CN116218041A - Long-acting antibacterial agent for polyolefin matrix, and preparation method and application thereof - Google Patents
Long-acting antibacterial agent for polyolefin matrix, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of plastics, and discloses a polyolefin matrix long-acting antibacterial agent, a preparation method and application thereof. The polyolefin matrix long-acting antibacterial agent comprises the following raw materials: zeolite, polyethylene grafted maleic anhydride, silver nitrate and a coupling agent. Modifying the surface of the antibacterial agent carrier nano zeolite by using polyethylene grafted maleic anhydride, then carrying out silver ion replacement, and then carrying out coupling agent treatment to obtain the modified antibacterial agent. And then linear polyethylene is used as a carrier, and a fluoropolymer modifier and a modified antibacterial agent are added to prepare the high-content antibacterial lubricating master batch. The master batch and the polyolefin raw material are mixed as the inner wall of the pipeline and the conventional polyolefin outer layer are subjected to coextrusion to prepare the polyolefin antibacterial pipe through a coextrusion process, and the pipe has the advantages of high inner wall smoothness, low adhesion and lasting antibacterial property.
Description
Technical Field
The invention belongs to the technical field of plastics, and particularly relates to a polyolefin matrix long-acting antibacterial agent, a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The polyolefin antibacterial pipe is used as a household pipe for a household water pipeline nowadays so as to reduce bacterial breeding in the pipeline and enable water quality to meet the direct drinking requirement. However, it is mostly achieved by precipitation of an antimicrobial agent such as a metal ion or an organic compound into the water, inhibition of bacterial growth in the water, killing of the bacteria, and once the antimicrobial agent contained in the tube is totally precipitated, the antimicrobial effect is no longer achieved. The design service life of the water pipe is longer than 30 years, and the antibacterial property of most antibacterial pipes can be maintained for years. The metal ion antibacterial agent has the effect that the metal ions are separated out to kill microorganisms, so that the metal ions can reach the concentration capable of killing microorganisms in water within a certain period of time, the metal content can meet the release amount of decades, the antibacterial layer is thickened in order to strengthen the antibacterial period of the antibacterial tube in the market, but the rate of separating out the metal ions into the tube is slower as the antibacterial layer is far away from the inner wall, the later antibacterial effect cannot be guaranteed, and the too high metal ion content can cause human harm.
In summary, how to solve the problem that the antibacterial performance in the whole life cycle of the water pipe cannot be guaranteed in the later period has become an urgent need.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a polyolefin matrix long-acting antibacterial agent, a preparation method and application thereof, wherein the antibacterial agent is modified to be completely coated by resin, so that metal ion precipitation is reduced, the dispersibility is enhanced, and the combination effect with a matrix meets the dispersion requirement under the condition of high addition amount; the antibacterial layer is modified, the hydrophobicity of the antibacterial layer is enhanced, the permeation of water into the antibacterial layer is weakened, and the metal ion precipitation rate is reduced, so that the precipitation amount of the antibacterial layer is lower and the precipitation is lasting under the condition of higher antibacterial agent content.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the first aspect of the invention provides a polyolefin matrix long-acting antibacterial agent, which comprises the following components in parts by mass: 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 part of coupling agent.
The second aspect of the present invention provides a method for preparing the above-mentioned polyolefin matrix long-acting antibacterial agent, comprising the steps of:
1) Ultrasonic treatment of zeolite in mixed acid, reflux reaction, washing with deionized water after reaction, filtering until the filtrate is neutral, and drying to obtain oxidized zeolite;
ultrasonic treatment of oxidized zeolite in anhydrous ethylenediamine and N, N-dicyclohexyl carbodiimide, reflux reaction, washing with absolute ethanol after the reaction, filtering to neutrality, and drying to obtain aminated zeolite powder;
2) Dissolving polyethylene grafted maleic anhydride in dimethylbenzene, adding aminated zeolite powder, carrying out ultrasonic treatment, carrying out reflux reaction, washing and filtering by using absolute ethyl alcohol after the reaction is finished, and drying to obtain polyethylene grafted maleic anhydride modified zeolite powder;
3) Dissolving polyethylene grafted maleic anhydride modified zeolite powder in silver nitrate solution, regulating pH value, heating in water bath, stirring in dark, centrifugally separating, washing with distilled water, drying, and mixing with coupling agent and anhydrous alcohol mixture at high speed.
The third aspect of the invention provides an antibacterial hydrophobically modified master batch, which comprises the following components in parts by mass: 50 parts of polyolefin matrix 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;
weighing the raw materials according to a proportion, banburying the raw materials at 150 ℃ for 20 minutes in an internal mixer, and extruding and granulating the raw materials by a single screw rod.
The fourth aspect of the invention provides a polyolefin antibacterial tube, which is divided into an outer layer and an antibacterial layer, wherein the outer layer comprises 96 parts of polyolefin and 4 parts of coloring master batch, and the inner layer comprises 80 parts of polyolefin, 16 parts of antibacterial hydrophobically modified master batch and 4 parts of coloring master batch;
the polyolefin antibacterial tube is prepared by a coextrusion process.
The fifth aspect of the present invention provides the use of the above-described polyolefin matrix long-acting antimicrobial or antimicrobial hydrophobically modified masterbatch or polyolefin antimicrobial tubing.
The polyolefin matrix long-acting antibacterial agent or the antibacterial hydrophobically modified master batch or the polyolefin antibacterial pipe is applied to the fields of household water supply, building floor heating, food packaging or medical and health instruments.
The beneficial effects of the invention are as follows:
1. the invention uses polyethylene grafted maleic anhydride to modify the surface of the antibacterial agent carrier nano zeolite, then carries out silver ion replacement, and then carries out coupling agent treatment to obtain the polyolefin matrix long-acting antibacterial agent. After the polyethylene grafted maleic anhydride modified and matched with the coupling agent, the zeolite and the polyolefin base can ensure excellent composite effect, and the dispersion performance is improved. The antibacterial agent is modified to be completely coated by the resin, so that metal ions are reduced to be separated out, the dispersibility of the antibacterial agent is enhanced, and the antibacterial agent and a matrix are combined to meet the dispersing requirement under the condition of high addition.
2. The invention prepares the high-content antibacterial lubricating master batch by using linear polyethylene as a carrier and adding a fluorine-containing polymer modifier and a modified antibacterial agent.
3. According to the invention, the modified master batch and the polyolefin raw material are mixed as the inner wall of the pipeline and the conventional polyolefin outer layer are subjected to coextrusion to prepare the polyolefin antibacterial pipe by the coextrusion process, and the pipe has the advantages of high inner wall smoothness, low adhesion and lasting antibacterial property. The antibacterial layer is modified, the hydrophobicity of the antibacterial layer is enhanced, the permeation of water into the antibacterial layer is weakened, and the metal ion precipitation rate is reduced, so that the antibacterial tube has lower precipitation amount and lasting precipitation under the condition of higher antibacterial agent content.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In view of the fact that the conventional polyolefin antibacterial pipe cannot be guaranteed after being used as a water pipe in an antibacterial performance period within a whole life cycle, and meanwhile, the human body is damaged due to the fact that the content of metal ions is too high, the invention provides a preparation method of a polyolefin matrix long-acting antibacterial agent.
The invention provides a polyolefin matrix long-acting antibacterial agent, which comprises the following components in parts by mass: 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 part of coupling agent.
In some examples of this embodiment, the composition comprises, in parts 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 part of coupling agent.
In an exemplary embodiment of the present invention, a method for preparing a long-acting antibacterial agent for a polyolefin matrix is provided, which comprises the following steps:
1) Ultrasonic treatment of zeolite in mixed acid, reflux reaction, washing with deionized water after reaction, filtering until the filtrate is neutral, and drying to obtain oxidized zeolite;
ultrasonic treatment of oxidized zeolite in anhydrous ethylenediamine and N, N-dicyclohexyl carbodiimide, reflux reaction, washing with absolute ethanol after the reaction, filtering to neutrality, and drying to obtain aminated zeolite powder;
2) Dissolving polyethylene grafted maleic anhydride in dimethylbenzene, adding aminated zeolite powder, carrying out ultrasonic treatment, carrying out reflux reaction, washing and filtering by using absolute ethyl alcohol after the reaction is finished, and drying to obtain polyethylene grafted maleic anhydride modified zeolite powder;
3) Dissolving polyethylene grafted maleic anhydride modified zeolite powder in silver nitrate solution, regulating pH value, heating in water bath, stirring in dark, centrifugally separating, washing with distilled water, drying, and mixing with coupling agent and anhydrous alcohol mixture at high speed.
In the step 1) of the invention, the zeolite is oxidized and amidated, the mixed acid can enable the zeolite to generate more oxidation groups, the amine compound reacts with the oxidation groups to enable the oxidation zeolite to be amidated, the amide groups can react with anhydride groups in polyethylene grafted maleic anhydride, the grafting rate is higher, and the process is indispensable; in the step 2), the polymer grafted coated surface (polyethylene grafted maleic anhydride is grafted to the surface of zeolite) enhances the embeddability, reduces the infiltration of water to zeolite, and improves the dispersion, avoids agglomeration, improves the binding force with a matrix and avoids freeness by coacervation with a coupling agent; in the step 3), the zeolite powder modified by polyethylene grafted maleic anhydride is used as a carrier, silver ions and metal ions on the surface of the zeolite are replaced by silver nitrate and zeolite through a replacement reaction, so that the purpose of carrying silver by the zeolite is achieved, and the silver carrying amount obtained at the pH of 6-8 is higher and is 5% -10%.
In some examples of this embodiment, the mixed acid is concentrated H 2 SO 4 And concentrated HNO 3 The volume ratio is 3:1.
In some examples of this embodiment, the mass ratio of zeolite to mixed acid is 2:3.
In some examples of this embodiment, in step 1), the zeolite is sonicated for 10min; the temperature of the reflux reaction is 70 ℃, and the reflux reaction time is 24 hours; the drying time is 12h, and the drying temperature is 100-120 ℃.
In some examples of this embodiment, in step 1), the ultrasonic treatment of the oxidized zeolite is performed for 10 minutes; the temperature of the reflux reaction is 120 ℃, and the reflux reaction time is 48 hours; the drying time is 12h, and the drying temperature is 100-120 ℃.
In some examples of this embodiment, in step 1), the mass ratio of oxidized zeolite to anhydrous ethylenediamine, N-dicyclohexylcarbodiimide is 1:1:1.
in some examples of this embodiment, in step 2), the polyethylene grafted maleic anhydride to xylene mass ratio is from 0.5 to 4.5:15.
In some examples of this embodiment, in step 2), the ultrasonic treatment is performed for 20min; the temperature of the reflux reaction is 70 ℃, and the reflux reaction time is 24 hours; the drying temperature is 70-80 ℃.
In some examples of this embodiment, in step 3), the pH is from 5 to 9, preferably from 6 to 8; heating in water bath at 70-80deg.C; the drying temperature is 105 ℃ and the drying time is 8 hours; the stirring temperature was 150℃and the stirring time was 30min.
In some examples of this embodiment, in step 3), the coupling agent is one or both of an aminosilane, a vinyl silane; the volume ratio of the coupling agent to the absolute ethyl alcohol mixed solution is 1:10.
The third embodiment of the invention provides an antibacterial hydrophobically modified master batch, which comprises the following components in parts by weight: 50 parts of polyolefin matrix 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.
In some examples of this embodiment, a method of preparing an antimicrobial hydrophobically modified masterbatch comprising: weighing the raw materials according to a proportion, banburying the raw materials at 150 ℃ for 20 minutes in an internal mixer, and extruding and granulating the raw materials by a single screw rod.
In some examples of this embodiment, the fluorine-containing processing aid is U.S. 3M fluorine-containing processing aid FX-5914; the single screw extrusion temperature is 160-180 ℃.
The fourth embodiment of the invention provides a polyolefin antibacterial tube, which is divided into an outer layer and an antibacterial layer, wherein the outer layer comprises 96 parts of polyolefin and 4 parts of coloring master batch, and the inner layer comprises 80 parts of polyolefin, 16 parts of antibacterial hydrophobically modified master batch and 4 parts of coloring master batch.
In some examples of this embodiment, the polyolefin antimicrobial tube is made by a coextrusion process.
The fifth aspect of the present invention provides the use of the above-described polyolefin matrix long-acting antimicrobial or antimicrobial hydrophobically modified masterbatch or polyolefin antimicrobial tubing.
The polyolefin matrix long-acting antibacterial agent or the antibacterial hydrophobically modified master batch or the polyolefin antibacterial pipe is applied to the fields of household water supply, building floor heating, food packaging or medical and health instruments.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1:
the polyolefin matrix long-acting antibacterial agent comprises the following components in parts 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 coupling agent.
The preparation method of the olefin matrix long-acting antibacterial agent comprises the following steps:
1) The zeolite is treated in mixed acid (concentrated H 2 SO 4 And concentrated HNO 3 Ultrasonic treating in mixed acid 15 parts in a volume ratio of 3:1 for 10min, then carrying out reflux reaction at 70 ℃ for 24h, washing with deionized water after the reaction is finished, filtering for several times until the filtrate is neutral, drying in an oven for 12h at a drying temperature of 100-120 ℃ to obtain oxidized zeolite; ultrasonic treating oxidized zeolite in anhydrous ethylenediamine and N, N-dicyclohexyl carbodiimide (10 parts of anhydrous ethylenediamine and 10 parts of N, N-dicyclohexyl carbodiimide) for 10min, then reacting for 48h in a reflux device at 120 ℃, washing with absolute ethyl alcohol after the reaction is finished, filtering, repeating for several times until the filtrate is neutral, and drying in a vacuum oven for 12h at a drying temperature of 100-120 ℃ to obtain aminated zeolite powder;
2) Dissolving polyethylene grafted maleic anhydride in dimethylbenzene (15 parts of dimethylbenzene), adding aminated zeolite powder, carrying out ultrasonic treatment for 20min, carrying out reflux reaction at 70 ℃ for 24h, washing and filtering by using absolute ethyl alcohol after the reaction is finished, and drying a sample in a vacuum oven at the drying temperature of 70-80 ℃ to obtain polyethylene grafted maleic anhydride modified zeolite powder;
3) Dissolving polyethylene grafted maleic anhydride modified zeolite powder in silver nitrate solution, regulating pH value to 6-8, heating in water bath at 70-80 ℃, stirring for a certain time in a dark place, centrifuging, washing for several times with distilled water, drying at 105 ℃ for 8 hours, and mixing with a coupling agent and absolute ethyl alcohol mixed solution (volume ratio 1:10 High-speed stirring and mixing for 30min at 150 ℃ to obtain the polyolefin matrix long-acting antibacterial agent.
Antibacterial hydrophobic modified master batch
An antibacterial hydrophobically modified master batch comprises the following components in parts by mass: 50 parts of polyolefin matrix long-acting antibacterial agent, 3 parts of silicone, 3 parts of fluorine-containing processing aid (FX-5914) of U.S. 3M fluorine-containing processing aid, 4 parts of oxidized polyethylene wax and 40 parts of linear polyethylene.
The preparation method of the antibacterial hydrophobically modified master batch comprises the following steps:
raw materials are weighed according to a proportion, banburying is carried out for 20 minutes at 150 ℃ in an internal mixer, and single screw extrusion granulation is carried out at 160-180 ℃ to obtain the antibacterial hydrophobic modified master batch.
Polyolefin antibacterial tube
The polyolefin antibacterial pipe is divided into an outer layer and an antibacterial layer, wherein the formula of the outer layer comprises 96 parts of polyolefin and 4 parts of coloring master batch, and the formula of the inner layer comprises 80 parts of polyolefin, 16 parts of antibacterial hydrophobically modified master batch and 4 parts of coloring master batch according to claim 6;
the polyolefin antibacterial tube is prepared by a coextrusion process.
Example 2
The polyolefin matrix long-acting antibacterial agent comprises the following components in parts 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 coupling agent.
The preparation method of the olefin matrix long-acting antibacterial agent comprises the following steps:
1) The zeolite is treated in mixed acid (concentrated H 2 SO 4 And concentrated HNO 3 Ultrasonic treating in mixed acid 15 parts in a volume ratio of 3:1 for 10min, then carrying out reflux reaction at 70 ℃ for 24h, washing with deionized water after the reaction is finished, filtering for several times until the filtrate is neutral, drying in an oven for 12h at a drying temperature of 100-120 ℃ to obtain oxidized zeolite; ultrasonic treating oxidized zeolite in anhydrous ethylenediamine and N, N-dicyclohexyl carbodiimide (10 parts of anhydrous ethylenediamine and 10 parts of N, N-dicyclohexyl carbodiimide) for 10min, then reacting for 48h in a reflux device at 120 ℃, washing with absolute ethyl alcohol after the reaction is finished, filtering, repeating for several times until the filtrate is neutral, and drying in a vacuum oven for 12h at a drying temperature of 100-120 ℃ to obtain aminated zeolite powder;
2) Dissolving polyethylene grafted maleic anhydride in dimethylbenzene (15 parts of dimethylbenzene), adding aminated zeolite powder, carrying out ultrasonic treatment for 20min, carrying out reflux reaction at 70 ℃ for 24h, washing and filtering by using absolute ethyl alcohol after the reaction is finished, and drying a sample in a vacuum oven at the drying temperature of 70-80 ℃ to obtain polyethylene grafted maleic anhydride modified zeolite powder;
3) Dissolving polyethylene grafted maleic anhydride modified zeolite powder in silver nitrate solution, regulating pH value to 6-8, heating in water bath at 70-80 ℃, stirring for a certain time in a dark place, centrifuging, washing for several times with distilled water, drying at 105 ℃ for 8 hours, and mixing with a coupling agent and absolute ethyl alcohol mixed solution (volume ratio 1:10 High-speed stirring and mixing for 30min at 150 ℃ to obtain the polyolefin matrix long-acting antibacterial agent.
Antibacterial hydrophobic modified master batch
An antibacterial hydrophobically modified master batch comprises the following components in parts by mass: 50 parts of polyolefin matrix long-acting antibacterial agent, 3 parts of silicone, 3 parts of fluorine-containing processing aid (FX-5914) of U.S. 3M fluorine-containing processing aid, 4 parts of oxidized polyethylene wax and 40 parts of linear polyethylene.
The preparation method of the antibacterial hydrophobically modified master batch comprises the following steps:
raw materials are weighed according to a proportion, banburying is carried out for 20 minutes at 150 ℃ in an internal mixer, and single screw extrusion granulation is carried out at 160-180 ℃ to obtain the antibacterial hydrophobic modified master batch.
Polyolefin antibacterial tube
The polyolefin antibacterial pipe is divided into an outer layer and an antibacterial layer, wherein the formula of the outer layer comprises 96 parts of polyolefin and 4 parts of coloring master batch, and the formula of the inner layer comprises 80 parts of polyolefin, 16 parts of antibacterial hydrophobically modified master batch and 4 parts of coloring master batch according to claim 6;
the polyolefin antibacterial tube is prepared by a coextrusion process.
Example 3
The polyolefin matrix long-acting antibacterial agent comprises the following components in parts 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 coupling agent.
The preparation method of the olefin matrix long-acting antibacterial agent comprises the following steps:
1) The zeolite is treated in mixed acid (concentrated H 2 SO 4 And concentrated HNO 3 Ultrasonic treating in mixed acid 15 parts in a volume ratio of 3:1 for 10min, then carrying out reflux reaction at 70 ℃ for 24h, washing with deionized water after the reaction is finished, filtering for several times until the filtrate is neutral, drying in an oven for 12h at a drying temperature of 100-120 ℃ to obtain oxidized zeolite; ultrasonic treating oxidized zeolite in anhydrous ethylenediamine and N, N-dicyclohexyl carbodiimide (anhydrous ethylenediamine 10 parts, N, N-dicyclohexyl carbodiimide 10 parts) for 10min, reacting at 120deg.C in reflux device for 48 hr, and adding anhydrousWashing with ethanol, filtering, repeating for several times until the filtrate is neutral, and drying in a vacuum oven for 12h at 100-120deg.C to obtain aminated zeolite powder;
2) Dissolving polyethylene grafted maleic anhydride in dimethylbenzene (15 parts of dimethylbenzene), adding aminated zeolite powder, carrying out ultrasonic treatment for 20min, carrying out reflux reaction at 70 ℃ for 24h, washing and filtering by using absolute ethyl alcohol after the reaction is finished, and drying a sample in a vacuum oven at the drying temperature of 70-80 ℃ to obtain polyethylene grafted maleic anhydride modified zeolite powder;
3) Dissolving polyethylene grafted maleic anhydride modified zeolite powder in silver nitrate solution, regulating pH value to 6-8, heating in water bath at 70-80 ℃, stirring for a certain time in a dark place, centrifuging, washing for several times with distilled water, drying at 105 ℃ for 8 hours, and mixing with a coupling agent and absolute ethyl alcohol mixed solution (volume ratio 1:10 High-speed stirring and mixing for 30min at 150 ℃ to obtain the polyolefin matrix long-acting antibacterial agent.
Antibacterial hydrophobic modified master batch
An antibacterial hydrophobically modified master batch comprises the following components in parts by mass: 50 parts of polyolefin matrix long-acting antibacterial agent, 3 parts of silicone, 3 parts of fluorine-containing processing aid (FX-5914) of U.S. 3M fluorine-containing processing aid, 4 parts of oxidized polyethylene wax and 40 parts of linear polyethylene.
The preparation method of the antibacterial hydrophobically modified master batch comprises the following steps:
raw materials are weighed according to a proportion, banburying is carried out for 20 minutes at 150 ℃ in an internal mixer, and single screw extrusion granulation is carried out at 160-180 ℃ to obtain the antibacterial hydrophobic modified master batch.
Polyolefin antibacterial tube
The polyolefin antibacterial pipe is divided into an outer layer and an antibacterial layer, wherein the formula of the outer layer comprises 96 parts of polyolefin and 4 parts of coloring master batch, and the formula of the inner layer comprises 80 parts of polyolefin, 16 parts of antibacterial hydrophobically modified master batch and 4 parts of coloring master batch according to claim 6;
the polyolefin antibacterial tube is prepared by a coextrusion process.
Example 4
The polyolefin matrix long-acting antibacterial agent comprises the following components in parts 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 coupling agent.
The preparation method of the olefin matrix long-acting antibacterial agent comprises the following steps:
1) The zeolite is treated in mixed acid (concentrated H 2 SO 4 And concentrated HNO 3 Ultrasonic treating in mixed acid 15 parts in a volume ratio of 3:1 for 10min, then carrying out reflux reaction at 70 ℃ for 24h, washing with deionized water after the reaction is finished, filtering for several times until the filtrate is neutral, drying in an oven for 12h at a drying temperature of 100-120 ℃ to obtain oxidized zeolite; ultrasonic treating oxidized zeolite in anhydrous ethylenediamine and N, N-dicyclohexyl carbodiimide (10 parts of anhydrous ethylenediamine and 10 parts of N, N-dicyclohexyl carbodiimide) for 10min, then reacting for 48h in a reflux device at 120 ℃, washing with absolute ethyl alcohol after the reaction is finished, filtering, repeating for several times until the filtrate is neutral, and drying in a vacuum oven for 12h at a drying temperature of 100-120 ℃ to obtain aminated zeolite powder;
2) Dissolving polyethylene grafted maleic anhydride in dimethylbenzene (15 parts of dimethylbenzene), adding aminated zeolite powder, carrying out ultrasonic treatment for 20min, carrying out reflux reaction at 70 ℃ for 24h, washing and filtering by using absolute ethyl alcohol after the reaction is finished, and drying a sample in a vacuum oven at the drying temperature of 70-80 ℃ to obtain polyethylene grafted maleic anhydride modified zeolite powder;
3) Dissolving polyethylene grafted maleic anhydride modified zeolite powder in silver nitrate solution, regulating pH value to 6-8, heating in water bath at 70-80 ℃, stirring for a certain time in a dark place, centrifuging, washing for several times with distilled water, drying at 105 ℃ for 8 hours, and mixing with a coupling agent and absolute ethyl alcohol mixed solution (volume ratio 1:10 High-speed stirring and mixing for 30min at 150 ℃ to obtain the polyolefin matrix long-acting antibacterial agent.
Antibacterial hydrophobic modified master batch
An antibacterial hydrophobically modified master batch comprises the following components in parts by mass: 50 parts of polyolefin matrix long-acting antibacterial agent, 3 parts of silicone, 3 parts of fluorine-containing processing aid (FX-5914) of U.S. 3M fluorine-containing processing aid, 4 parts of oxidized polyethylene wax and 40 parts of linear polyethylene.
The preparation method of the antibacterial hydrophobically modified master batch comprises the following steps:
raw materials are weighed according to a proportion, banburying is carried out for 20 minutes at 150 ℃ in an internal mixer, and single screw extrusion granulation is carried out at 160-180 ℃ to obtain the antibacterial hydrophobic modified master batch.
Polyolefin antibacterial tube
The polyolefin antibacterial pipe is divided into an outer layer and an antibacterial layer, wherein the formula of the outer layer comprises 96 parts of polyolefin and 4 parts of coloring master batch, and the formula of the inner layer comprises 80 parts of polyolefin, 16 parts of antibacterial hydrophobically modified master batch and 4 parts of coloring master batch according to claim 6;
the polyolefin antibacterial tube is prepared by a coextrusion process.
Example 5
The polyolefin matrix long-acting antibacterial agent comprises the following components in parts 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 coupling agent.
The preparation method of the olefin matrix long-acting antibacterial agent comprises the following steps:
1) The zeolite is treated in mixed acid (concentrated H 2 SO 4 And concentrated HNO 3 Ultrasonic treating in mixed acid 15 parts in a volume ratio of 3:1 for 10min, then carrying out reflux reaction at 70 ℃ for 24h, washing with deionized water after the reaction is finished, filtering for several times until the filtrate is neutral, drying in an oven for 12h at a drying temperature of 100-120 ℃ to obtain oxidized zeolite; ultrasonic treating oxidized zeolite in anhydrous ethylenediamine and N, N-dicyclohexyl carbodiimide (10 parts of anhydrous ethylenediamine and 10 parts of N, N-dicyclohexyl carbodiimide) for 10min, then reacting for 48h in a reflux device at 120 ℃, washing with absolute ethyl alcohol after the reaction is finished, filtering, repeating for several times until the filtrate is neutral, and drying in a vacuum oven for 12h at a drying temperature of 100-120 ℃ to obtain aminated zeolite powder;
2) Dissolving polyethylene grafted maleic anhydride in dimethylbenzene (15 parts of dimethylbenzene), adding aminated zeolite powder, carrying out ultrasonic treatment for 20min, carrying out reflux reaction at 70 ℃ for 24h, washing and filtering by using absolute ethyl alcohol after the reaction is finished, and drying a sample in a vacuum oven at the drying temperature of 70-80 ℃ to obtain polyethylene grafted maleic anhydride modified zeolite powder;
3) Dissolving polyethylene grafted maleic anhydride modified zeolite powder in silver nitrate solution, regulating pH value to 6-8, heating in water bath at 70-80 ℃, stirring for a certain time in a dark place, centrifuging, washing for several times with distilled water, drying at 105 ℃ for 8 hours, and mixing with a coupling agent and absolute ethyl alcohol mixed solution (volume ratio 1:10 High-speed stirring and mixing for 30min at 150 ℃ to obtain the polyolefin matrix long-acting antibacterial agent.
Antibacterial hydrophobic modified master batch
An antibacterial hydrophobically modified master batch comprises the following components in parts by mass: 50 parts of polyolefin matrix long-acting antibacterial agent, 3 parts of silicone, 3 parts of fluorine-containing processing aid (FX-5914) of U.S. 3M fluorine-containing processing aid, 4 parts of oxidized polyethylene wax and 40 parts of linear polyethylene.
The preparation method of the antibacterial hydrophobically modified master batch comprises the following steps:
raw materials are weighed according to a proportion, banburying is carried out for 20 minutes at 150 ℃ in an internal mixer, and single screw extrusion granulation is carried out at 160-180 ℃ to obtain the antibacterial hydrophobic modified master batch.
Polyolefin antibacterial tube
The polyolefin antibacterial pipe is divided into an outer layer and an antibacterial layer, wherein the formula of the outer layer comprises 96 parts of polyolefin and 4 parts of coloring master batch, and the formula of the inner layer comprises 80 parts of polyolefin, 16 parts of antibacterial hydrophobically modified master batch and 4 parts of coloring master batch according to claim 6;
the polyolefin antibacterial tube is prepared by a coextrusion process.
Example 6
The polyolefin matrix long-acting antibacterial agent comprises the following components in parts by weight: 10 parts of zeolite, 1 part of polyethylene grafted maleic anhydride, 20 parts of 5% silver nitrate solution and 0.3 part of coupling agent.
The preparation method of the olefin matrix long-acting antibacterial agent comprises the following steps:
1) The zeolite is treated in mixed acid (concentrated H 2 SO 4 And concentrated HNO 3 Ultrasonic treating in mixed acid 15 parts in volume ratio of 3:1) for 10min, reflux reacting at 70deg.C for 24 hr, washing with deionized water, filtering for several times until the filtrate is neutral, and dryingDrying in a box for 12h at 100-120 ℃ to obtain oxidized zeolite; ultrasonic treating oxidized zeolite in anhydrous ethylenediamine and N, N-dicyclohexyl carbodiimide (10 parts of anhydrous ethylenediamine and 10 parts of N, N-dicyclohexyl carbodiimide) for 10min, then reacting for 48h in a reflux device at 120 ℃, washing with absolute ethyl alcohol after the reaction is finished, filtering, repeating for several times until the filtrate is neutral, and drying in a vacuum oven for 12h at a drying temperature of 100-120 ℃ to obtain aminated zeolite powder;
2) Dissolving polyethylene grafted maleic anhydride in dimethylbenzene (15 parts of dimethylbenzene), adding aminated zeolite powder, carrying out ultrasonic treatment for 20min, carrying out reflux reaction at 70 ℃ for 24h, washing and filtering with absolute ethyl alcohol after the reaction is finished, and drying a sample in a vacuum oven at a drying temperature of 70-80 ℃ to obtain polyethylene grafted maleic anhydride modified zeolite powder;
3) Dissolving polyethylene grafted maleic anhydride modified zeolite powder in silver nitrate solution, regulating pH value to 6-8, heating in water bath at 70-80 ℃, stirring for a certain time in a dark place, centrifuging, washing for several times with distilled water, drying at 105 ℃ for 8 hours, and mixing with a coupling agent and absolute ethyl alcohol mixed solution (volume ratio 1:10 High-speed stirring and mixing for 30min at 150 ℃ to obtain the polyolefin matrix long-acting antibacterial agent.
Antibacterial hydrophobic modified master batch
An antibacterial hydrophobically modified master batch comprises the following components in parts by mass: 50 parts of polyolefin matrix long-acting antibacterial agent, 3 parts of silicone, 3 parts of fluorine-containing processing aid (FX-5914) of U.S. 3M fluorine-containing processing aid, 4 parts of oxidized polyethylene wax and 40 parts of linear polyethylene.
The preparation method of the antibacterial hydrophobically modified master batch comprises the following steps:
raw materials are weighed according to a proportion, banburying is carried out for 20 minutes at 150 ℃ in an internal mixer, and single screw extrusion granulation is carried out at 160-180 ℃ to obtain the antibacterial hydrophobic modified master batch.
Polyolefin antibacterial tube
The polyolefin antibacterial pipe is divided into an outer layer and an antibacterial layer, wherein the formula of the outer layer comprises 96 parts of polyolefin and 4 parts of coloring master batch, and the formula of the inner layer comprises 80 parts of polyolefin, 16 parts of antibacterial hydrophobically modified master batch and 4 parts of coloring master batch according to claim 6;
the polyolefin antibacterial tube is prepared by a coextrusion process.
Comparative example 1
The difference between comparative example 1 and example 1 is that comparative example 1 does not have step (2), i.e., the surface of the antimicrobial carrier nano zeolite is not modified by polyethylene grafted maleic anhydride. The rest of the procedure is the same as in example 1.
Comparative example 2
The difference between comparative example 2 and example 1 is that step (3) is not performed in comparative example 2, i.e., the polyethylene grafted maleic anhydride modified zeolite is not subjected to the coupling agent treatment. The rest of the procedure is the same as in example 1.
Comparative example 3
Comparative example 4 differs from example 1 in that comparative example 4 lacks a fluorine-containing processing aid, and the remainder of the procedure is the same as example 1.
Antibacterial test
1. Durability test for antibacterial tube products
Cutting a section of pipe with the length of about 10cm from the prepared antibacterial pipe, soaking in water at 80 ℃ for 100 hours, taking out, washing, soaking in water at 20 ℃ for 24 hours, and testing the mass m of silver ions in the soaking solution 1 The method comprises the steps of carrying out a first treatment on the surface of the Soaking the pipe section in 80deg.C water for 1000 hr, taking out, washing, soaking in 20deg.C water for 24 hr, and testing silver ion mass m 2 。
Note that: silver ion content testing method
Direct titration: in an acidic medium, with ammonium thiocyanate (NH 4 SCN) standard solution direct titration of silver-containing solution, after silver thiocyanate (AgSCN) precipitation is complete, a slight excess of SCN - With Fe 3+ The reaction produced a red complex ion indicating that the titration endpoint had been reached. Wherein the acidic medium is diluted with nitric acid to adjust hydrogen ion concentration to 0.1-1mol/L, and ammonium thiocyanate (NH) 4 SCN) standard solution concentration was 0.015mol/L.
2. Antibacterial property test of antibacterial composite layer of antibacterial tube
According to the method test in the standard QB/T2591-2003, the sample plate is soaked in water at 80 ℃ for 1000 hours before the test, and the antibacterial grade is not lower than the grade II requirement.
The durability test and antibacterial property of the antibacterial tube prepared in each of the examples and comparative examples are shown in table 1.
Table 1 durability test and antibacterial property of antibacterial tubes prepared in each example and comparative example
As can be seen from the table, the antibacterial grade of the prepared polyolefin antibacterial tube meets the grade II requirement by using polyethylene grafted maleic anhydride to modify the surface of the nano zeolite of the antibacterial agent carrier, then carrying out silver ion replacement and then carrying out coupling agent treatment, and the difference of the tested silver ions is not more than 20 percent (examples 1-6). It was found by subjecting it to endurance test analysis respectively: firstly, the polyethylene grafted maleic anhydride is grafted to the surface of zeolite to enhance the silver ion intercalation (examples and comparative example 1), the polyethylene grafted maleic anhydride influences the silver ion precipitation speed, and the more the polyethylene grafted maleic anhydride is, the slower the silver ion precipitation speed is (examples 3-5); secondly, silver nitrate affects the silver loading of zeolite, the silver loading is high, the precipitation rate is high (example 1 and example 2), and the coupling agent prevents silver ions from precipitating to a certain extent (example 1 and example 6). The invention can show that the antibacterial agent is modified, so that the antibacterial agent is completely coated by resin, the precipitation of metal ions is reduced, the dispersibility of the antibacterial agent is enhanced, the dispersion requirement under the condition of high addition amount is met by the combination of the antibacterial agent and a matrix, the precipitation amount is lower under the condition of higher antibacterial agent content, the precipitation is lasting, and the antibacterial service life is effectively prolonged.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The polyolefin matrix long-acting antibacterial agent is characterized by comprising the following components in parts by mass: 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 part of coupling agent.
2. The polyolefin matrix long-acting antibacterial agent according to claim 1, characterized by comprising, in parts by mass: 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 part of coupling agent.
3. A process for the preparation of a polyolefin matrix long-acting antimicrobial agent according to any one of claims 1-2, characterized by the steps of:
1) Ultrasonic treatment of zeolite in mixed acid, reflux reaction, washing with deionized water after reaction, filtering until the filtrate is neutral, and drying to obtain oxidized zeolite;
ultrasonic treatment of oxidized zeolite in anhydrous ethylenediamine and N, N-dicyclohexyl carbodiimide, reflux reaction, washing with absolute ethanol after the reaction, filtering to neutrality, and drying to obtain aminated zeolite powder;
2) Dissolving polyethylene grafted maleic anhydride in dimethylbenzene, adding aminated zeolite powder, carrying out ultrasonic treatment, carrying out reflux reaction, washing and filtering by using absolute ethyl alcohol after the reaction is finished, and drying to obtain polyethylene grafted maleic anhydride modified zeolite powder;
3) Dissolving polyethylene grafted maleic anhydride modified zeolite powder in silver nitrate solution, regulating pH value, heating in water bath, stirring in dark, centrifugally separating, washing with distilled water, drying, and mixing with coupling agent and anhydrous alcohol mixture at high speed.
4. The method according to claim 1, wherein in step 1), the mixed acid is concentrated H 2 SO 4 And concentrated HNO 3 The volume ratio is 3:1; the mass ratio of zeolite to mixed acid is 2:3;
preferably, the zeolite is sonicated for 10 minutes; the temperature of the reflux reaction is 70 ℃, and the reflux reaction time is 24 hours; the drying time is 12 hours, and the drying temperature is 100-120 ℃;
preferably, the zeolite is oxidized by ultrasonic treatment for 10min; the temperature of the reflux reaction is 120 ℃, and the reflux reaction time is 48 hours; the drying time in the oven is 12 hours, and the drying temperature is 100-120 ℃; the mass ratio of the oxidized zeolite to anhydrous ethylenediamine to N, N-dicyclohexyl carbodiimide is 1:1:1.
5. the method according to claim 1, wherein in step 2), the ultrasonic treatment is performed for 20 minutes; the temperature of the reflux reaction is 70 ℃, and the reflux reaction time is 24 hours; the drying temperature is 70-80 ℃.
6. The method according to claim 1, wherein in step 3), the pH is 5-9, preferably 6-8; heating in water bath at 70-80deg.C; the drying temperature is 105 ℃ and the drying time is 8 hours; stirring at 150deg.C for 30min; preferably, the volume ratio of the coupling agent to the absolute ethyl alcohol mixed solution is 1:10.
7. The antibacterial hydrophobically modified master batch is characterized by comprising the following components in parts by weight: the polyolefin matrix long-acting antimicrobial agent of claims 1-2, 50 parts of silicone, 3 parts of fluorine-containing processing aid, 4 parts of oxidized polyethylene wax, and 40 parts of linear polyethylene;
weighing the raw materials according to a proportion, banburying the raw materials at 150 ℃ for 20 minutes in an internal mixer, and extruding and granulating the raw materials by a single screw rod.
8. The antibacterial hydrophobically modified masterbatch of claim 7 wherein the single screw extrusion temperature is 160-180 ℃.
9. The polyolefin antibacterial tube is characterized by comprising an outer layer and an antibacterial layer, wherein the outer layer comprises 96 parts of polyolefin and 4 parts of coloring master batch, and the inner layer comprises 80 parts of polyolefin, 16 parts of antibacterial hydrophobically modified master batch and 4 parts of coloring master batch according to any one of claims 7-8;
the polyolefin antibacterial tube is prepared by a coextrusion process.
10. Use of the polyolefin matrix long-acting antimicrobial agent of any one of claims 1-2 or the antimicrobial hydrophobically modified masterbatch of claims 7-8 or the polyolefin antimicrobial tube of claim 9 in the field of household water supply, building floor heating, food packaging or medical and health appliances.
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| CN117683298A (en) * | 2023-12-26 | 2024-03-12 | 青岛中新华美塑料有限公司 | Antibacterial PP material and preparation method thereof |
| CN117700793A (en) * | 2023-12-25 | 2024-03-15 | 合肥科拜尔新材料股份有限公司 | Nano silver suicide resin material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117700793A (en) * | 2023-12-25 | 2024-03-15 | 合肥科拜尔新材料股份有限公司 | Nano silver suicide resin material and preparation method thereof |
| CN117683298A (en) * | 2023-12-26 | 2024-03-12 | 青岛中新华美塑料有限公司 | Antibacterial PP material and preparation method thereof |
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