolite, 1-3 parts of polyethylene-grafted maleic anhydride, 20-40 parts of 5% silver nitrate solution, and 0.1-0.3 parts of a coupling agent.
4. The antibacterial hydrophobic modified masterbatch according to claim 1, characterized in that: In step 1), the mixed acid is concentrated H2SO4 and concentrated HNO3, the volume ratio is 3:1; the mass ratio of zeolite to mixed acid is 2:3; The zeolite was ultrasonically treated for 10 minutes; the reflux temperature was 70°C, the reflux time was 24 hours; the drying time was 12 hours, and the drying temperature was 100-120°C; The oxidized zeolite was ultrasonically treated for 10 minutes; the reflux reaction temperature was 120°C, and the reflux reaction time was 48 hours; the drying time in the oven was 12 hours, and the drying temperature was 100-120°C; the mass ratio of the oxidized zeolite to anhydrous ethylenediamine and N,N-dicyclohexylcarboximide was 1:1:
1.
5. The antibacterial hydrophobic modified masterbatch according to claim 1, characterized in that: In step 2), the ultrasonic treatment is performed for 20 minutes; the reflux reaction temperature is 70°C, the reflux reaction time is 24 hours; and the drying temperature is 70-80°C.
6. The antibacterial hydrophobic modified masterbatch according to claim 1, characterized in that: In step 3), the pH value is 5-9; the water bath heating temperature is 70-80°C; the drying temperature is 105°C, and the drying time is 8h; the stirring temperature is 150°C, and the stirring time is 30min; the volume ratio of the coupling agent and the anhydrous ethanol mixed solution is 1:
10.
7. The antibacterial hydrophobic modified masterbatch according to claim 6, characterized in that: In step 3), the pH value is 6-8.
8. A polyolefin antibacterial tube, characterized in that: The polyolefin antibacterial tube is divided into an outer layer and an antibacterial layer. The outer layer formula is 96 parts of polyolefin and 4 parts of masterbatch. The antibacterial layer formula is 80 parts of polyolefin, 16 parts of the antibacterial hydrophobic modified masterbatch according to any one of claims 1 to 7, and 4 parts of masterbatch. The polyolefin antibacterial tube is made by a co-extrusion process.
9. Use of the antibacterial hydrophobic modified masterbatch according to any one of claims 1 to 7 or the polyolefin antibacterial tube according to claim 8 in the fields of home water supply, building floor heating, food packaging or medical and sanitary equipment.