CN116640339B - Antibacterial and mildew-proof plastic film and preparation method thereof - Google Patents

Antibacterial and mildew-proof plastic film and preparation method thereof Download PDF

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CN116640339B
CN116640339B CN202310726208.0A CN202310726208A CN116640339B CN 116640339 B CN116640339 B CN 116640339B CN 202310726208 A CN202310726208 A CN 202310726208A CN 116640339 B CN116640339 B CN 116640339B
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antibacterial
mildew
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CN116640339A (en
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刘鉴威
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Guangdong Yu Tai Industrial Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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Abstract

The invention relates to the technical field of plastics, and discloses an antibacterial and mildew-proof plastic film and a preparation method thereof. Under the action of the compatibilizer, the cross-linked cellulose loaded silver antibacterial agent can be dispersed in the polyvinyl chloride plastic film, the cross-linked cellulose loaded high-content silver ion antibacterial agent has excellent sterilization and mildew resistance, and the silver ion antibacterial agent is uniformly dispersed and anchored in a cross-linked cellulose matrix, so that the problem of silver ion precipitation migration after contact with water can be reduced, and the polyvinyl chloride plastic film has long-acting antibacterial and mildew resistance.

Description

Antibacterial and mildew-proof plastic film and preparation method thereof
Technical Field
The invention relates to the technical field of plastics, in particular to an antibacterial and mildew-proof plastic film and a preparation method thereof.
Background
Polyvinyl chloride is one of the general plastics with the largest output in the world, has wide application in packaging films, building materials, wires and cables, foaming materials, sealing materials, fibers and the like, has poor antibacterial and mildew-proof properties, and prevents the application of the polyvinyl chloride in the aspects of food packaging, sanitary products, medical fields and the like; the silver antibacterial agent has the advantages of no toxicity, environmental protection, high sterilization speed and excellent mildew-proof effect, and has important application in the antibacterial mildew-proof invention of high polymer materials.
The silver antibacterial agent is directly added into plastic products, so that the performance of the materials is reduced, the color change is serious, and when the plastic contacts water, silver ions are separated out, so that the long-acting antibacterial and mildew-proof performances of the materials are affected. The silver antibacterial agent is loaded on the surface of the carrier, so that the problems, such as zirconium phosphate, titanium dioxide, chitosan and polyethyleneimine, can be effectively solved.
Cellulose is a natural high molecular compound with the most abundant reserves in nature, is green and pollution-free, has good mechanical property, is easy to chemically modify, can be used as an antibacterial agent, a reinforcing agent, a dispersing agent and the like, and has wide application in the aspects of antibacterial materials, plastic films, wood plastic materials, chemical fibers and the like as a carrier of the silver antibacterial agent.
Disclosure of Invention
The invention solves the technical problems that: provides a cross-linked cellulose loaded silver antibacterial agent, which solves the problem of poor antibacterial and mildew-proof properties of the traditional polyvinyl chloride material.
The technical scheme of the invention is as follows:
a preparation method of an antibacterial and mildew-proof plastic film comprises the following steps:
adding 100% of polyvinyl chloride, 1-8% of cross-linked cellulose loaded silver antibacterial agent, 30-45% of plasticizer, 1-6% of epoxidized soybean oil, 0.3-2% of compatibilizer, 2-6% of chlorinated paraffin and 1.5-2% of stabilizer into a mixer for mixing, and then carrying out banburying in an internal mixer; then placing the mixture into an open mill for open-scouring; extruding the mixture in an extrusion calender to form strips; finally, rolling into a film shape through rolling equipment to obtain the antibacterial and mildew-proof plastic film.
Further, the plasticizer is selected from dioctyl phthalate, the compatibilizer is selected from maleic anhydride grafted polyvinyl chloride, and the stabilizer is selected from organotin stabilizers.
Further, the temperature in the internal mixer is 160-170 ℃ and the internal mixing time is 2-4min; the temperature in the open mill is 150-160 ℃, and the open mill time is 1.5-3min.
Further, the pyridine amide Schiff base crosslinked cellulose is prepared according to the following method:
dissolving 2-formyl-5-hydroxypyridine and terephthalic acid dihydrazide into a 1, 4-dioxane solvent, dropwise adding an acetic acid solution under the protection of nitrogen, cooling after reaction, adding a sodium hydroxide aqueous solution for neutralization, concentrating to remove the 1, 4-dioxane, adding ethyl acetate and water for extraction, drying an organic phase with anhydrous sodium sulfate, filtering, concentrating a filtrate, and recrystallizing a product in ethanol to obtain the terephthalic acid bis (pyridine amide Schiff base) intermediate. The reaction formula is as follows:
adding carboxymethyl cellulose into N, N-dimethylformamide, stirring and swelling, adding a bis (pyridine amide Schiff base) terephthalate intermediate, N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, reacting for 24-72h at room temperature, filtering, sequentially washing with water and ethanol, and drying to obtain the pyridine amide Schiff base crosslinked cellulose.
Adding pyridine amide Schiff base crosslinked cellulose into an ethanol solvent, performing ultrasonic vibration to disperse, then adding silver nitrate, performing ultrasonic vibration at room temperature for 4-10 hours, filtering, washing with water and ethanol, and drying to obtain a crosslinked cellulose loaded silver antibacterial agent; the reaction process is as follows:
further, the mass of the silver nitrate is 80-200% of that of the pyridine amide Schiff base crosslinked cellulose; the mass fraction of silver nitrate in the solution is controlled to be (5-30) g/L.
Further, the molar amount of 2-formyl-5-hydroxypyridine is (180-240)% of terephthalic acid dihydrazide.
Further, the concentration of the acetic acid solution is not less than 90%, CH in the acetic acid solution 3 COOH) is used in a molar amount of (500-800)% of terephthalic acid dihydrazide.
Further, the reaction is refluxed at a temperature of 90-110 ℃ for 6-24 hours.
Further, the mass percentages of the bis (pyridine amide Schiff base) phthalate intermediate, the N-hydroxysuccinimide and the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride are respectively (50-150)%, (30-80)% and (70-220)% of carboxymethyl cellulose.
The beneficial technical effects of the invention are as follows: the preparation method comprises the steps of taking terephthalic acid dihydrazide, terephthalic acid dihydrazide and 2-formyl-5-hydroxypyridine as raw materials to prepare a terephthalic acid di (pyridine amide Schiff base) intermediate, and then carrying out esterification reaction on double-end hydroxyl contained in the intermediate and carboxymethyl cellulose to carry out chemical crosslinking to obtain pyridine amide Schiff base crosslinked cellulose, wherein the crosslinked cellulose forms a three-dimensional space structure and has the advantages of large specific surface area and multiple load sites; and the cellulose contains a pyridine amide Schiff base structure, and oxygen atoms, schiff base nitrogen sources and pyridine nitrogen atoms in the amide structure can be well coordinated and chelated with silver ions, so that the silver ions are uniformly dispersed and anchored in a crosslinked cellulose matrix while the loading capacity of the silver ion antibacterial agent is improved.
Polyvinyl chloride, crosslinked cellulose loaded silver antibacterial agent, rong Jima maleic anhydride grafted polyvinyl chloride and the like are subjected to banburying, open scouring, extrusion into strips and calendaring to form a film, so that the polyvinyl chloride antibacterial and mildew-proof plastic film is obtained. Under the action of the compatibilizer, the cross-linked cellulose loaded silver antibacterial agent can be dispersed in the polyvinyl chloride plastic film, the cross-linked cellulose loaded high-content silver ion antibacterial agent has excellent sterilization and mildew resistance, and the silver ion antibacterial agent is uniformly dispersed and anchored in a cross-linked cellulose matrix, so that the problem of silver ion precipitation migration after contact with water can be reduced, and the polyvinyl chloride plastic film has long-acting antibacterial and mildew resistance.
Detailed Description
The technical scheme of the present invention will be further described by the following specific examples, and it should be understood that the specific examples described herein are only for aiding in understanding the present invention, and are not intended to be limiting. Unless otherwise indicated, all materials used in the examples of the present invention are those commonly used in the art, and all methods used in the examples are those commonly used in the art.
Example 1
Preparing a bis (pyridine amide schiff base) terephthalate intermediate: dissolving terephthalic acid dihydrazide, 2-formyl-5-hydroxypyridine accounting for 240% of the molar dosage of the terephthalic acid dihydrazide and the acetic acid solution with the concentration of 99.5% in a 1, 4-dioxane solvent under the protection of nitrogen, and controlling CH in the acetic acid solution 3 The molar quantity of COOH is 800% of that of terephthalic acid dihydrazide, reflux is carried out for 6 hours at the temperature of 110 ℃, the reaction is carried out, cooling is carried out, sodium hydroxide aqueous solution is added for neutralization, 1, 4-dioxane is concentrated and removed, ethyl acetate and water are added for extraction, the organic phase is dried by anhydrous sodium sulfate, the filtrate is concentrated after filtration, and the product is recrystallized in ethanol to obtain the terephthalic acid bis (pyridine amide Schiff base) intermediate.
Preparation of pyridine amide Schiff base crosslinked cellulose: adding carboxymethyl cellulose into N, N-dimethylformamide, stirring and swelling, then respectively adding 70% of terephthalic acid di (pyridine amide Schiff base) intermediate, 45% of N-hydroxysuccinimide and 110% of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride by mass of carboxymethyl cellulose, reacting for 36 hours at room temperature, filtering, sequentially washing with water and ethanol, and drying to obtain the pyridine amide Schiff base crosslinked cellulose.
Preparing a crosslinked cellulose-loaded silver antibacterial agent: adding the pyridine amide Schiff base crosslinked cellulose into an ethanol solvent, performing ultrasonic vibration to disperse, then adding 80% silver nitrate of the mass of the pyridine amide Schiff base crosslinked cellulose, controlling the mass fraction of the silver nitrate in the solution to be 5g/L, performing ultrasonic vibration for 8 hours at room temperature, filtering, washing with water and ethanol, and drying to obtain the crosslinked cellulose supported silver antibacterial agent.
Preparing an antibacterial and mildew-proof plastic film: adding 100% of polyvinyl chloride, 1% of cross-linked cellulose-loaded silver antibacterial agent, 30% of plasticizer dioctyl phthalate, 6% of epoxidized soybean oil, 0.3% of Rong Jima-anhydride-grafted polyvinyl chloride, 6% of chlorinated paraffin and 1.5% of stabilizer organotin stabilizer into a mixer for mixing, and then carrying out banburying in an internal mixer at the temperature of 165 ℃ for 4min; then placing the mixture into an open mill for open-scouring, wherein the temperature in the open mill is 155 ℃, and the open-scouring time is 3min; extruding the mixture in an extrusion calender to form strips; finally, rolling into a film shape through rolling equipment to obtain the antibacterial and mildew-proof plastic film.
Example 2
Preparing a bis (pyridine amide schiff base) terephthalate intermediate: dissolving terephthalic acid dihydrazide, 2-formyl-5-hydroxypyridine accounting for 180 percent of the molar dosage of the terephthalic acid dihydrazide and the acetic acid solution with the concentration of 99.5 percent in a 1, 4-dioxane solvent under the protection of nitrogen, and controlling CH in the acetic acid solution 3 The molar quantity of COOH is 500 percent of that of terephthalic acid dihydrazide, reflux is carried out for 6 hours at the temperature of 110 ℃, the reaction is cooled, sodium hydroxide aqueous solution is added for neutralization, and 1, 4-percent is removed by concentrationExtracting dioxane with ethyl acetate and water, drying the organic phase with anhydrous sodium sulfate, filtering, concentrating the filtrate, and recrystallizing the product in ethanol to obtain the di (pyridine amide Schiff base) terephthalate intermediate.
Preparation of pyridine amide Schiff base crosslinked cellulose: adding carboxymethyl cellulose into N, N-dimethylformamide, stirring and swelling, then respectively adding 50% of terephthalic acid di (pyridine amide Schiff base) intermediate, 30% of N-hydroxysuccinimide and 70% of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride by mass of carboxymethyl cellulose, reacting for 72 hours at room temperature, filtering, sequentially washing with water and ethanol, and drying to obtain the pyridine amide Schiff base crosslinked cellulose.
Preparing a crosslinked cellulose-loaded silver antibacterial agent: adding the pyridine amide Schiff base crosslinked cellulose into an ethanol solvent, performing ultrasonic vibration to disperse, then adding 120% silver nitrate by mass of the pyridine amide Schiff base crosslinked cellulose, controlling the mass fraction of the silver nitrate in the solution to be 10g/L, performing ultrasonic vibration at room temperature for 6 hours, filtering, washing with water and ethanol, and drying to obtain the crosslinked cellulose silver-loaded antibacterial agent.
Preparing an antibacterial and mildew-proof plastic film: adding 100% of polyvinyl chloride, 1% of cross-linked cellulose-loaded silver antibacterial agent, 35% of plasticizer dioctyl phthalate, 2% of epoxidized soybean oil, 0.3% of Rong Jima-anhydride grafted polyvinyl chloride, 2% of chlorinated paraffin and 2% of stabilizer organotin stabilizer into a mixer for mixing, and then banburying in an internal mixer at the temperature of 170 ℃ for 2min; then placing the mixture into an open mill for open-scouring, wherein the temperature in the open mill is 160 ℃, and the open-scouring time is 1.5min; extruding the mixture in an extrusion calender to form strips; finally, rolling into a film shape through rolling equipment to obtain the antibacterial and mildew-proof plastic film.
Example 3
Preparing a bis (pyridine amide schiff base) terephthalate intermediate: 2-formyl-5-hydroxypyridine with the molar amount of terephthalic acid dihydrazide accounting for 210 percent and dissolved in a 1, 4-dioxane solvent are added dropwise under the protection of nitrogen, wherein the concentration is 99.5 percentAcetic acid solution, control CH in acetic acid solution 3 The molar quantity of COOH is 650% of terephthalic acid dihydrazide, reflux is carried out for 6 hours at the temperature of 100 ℃, the reaction is carried out, cooling is carried out, sodium hydroxide aqueous solution is added for neutralization, 1, 4-dioxane is concentrated and removed, ethyl acetate and water are added for extraction, the organic phase is dried by anhydrous sodium sulfate, the filtrate is concentrated after filtration, and the product is recrystallized in ethanol to obtain the terephthalic acid di (pyridine amide Schiff base) intermediate.
Preparation of pyridine amide Schiff base crosslinked cellulose: adding carboxymethyl cellulose into N, N-dimethylformamide, stirring and swelling, then respectively adding 120% of terephthalic acid di (pyridine amide Schiff base) intermediate, 50% of N-hydroxysuccinimide and 150% of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride by mass of carboxymethyl cellulose, reacting for 36 hours at room temperature, filtering, sequentially washing with water and ethanol, and drying to obtain the pyridine amide Schiff base crosslinked cellulose.
Preparing a crosslinked cellulose-loaded silver antibacterial agent: adding the pyridine amide Schiff base crosslinked cellulose into an ethanol solvent, performing ultrasonic vibration to disperse, then adding 150% silver nitrate by mass of the pyridine amide Schiff base crosslinked cellulose, controlling the mass fraction of the silver nitrate in the solution to be 15g/L, performing ultrasonic vibration for 8 hours at room temperature, filtering, washing with water and ethanol, and drying to obtain the crosslinked cellulose supported silver antibacterial agent.
Preparing an antibacterial and mildew-proof plastic film: adding 100% of polyvinyl chloride, 4% of crosslinked cellulose-loaded silver antibacterial agent, 40% of dioctyl phthalate serving as a plasticizer, 4% of epoxidized soybean oil, 1% of Rong Jima-anhydride grafted polyvinyl chloride, 6% of chlorinated paraffin and 1.5% of stabilizer organotin stabilizer into a mixer for mixing, and then banburying in an internal mixer at the temperature of 170 ℃ for 2min; then placing the mixture into an open mill for open-scouring, wherein the temperature in the open mill is 155 ℃, and the open-scouring time is 2min; extruding the mixture in an extrusion calender to form strips; finally, rolling into a film shape through rolling equipment to obtain the antibacterial and mildew-proof plastic film.
Example 4
Preparation of bis (picolinamide) terephthalate matFraine) intermediate: dissolving terephthalic acid dihydrazide, 2-formyl-5-hydroxypyridine accounting for 240% of the molar dosage of the terephthalic acid dihydrazide and the acetic acid solution with the concentration of 99.5% in a 1, 4-dioxane solvent under the protection of nitrogen, and controlling CH in the acetic acid solution 3 The molar quantity of COOH is 750% of terephthalic acid dihydrazide, reflux is carried out for 18 hours at the temperature of 100 ℃, the reaction is carried out, cooling is carried out, sodium hydroxide aqueous solution is added for neutralization, 1, 4-dioxane is concentrated and removed, ethyl acetate and water are added for extraction, the organic phase is dried by anhydrous sodium sulfate, the filtrate is concentrated after filtration, and the product is recrystallized in ethanol to obtain the terephthalic acid di (pyridine amide Schiff base) intermediate.
Preparation of pyridine amide Schiff base crosslinked cellulose: adding carboxymethyl cellulose into N, N-dimethylformamide, stirring and swelling, then respectively adding 120% of terephthalic acid di (pyridine amide Schiff base) intermediate, 60% of N-hydroxysuccinimide and 190% of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride by mass of carboxymethyl cellulose, reacting for 72 hours at room temperature, filtering, sequentially washing with water and ethanol, and drying to obtain the pyridine amide Schiff base crosslinked cellulose.
Preparing a crosslinked cellulose-loaded silver antibacterial agent: adding pyridine amide Schiff base crosslinked cellulose into an ethanol solvent, performing ultrasonic vibration to disperse, then adding 170% silver nitrate by mass of the pyridine amide Schiff base crosslinked cellulose, controlling the mass fraction of the silver nitrate in the solution to be 25g/L, performing ultrasonic vibration for 8 hours at room temperature, filtering, washing with water and ethanol, and drying to obtain the crosslinked cellulose supported silver antibacterial agent.
Preparing an antibacterial and mildew-proof plastic film: adding 100% of polyvinyl chloride, 6% of cross-linked cellulose-loaded silver antibacterial agent, 40% of plasticizer dioctyl phthalate, 6% of epoxidized soybean oil, 1.4% of Rong Jima-anhydride grafted polyvinyl chloride, 2% of chlorinated paraffin and 2% of stabilizer organotin stabilizer into a mixer for mixing, and then banburying in an internal mixer at the temperature of 165 ℃ for 3min; then placing the mixture into an open mill for open-scouring, wherein the temperature in the open mill is 160 ℃, and the open-scouring time is 1.5min; extruding the mixture in an extrusion calender to form strips; finally, rolling into a film shape through rolling equipment to obtain the antibacterial and mildew-proof plastic film.
Example 5
Preparing a bis (pyridine amide schiff base) terephthalate intermediate: dissolving terephthalic acid dihydrazide, 2-formyl-5-hydroxypyridine accounting for 180 percent of the molar dosage of the terephthalic acid dihydrazide and the acetic acid solution with the concentration of 99.5 percent in a 1, 4-dioxane solvent under the protection of nitrogen, and controlling CH in the acetic acid solution 3 The molar quantity of COOH is 650% of terephthalic acid dihydrazide, reflux is carried out for 6 hours at the temperature of 110 ℃, the reaction is carried out, cooling is carried out, sodium hydroxide aqueous solution is added for neutralization, 1, 4-dioxane is concentrated and removed, ethyl acetate and water are added for extraction, the organic phase is dried by anhydrous sodium sulfate, the filtrate is concentrated after filtration, and the product is recrystallized in ethanol to obtain the terephthalic acid di (pyridine amide Schiff base) intermediate.
Preparation of pyridine amide Schiff base crosslinked cellulose: adding carboxymethyl cellulose into N, N-dimethylformamide, stirring and swelling, then respectively adding 150% of terephthalic acid di (pyridine amide Schiff base) intermediate, 80% of N-hydroxysuccinimide and 220% of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride by mass of carboxymethyl cellulose, reacting for 36 hours at room temperature, filtering, sequentially washing with water and ethanol, and drying to obtain the pyridine amide Schiff base crosslinked cellulose.
Preparing a crosslinked cellulose-loaded silver antibacterial agent: adding the pyridine amide Schiff base crosslinked cellulose into an ethanol solvent, performing ultrasonic vibration to disperse, then adding 200% silver nitrate by mass of the pyridine amide Schiff base crosslinked cellulose, controlling the mass fraction of the silver nitrate in the solution to be 30g/L, performing ultrasonic vibration at room temperature for 6 hours, filtering, washing with water and ethanol, and drying to obtain the crosslinked cellulose supported silver antibacterial agent.
Preparing an antibacterial and mildew-proof plastic film: adding 100% of polyvinyl chloride, 8% of cross-linked cellulose-loaded silver antibacterial agent, 40% of dioctyl phthalate serving as a plasticizer, 4% of epoxidized soybean oil, 2% of Rong Jima-anhydride grafted polyvinyl chloride, 4% of chlorinated paraffin and 1.5% of stabilizer organotin stabilizer into a mixer for mixing, and then banburying in an internal mixer at 160 ℃ for 4min; then placing the mixture into an open mill for open-scouring, wherein the temperature in the open mill is 150 ℃, and the open-scouring time is 2min; extruding the mixture in an extrusion calender to form strips; finally, rolling into a film shape through rolling equipment to obtain the antibacterial and mildew-proof plastic film.
Comparative example 1
Preparing a plastic film: adding 100% of polyvinyl chloride, 1% of pyridine amide Schiff base crosslinked cellulose prepared in example 1, 30% of plasticizer dioctyl phthalate, 5% of epoxidized soybean oil, 0.3% of Rong Jima-modified maleic anhydride grafted polyvinyl chloride, 4% of chlorinated paraffin and 1.5% of stabilizer organotin stabilizer into a mixer for mixing, and then banburying in an internal mixer at 165 ℃ for 3min; then placing the mixture into an open mill for open-scouring, wherein the temperature in the open mill is 155 ℃, and the open-scouring time is 3min; extruding the mixture in an extrusion calender to form strips; finally, rolling into a film shape through rolling equipment to obtain the plastic film.
Comparative example 2
Preparing a cellulose-loaded silver antibacterial agent: adding carboxymethyl cellulose into an ethanol solvent, dispersing by ultrasonic vibration, then adding 80% silver nitrate by mass of the carboxymethyl cellulose, controlling the mass fraction of the silver nitrate in the solution to be 5g/L, performing ultrasonic vibration for 4 hours at room temperature, filtering, washing with water and ethanol, and drying to obtain the cellulose-loaded silver antibacterial agent.
Preparing an antibacterial and mildew-proof plastic film: adding 100% of polyvinyl chloride, 1% of cellulose-loaded silver antibacterial agent, 30% of plasticizer dioctyl phthalate, 4% of epoxidized soybean oil, 0.3% of Rong Jima-anhydride grafted polyvinyl chloride, 3% of chlorinated paraffin and 2% of stabilizer organotin stabilizer into a mixer for mixing, and then banburying in an internal mixer at the temperature of 165 ℃ for 3min; then placing the mixture into an open mill for open-scouring, wherein the temperature in the open mill is 155 ℃, and the open-scouring time is 3min; extruding the mixture in an extrusion calender to form strips; finally, rolling into a film shape through rolling equipment to obtain the antibacterial and mildew-proof plastic film.
Antibacterial performance test: referring to QB/T2591-2003, the antibacterial performance of the antibacterial and mildew-proof plastic film is tested by adopting a film pasting method, the specification of the plastic film is a disc with the half price of 0.5cm, and the test strains are escherichia coli and candida albicans respectively, and the culture temperature is 37 ℃ and the culture time is 48 hours.
Antibacterial ratio= (a-B)/a×100%, a being the number of recovered bacteria (CFU/mL) of the blank control sample; and B is the number of recovered bacteria (CFU/mL) of the antibacterial and mildew-proof plastic film sample.
Table 1 the antibacterial rate results of escherichia coli are as follows:
table 2 candida albicans antibacterial rate results are as follows:
mildew-proof experiments were performed with reference to ASTM E1428-2015 standard to test the mildew-proof performance of the antibacterial and mildew-proof plastic film against aspergillus niger. The mildew-proof grade is 0-4, and the grade 0 is that the surface of the film has no obvious mildew erosion trace; the level 1 is that the area of the mould erosion trace is less than 10%; the level 2 is 10-30% of the area of the mould erosion trace; the level 3 is 30-50% of the area of the mould erosion trace; the grade 4 is that the area of the mould erosion trace is not less than 50 percent.
Mildew resistant grade
Example 1 1
Example 2 0
Example 3 0
Example 4 0
Example 5 0
Comparative example 1 4
Comparative example 2 2
According to antibacterial performance and mildew resistance tests, the cross-linked cellulose loaded silver antibacterial agent is added in the embodiment, the Schiff base structure containing pyridine amide can be coordinated and chelated with silver ions, the specific surface area of the cross-linked fiber is more, and the loading sites are more, so that more silver ions are loaded, and the antibacterial and mildew resistance of the polyvinyl chloride plastic film is remarkably enhanced by adding the cross-linked cellulose loaded silver antibacterial agent into the polyvinyl chloride plastic film. In comparative example 1, only pyridine amide Schiff base crosslinked cellulose was added, and no silver antibacterial agent was loaded, so that the prepared plastic film was poor in antibacterial and mildew-proof properties. Comparative example 2 silver ions were supported with carboxymethyl cellulose, and since carboxymethyl cellulose was not chemically crosslinked and contained no pyridine amide schiff base coordination chelate structure, the molecular weight of silver ions was small, and the antibacterial and mildew-proof properties of the prepared plastic film were general.
The specific embodiments described herein are offered by way of illustration only and not as limitations on the practice of the invention. Those skilled in the art to which the invention pertains may make various modifications or additions to the described embodiments or may be substituted in a similar way.

Claims (9)

1. A preparation method of an antibacterial and mildew-proof plastic film is characterized by comprising the following steps: the antibacterial mildew-proof plastic film is prepared according to the following method:
(1) Adding pyridine amide Schiff base crosslinked cellulose into an ethanol solvent, dispersing by ultrasonic vibration, then adding silver nitrate, carrying out ultrasonic vibration at room temperature for 4-10h, filtering, washing and drying to obtain a crosslinked cellulose-loaded silver antibacterial agent;
(2) Adding 100% of polyvinyl chloride, 1-8% of cross-linked cellulose loaded silver antibacterial agent, 30-45% of plasticizer, 1-6% of epoxidized soybean oil, 0.3-2% of compatibilizer, 2-6% of chlorinated paraffin and 1.5-2% of stabilizer into a mixer for mixing, and then carrying out banburying in an internal mixer; then placing the mixture into an open mill for open-scouring; extruding the mixture in an extrusion calender to form strips; finally, rolling into a film shape through rolling equipment to obtain an antibacterial and mildew-proof plastic film;
wherein, the pyridine amide Schiff base crosslinked cellulose is prepared according to the following method:
step 1), dissolving 2-formyl-5-hydroxypyridine and terephthalic acid dihydrazide into a 1, 4-dioxane solvent, dropwise adding an acetic acid solution under the protection of nitrogen, cooling after reaction, adding a sodium hydroxide aqueous solution for neutralization, concentrating, extracting and recrystallizing to obtain a terephthalic acid bis (pyridine amide Schiff base) intermediate;
step 2), adding carboxymethyl cellulose into N, N-dimethylformamide, stirring and swelling, then adding a bis (pyridine amide Schiff base) terephthalate intermediate, N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, reacting at room temperature for 24-72h, filtering, washing and drying to obtain the pyridine amide Schiff base crosslinked cellulose.
2. The method for preparing the antibacterial and mildew-proof plastic film according to claim 1, wherein the method comprises the following steps: the mass of the silver nitrate in the step (1) is 80-200% of that of the pyridine amide Schiff base crosslinked cellulose; the mass fraction of silver nitrate in the solution is controlled to be (5-30) g/L.
3. The method for preparing the antibacterial and mildew-proof plastic film according to claim 1, wherein the method comprises the following steps: the plasticizer in the step (2) is selected from dioctyl phthalate, the compatibilizer is selected from maleic anhydride grafted polyvinyl chloride, and the stabilizer is selected from organotin stabilizer.
4. The method for preparing the antibacterial and mildew-proof plastic film according to claim 1, wherein the method comprises the following steps: the temperature in the internal mixer in the step (2) is 160-170 ℃ and the internal mixing time is 2-4min.
5. The method for preparing the antibacterial and mildew-proof plastic film according to claim 1, wherein the method comprises the following steps: the temperature in the open mill in the step (2) is 150-160 ℃, and the open mill time is 1.5-3min.
6. The method for preparing the antibacterial and mildew-proof plastic film according to claim 1, wherein the method comprises the following steps: the molar amount of 2-formyl-5-hydroxypyridine in step (3) is (180-240)% of terephthalic acid dihydrazide.
7. The method for preparing the antibacterial and mildew-proof plastic film according to claim 1, wherein the method comprises the following steps: in the step (3), the concentration of the acetic acid solution is not less than 90%, and CH in the acetic acid solution 3 The molar amount of COOH is (500-800)% of terephthalic acid dihydrazide.
8. The method for preparing the antibacterial and mildew-proof plastic film according to claim 1, wherein the method comprises the following steps: the reaction in step (3) is refluxed at a temperature of 90-110 ℃ for 6-24h.
9. The method for preparing the antibacterial and mildew-proof plastic film according to claim 1, wherein the method comprises the following steps: in the step (4), the mass percentages of the phthalic acid bis (pyridine amide Schiff base) intermediate, the N-hydroxysuccinimide and the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the carboxymethyl cellulose are respectively (50-150)%, (30-80)% and (70-220)%.
CN202310726208.0A 2023-06-19 2023-06-19 Antibacterial and mildew-proof plastic film and preparation method thereof Active CN116640339B (en)

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WO2008100163A1 (en) * 2007-02-13 2008-08-21 Instytut Wlókien Naturalnych Method of manufacturing silver nanoparticles, cellulosic fibers and nanofibers containing silver nanoparticles, fibers and nanofibers containing silver nanoparticles, use of silver nanoparticles to the manufacture of cellulosic fibers and nanofibers, and wound dressing containing silver nanoparticles
CN102698313A (en) * 2012-01-11 2012-10-03 北京大学 Nano-silver antibacterial hydrogel and preparation method thereof
CN111849119A (en) * 2020-08-25 2020-10-30 广州珈鹏科技有限公司 Antibacterial plastic particles and preparation method thereof

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US9155310B2 (en) * 2011-05-24 2015-10-13 Agienic, Inc. Antimicrobial compositions for use in products for petroleum extraction, personal care, wound care and other applications

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Publication number Priority date Publication date Assignee Title
WO2008100163A1 (en) * 2007-02-13 2008-08-21 Instytut Wlókien Naturalnych Method of manufacturing silver nanoparticles, cellulosic fibers and nanofibers containing silver nanoparticles, fibers and nanofibers containing silver nanoparticles, use of silver nanoparticles to the manufacture of cellulosic fibers and nanofibers, and wound dressing containing silver nanoparticles
CN102698313A (en) * 2012-01-11 2012-10-03 北京大学 Nano-silver antibacterial hydrogel and preparation method thereof
CN111849119A (en) * 2020-08-25 2020-10-30 广州珈鹏科技有限公司 Antibacterial plastic particles and preparation method thereof

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