CN111205607A - Antibacterial environment-friendly film and preparation method thereof - Google Patents
Antibacterial environment-friendly film and preparation method thereof Download PDFInfo
- Publication number
- CN111205607A CN111205607A CN202010093827.7A CN202010093827A CN111205607A CN 111205607 A CN111205607 A CN 111205607A CN 202010093827 A CN202010093827 A CN 202010093827A CN 111205607 A CN111205607 A CN 111205607A
- Authority
- CN
- China
- Prior art keywords
- antibacterial
- film
- friendly film
- furan
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/18—Homopolymers or copolymers of nitriles
- C08J2433/20—Homopolymers or copolymers of acrylonitrile
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a preparation method of an antibacterial environment-friendly film, which is characterized by comprising the following steps: i, preparing furan thiazole-based polyester; II, preparing a copolymer based on fluorobenzene furan; III, casting to form a film; and IV, ion exchange. The invention also discloses the antibacterial environment-friendly film prepared by the preparation method of the antibacterial environment-friendly film. The antibacterial environment-friendly film disclosed by the invention is good in mechanical property, good in weather resistance and flame retardance, remarkable in antibacterial effect, excellent in environment friendliness and long in service life.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an antibacterial environment-friendly film and a preparation method thereof.
Background
In recent years, with the scientific and technological progress and the rapid development of modern industry, environmental problems become more serious, people gradually increase awareness on health and environmental protection, and higher requirements on the antibacterial property and environmental protection of various materials used in daily life are provided. Therefore, the development of materials with environmental protection and antibacterial functions is very urgent.
With the progress of polymer material synthesis technology, the film industry is driven to develop rapidly, and the film material is widely applied in daily life, such as packaging, geomembrane and the like. Regardless of the application, environmental antimicrobial properties are important and are one of the important indicators for measuring the quality of the film. The good environment-friendly antibacterial property is a reliable guarantee for preventing the film from being polluted by microorganisms or other substances in the processes of use, production, transportation, storage and sale, reducing the occurrence rate of oxidation and the like, and simultaneously playing roles in decoration and propaganda, appearance beautification, value increment and the like.
The environmental-friendly antibacterial film in the prior art is mainly realized by adding inorganic additives or coating antibacterial paint on the surface. After the inorganic antibacterial additive is added into the film, the problem of poor performance stability, limited antibacterial uniformity and durability of the material is caused by the compatibility problem of inorganic components and organic components, and the problem of film processing fluidity is caused by the addition of a large amount of the inorganic antibacterial additive. The antibacterial coating is also sterilized by a sterilizing component represented by nano silver, and the antibacterial coating has the advantages of short antibacterial time, easy oxidation and loss, easy dust pollution, easy water absorption and deterioration, low hardness, easy damage, easy shedding and poor environmental protection performance. In addition, conventional antibacterial agents usually have toxic substances, and formaldehyde, a carcinogenic substance, is generated after use.
The Chinese patent with application number 201610264755.1 discloses an antibacterial environment-friendly film and a preparation method thereof, wherein the antibacterial environment-friendly film is sequentially provided with a PET layer, an antibacterial layer, a PE layer and a bactericidal coating from inside to outside, wherein the antibacterial layer is prepared from polylactic acid, hydroxypropyl acrylate, acryloyl chloride, trifluoropropyl methyl dichlorosilane, vinyl triisopropoxysilane, hydroxypropyl methyl cellulose, chitosan, eugenol, polyvinyl alcohol, an emulsifier, an initiator and deionized water, and the bactericidal coating is prepared from ethanol, polyethylene glycol, deionized water, cinnamaldehyde, β -cyclodextrin, a titanate coupling agent, nano titanium dioxide, organic silicon resin, a dispersing agent and a defoaming agent.
Therefore, it is important to develop an antibacterial environment-friendly film with remarkable antibacterial effect, good environmental protection performance and excellent comprehensive performance.
Disclosure of Invention
In view of the above, the present invention provides an antibacterial and environment-friendly film, which has good mechanical properties, good weather resistance and flame retardancy, a significant antibacterial effect, excellent environmental protection properties, and a long service life. Meanwhile, the invention also provides a preparation method of the antibacterial environment-friendly film, and the preparation method has the advantages of easily available raw materials, low price, high preparation efficiency, simple formula and preparation process, convenience in operation and suitability for continuous large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that:
the preparation method of the antibacterial environment-friendly film is characterized by comprising the following steps:
preparation of furan thiazole-based polyester: adding 2, 5-furandimethanol, 1,2, 3-thiadiazole-4, 5-dicarboxylic acid, a catalyst and a high-boiling point solvent into a high-pressure reaction kettle, replacing air in the kettle with nitrogen or inert gas, then carrying out esterification reaction for 5-8 hours at the temperature of 220-230 ℃ and the absolute pressure of 20-80 KPa, ending esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature between 255 and 275 ℃, stirring and reacting for 18-24h, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 3-6 times by using ethanol, and finally drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the furan thiazole based polyester;
II preparation based on fluorobenzofuran copolymer: adding 4-vinyl-2, 6-dimethoxy-phenol, acrylic acid pentafluorophenol ester, vinyl benzene sulfonic acid, 4- (2-furyl) -3-butene-2-ketone, acrylonitrile and an initiator into N-methyl pyrrolidone, stirring and reacting for 3-5 hours at 70-80 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain a copolymer based on fluorobenzofuran;
III, casting to form a film: dissolving the furan thiazole-based polyester prepared in the step I and the fluorobenzene furan-based copolymer prepared in the step II in N, N-dimethylformamide to form a solution, then pouring the solution on a polytetrafluoroethylene template, and drying the polytetrafluoroethylene template for 8 to 12 hours at the temperature of 80 to 90 ℃ in an air drying oven to obtain a film;
IV, ion exchange: and (3) soaking the film cast in the step (III) in a chlorinated (1-butyl-3-methylimidazole) solution with the mass fraction of 2-5% at the temperature of 50-70 ℃ for 10-15 hours, taking out, washing with water for 3-5 times, and finally drying in a vacuum drying oven at the temperature of 80-90 ℃ to constant weight to obtain the antibacterial environment-friendly film.
Furthermore, in the step I, the mass ratio of the 2, 5-furandimethanol to the 1,2, 3-thiadiazole-4, 5-dicarboxylic acid to the catalyst to the high-boiling-point solvent is 1:1.36, (0.4-0.6) to (8-15).
Preferably, the catalyst is at least one of tetrabutyl titanate, methyl benzene sulfonic acid and titanium chloride.
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the inert gas is one of helium, neon and argon.
Furthermore, in the step II, the mass ratio of the 4-vinyl-2, 6-dimethoxy-phenol, the acrylic acid pentafluorophenol ester, the vinyl benzene sulfonic acid, the 4- (2-furyl) -3-butene-2-one, the acrylonitrile, the initiator and the N-methyl pyrrolidone is 1:0.2:0.2:0.3:2 (0.03-0.05): 10-20.
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Furthermore, the mass ratio of the furan thiazole-based polyester to the fluorobenzene furan-based copolymer to the N, N-dimethylformamide in the step III is 1 (0.8-1.2) to (30-50).
Furthermore, the mass ratio of the film to the (1-butyl-3-methylimidazole) chloride solution in the step IV is 1 (10-20).
The invention also aims to provide the antibacterial environment-friendly film prepared by the preparation method of the antibacterial environment-friendly film.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the antibacterial environment-friendly film provided by the invention has the advantages of easily available raw materials, low price, high preparation efficiency, simple formula and preparation process, convenience in operation and suitability for continuous large-scale production.
(2) The antibacterial environment-friendly film provided by the invention overcomes the defects that the traditional film is poor in antibacterial performance and needs to be further improved in performance stability and comprehensive performance, and has the advantages of good mechanical property, good weather resistance and flame retardance, remarkable antibacterial effect, excellent environmental protection performance and long service life.
(3) The antibacterial environment-friendly film provided by the invention takes furan thiazole-based polyester and fluorobenzene furan-based copolymer dissolved in N, N-dimethylformamide blend as a base material, combines the advantages of polyester, fluorobenzene and furan-based materials, and has good weather resistance and mechanical properties, and because two polymers both contain furyl, the compatibility of the two polymers is enhanced, the risk of phase separation is reduced, the material structure is more compact, the comprehensive performance is better, and benzenesulfonic acid on the side chain of the copolymer can be used as a curing agent in the casting film-forming stage, so that the furyl is crosslinked, a three-dimensional network structure is formed, and the comprehensive performance is further improved; a thiazole structure is introduced into the main chain of the furan thiazole polyester, so that the antibacterial performance of the film is effectively improved; and finally, soaking the membrane in a chlorinated (1-butyl-3-methylimidazole) solution to enable sulfonic groups which do not participate in reaction on the copolymer to be combined with imidazole cations through chemical bonds, so that the surface performance of the membrane is improved, the moisture-proof and waterproof performance of the membrane is improved, and an imidazole salt structure is introduced through ionic bonds to further improve the antibacterial performance, and the antibacterial active ingredients have synergistic effect, so that the antibacterial broad spectrum property is good, and the antibacterial durability is good.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The raw materials in the embodiment of the invention are all purchased commercially.
Example 1
The preparation method of the antibacterial environment-friendly film is characterized by comprising the following steps:
preparation of furan thiazole-based polyester: adding 10g of 2, 5-furandimethanol, 13.6g of 1,2, 3-thiadiazole-4, 5-dicarboxylic acid, 4g of tetrabutyl titanate and 80g of dimethyl sulfoxide into a high-pressure reaction kettle, replacing the air in the kettle with nitrogen, then carrying out esterification reaction for 5 hours at the temperature of 220 ℃ and the absolute pressure of 20KPa, ending the esterification, and relieving the pressure to the normal pressure; then under the vacuum condition, controlling the temperature between 255 ℃, stirring and reacting for 18h, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 3 times by using ethanol, and finally drying in a vacuum drying oven at 80 ℃ to constant weight to obtain the furan thiazole-based polyester;
II preparation based on fluorobenzofuran copolymer: adding 10g of 4-vinyl-2, 6-dimethoxy-phenol, 2g of acrylic acid pentafluorophenol ester, 2g of vinyl benzene sulfonic acid, 3g of 4- (2-furyl) -3-butene-2-one, 20g of acrylonitrile and 0.3g of azobisisobutyronitrile into 100g of N-methyl pyrrolidone, stirring and reacting for 3 hours at the temperature of 70 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 3 times by using ethanol, and finally drying in a vacuum drying oven at the temperature of 80 ℃ to constant weight to obtain a copolymer based on fluorobenzofuran;
III, casting to form a film: dissolving 10g of furan thiazole polyester prepared in the step I and 8g of fluorobenzene furan copolymer prepared in the step II in 300g of N, N-dimethylformamide to form a solution, then pouring the solution on a polytetrafluoroethylene template, and drying the polytetrafluoroethylene template for 8 hours at the temperature of 80 ℃ in an air drying oven to obtain a film;
IV, ion exchange: and (3) soaking 10g of the film cast in the step (III) in 100g of chlorinated (1-butyl-3-methylimidazole) solution with the mass fraction of 2% at 50 ℃ for 10 hours, taking out, washing with water for 3 times, and finally drying in a vacuum drying oven at 80 ℃ to constant weight to obtain the antibacterial environment-friendly film.
An antibacterial environment-friendly film prepared according to the preparation method of the antibacterial environment-friendly film.
Example 2
The preparation method of the antibacterial environment-friendly film is characterized by comprising the following steps:
preparation of furan thiazole-based polyester: adding 10g of 2, 5-furandimethanol, 13.6g of 1,2, 3-thiadiazole-4, 5-dicarboxylic acid, 4.5g of methylbenzenesulfonic acid and 100g of N, N-dimethylformamide into a high-pressure reaction kettle, replacing air in the kettle with helium, then carrying out esterification reaction for 6 hours at the temperature of 223 ℃ and the absolute pressure of 35KPa, ending the esterification, and releasing the pressure to the normal pressure; then under the vacuum condition, controlling the temperature to be 260 ℃, stirring and reacting for 20h, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 4 times, and finally drying in a vacuum drying oven at 82 ℃ to constant weight to obtain the furan thiazole-based polyester;
II preparation based on fluorobenzofuran copolymer: adding 10g of 4-vinyl-2, 6-dimethoxy-phenol, 2g of acrylic acid pentafluorophenol ester, 2g of vinyl benzene sulfonic acid, 3g of 4- (2-furyl) -3-butene-2-one, 20g of acrylonitrile and 0.35g of azobisisoheptonitrile into 130g of N-methylpyrrolidone, stirring and reacting for 3.5 hours at 73 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and finally drying in a vacuum drying oven at 82 ℃ to constant weight to obtain a copolymer based on fluorobenzofuran;
III, casting to form a film: dissolving 10g of furan thiazole polyester prepared in the step I and 9g of fluorobenzene furan copolymer prepared in the step II in 350g of N, N-dimethylformamide to form a solution, pouring the solution on a polytetrafluoroethylene template, and drying the polytetrafluoroethylene template for 9 hours at 83 ℃ in a forced air drying oven to obtain a film;
IV, ion exchange: and (3) soaking 10g of the film cast in the step (III) in 130g of chlorinated (1-butyl-3-methylimidazole) solution with the mass fraction of 3% at the temperature of 55 ℃ for 11 hours, taking out, washing with water for 4 times, and finally drying in a vacuum drying oven at the temperature of 82 ℃ to constant weight to obtain the antibacterial environment-friendly film.
An antibacterial environment-friendly film prepared according to the preparation method of the antibacterial environment-friendly film.
Example 3
The preparation method of the antibacterial environment-friendly film is characterized by comprising the following steps:
preparation of furan thiazole-based polyester: adding 10g of 2, 5-furandimethanol, 13.6g of 1,2, 3-thiadiazole-4, 5-dicarboxylic acid, 5g of titanium chloride and 120g of N, N-dimethylacetamide into a high-pressure reaction kettle, replacing air in the kettle with neon, then carrying out esterification reaction for 6.5 hours at the temperature of 225 ℃ and the absolute pressure of 50KPa, ending esterification, and releasing pressure to normal pressure; then under the vacuum condition, controlling the temperature between 265 ℃, stirring and reacting for 21h, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 5 times, and finally drying in a vacuum drying oven at 85 ℃ to constant weight to obtain the furan thiazole-based polyester;
II preparation based on fluorobenzofuran copolymer: adding 10g of 4-vinyl-2, 6-dimethoxy-phenol, 2g of acrylic acid pentafluorophenol ester, 2g of vinyl benzene sulfonic acid, 3g of 4- (2-furyl) -3-butene-2-one, 20g of acrylonitrile and 0.4g of azobisisobutyronitrile into 150g of N-methyl pyrrolidone, stirring and reacting for 4 hours at 75 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 5 times by using ethanol, and finally drying in a vacuum drying oven at 85 ℃ to constant weight to obtain a copolymer based on fluorobenzofuran;
III, casting to form a film: dissolving 10g of the furan thiazole polyester prepared in the step I and 10g of the fluorobenzene furan copolymer prepared in the step II in 400g of N, N-dimethylformamide to form a solution, then pouring the solution on a polytetrafluoroethylene template, and drying the polytetrafluoroethylene template for 10 hours at 85 ℃ in an air drying oven to obtain a film;
IV, ion exchange: and (3) soaking 10g of the film cast in the step (III) in 150g of chlorinated (1-butyl-3-methylimidazole) solution with the mass fraction of 3.5% at the temperature of 60 ℃ for 13 hours, taking out, washing with water for 4 times, and finally drying in a vacuum drying oven at the temperature of 85 ℃ to constant weight to obtain the antibacterial environment-friendly film.
An antibacterial environment-friendly film prepared according to the preparation method of the antibacterial environment-friendly film.
Example 4
The preparation method of the antibacterial environment-friendly film is characterized by comprising the following steps:
preparation of furan thiazole-based polyester: adding 10g of 2, 5-furandimethanol, 13.6g of 1,2, 3-thiadiazole-4, 5-dicarboxylic acid, 5.5g of catalyst and 140g of high-boiling-point solvent into a high-pressure reaction kettle, replacing the air in the kettle with argon, carrying out esterification reaction for 7.5 hours at the temperature of 228 ℃ and the absolute pressure of 70KPa, finishing esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature to be 270 ℃, stirring and reacting for 23h, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally drying to constant weight in a vacuum drying oven at 88 ℃ to obtain the furan thiazole-based polyester; the catalyst is formed by mixing tetrabutyl titanate, methyl benzenesulfonic acid and titanium chloride according to the mass ratio of 2:1: 3; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:3:5: 4;
II preparation based on fluorobenzofuran copolymer: adding 10g of 4-vinyl-2, 6-dimethoxy-phenol, 2g of acrylic acid pentafluorophenol ester, 2g of vinyl benzene sulfonic acid, 3g of 4- (2-furyl) -3-butene-2-one, 20g of acrylonitrile and 0.45g of initiator into 190g of N-methyl pyrrolidone, stirring and reacting for 4.5 hours at 78 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally drying in a vacuum drying oven at 89 ℃ to constant weight to obtain a copolymer based on fluorobenzene furan; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5;
III, casting to form a film: dissolving 10g of the furan thiazole polyester prepared in the step I and 11g of the fluorobenzene furan copolymer prepared in the step II in 480g of N, N-dimethylformamide to form a solution, then pouring the solution on a polytetrafluoroethylene template, and drying the polytetrafluoroethylene template for 11 hours at 88 ℃ in an air drying oven to obtain a film;
IV, ion exchange: and (3) soaking 10g of the film cast in the step (III) in 190g of chlorinated (1-butyl-3-methylimidazole) solution with the mass fraction of 4.5% at 68 ℃ for 14 hours, taking out, washing with water for 5 times, and finally drying in a vacuum drying oven at 88 ℃ to constant weight to obtain the antibacterial environment-friendly film.
An antibacterial environment-friendly film prepared according to the preparation method of the antibacterial environment-friendly film.
Example 5
The preparation method of the antibacterial environment-friendly film is characterized by comprising the following steps:
preparation of furan thiazole-based polyester: adding 10g of 2, 5-furandimethanol, 13.6g of 1,2, 3-thiadiazole-4, 5-dicarboxylic acid, 6g of methylbenzenesulfonic acid and 150g of N-methylpyrrolidone into a high-pressure reaction kettle, replacing the air in the kettle with nitrogen, then carrying out esterification reaction for 8 hours at the temperature of 230 ℃ and the absolute pressure of 80KPa, ending the esterification, and relieving the pressure to the normal pressure; then under the vacuum condition, controlling the temperature to 275 ℃, stirring and reacting for 24h, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 6 times, and finally drying in a vacuum drying oven at 90 ℃ to constant weight to obtain the furan thiazole-based polyester;
II preparation based on fluorobenzofuran copolymer: adding 10g of 4-vinyl-2, 6-dimethoxy-phenol, 2g of acrylic acid pentafluorophenol ester, 2g of vinyl benzene sulfonic acid, 3g of 4- (2-furyl) -3-butene-2-one, 20g of acrylonitrile and 0.5g of azobisisoheptonitrile into 200g of N-methylpyrrolidone, stirring and reacting for 5 hours at 80 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally drying at 90 ℃ in a vacuum drying oven to constant weight to obtain the copolymer based on fluorobenzene furan;
III, casting to form a film: dissolving 10g of furan thiazole polyester prepared in the step I and 12g of fluorobenzene furan copolymer prepared in the step II in 500g of N, N-dimethylformamide to form a solution, then pouring the solution on a polytetrafluoroethylene template, and drying the polytetrafluoroethylene template in an air-blast drying oven at 90 ℃ for 12 hours to obtain a film;
IV, ion exchange: and (3) soaking 10g of the film cast in the step (III) in 200g of chlorinated (1-butyl-3-methylimidazole) solution with the mass fraction of 5% at 70 ℃ for 15 hours, taking out, washing with water for 5 times, and finally drying in a vacuum drying oven at 90 ℃ to constant weight to obtain the antibacterial environment-friendly film.
An antibacterial environment-friendly film prepared according to the preparation method of the antibacterial environment-friendly film.
Comparative example 1
This example provides an antibacterial environmentally friendly film having substantially the same formulation and preparation method as example 1, except that the fluorobenzene furan-based copolymer is not added.
Comparative example 2
This example provides an antimicrobial environmentally friendly film having substantially the same formulation and preparation method as example 1, except that no furan thiazole based polyester is added.
Comparative example 3
This example provides an antimicrobial environmentally friendly film having substantially the same formulation and preparation method as example 1, except that no ion exchange step was performed.
The performance of the antibacterial and environmentally friendly film described in the above examples 1 to 5 and comparative examples 1 to 3 was tested, and the test method and test results are shown in table 1.
As can be seen from table 1, the antibacterial and environmental-friendly film disclosed in the examples of the present invention has more excellent antibacterial property and mechanical property than the comparative examples, which are the result of the synergistic effect of the components.
TABLE 1
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The preparation method of the antibacterial environment-friendly film is characterized by comprising the following steps:
preparation of furan thiazole-based polyester: adding 2, 5-furandimethanol, 1,2, 3-thiadiazole-4, 5-dicarboxylic acid, a catalyst and a high-boiling point solvent into a high-pressure reaction kettle, replacing air in the kettle with nitrogen or inert gas, then carrying out esterification reaction for 5-8 hours at the temperature of 220-230 ℃ and the absolute pressure of 20-80 KPa, ending esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature between 255 and 275 ℃, stirring and reacting for 18-24h, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer for 3-6 times by using ethanol, and finally drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the furan thiazole based polyester;
II preparation based on fluorobenzofuran copolymer: adding 4-vinyl-2, 6-dimethoxy-phenol, acrylic acid pentafluorophenol ester, vinyl benzene sulfonic acid, 4- (2-furyl) -3-butene-2-ketone, acrylonitrile and an initiator into N-methyl pyrrolidone, stirring and reacting for 3-5 hours at 70-80 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain a copolymer based on fluorobenzofuran;
III, casting to form a film: dissolving the furan thiazole-based polyester prepared in the step I and the fluorobenzene furan-based copolymer prepared in the step II in N, N-dimethylformamide to form a solution, then pouring the solution on a polytetrafluoroethylene template, and drying the polytetrafluoroethylene template for 8 to 12 hours at the temperature of 80 to 90 ℃ in an air drying oven to obtain a film;
IV, ion exchange: and (3) soaking the film cast in the step (III) in a chlorinated (1-butyl-3-methylimidazole) solution with the mass fraction of 2-5% at the temperature of 50-70 ℃ for 10-15 hours, taking out, washing with water for 3-5 times, and finally drying in a vacuum drying oven at the temperature of 80-90 ℃ to constant weight to obtain the antibacterial environment-friendly film.
2. The method for preparing the antibacterial environment-friendly film as claimed in claim 1, wherein the mass ratio of the 2, 5-furandimethanol, the 1,2, 3-thiadiazole-4, 5-dicarboxylic acid, the catalyst and the high-boiling point solvent in the step I is 1:1.36, (0.4-0.6): 8-15.
3. The method for preparing an antibacterial environment-friendly film according to claim 1, wherein the catalyst is at least one of tetrabutyl titanate, methyl benzene sulfonic acid and titanium chloride.
4. The method for preparing an antibacterial environment-friendly film according to claim 1, wherein the high boiling point solvent is at least one of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
5. The method for preparing an antibacterial environmental protection film according to claim 1, wherein the inert gas is one of helium, neon and argon.
6. The method for preparing an antibacterial environment-friendly film as claimed in claim 1, wherein in the step II, the mass ratio of the 4-vinyl-2, 6-dimethoxy-phenol, the acrylic acid pentafluorophenol ester, the vinyl benzene sulfonic acid, the 4- (2-furyl) -3-buten-2-one, the acrylonitrile, the initiator and the N-methyl pyrrolidone is 1:0.2:0.2:0.3:2 (0.03-0.05): 10-20.
7. The method of claim 1, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
8. The method for preparing an antibacterial environment-friendly film as claimed in claim 1, wherein the mass ratio of the furan thiazole-based polyester to the fluorobenzene furan-based copolymer to the N, N-dimethylformamide in the step III is 1 (0.8-1.2) to (30-50).
9. The method for preparing the antibacterial environment-friendly film according to claim 1, wherein the mass ratio of the film to the (1-butyl-3-methylimidazole) chloride solution in the step IV is 1 (10-20).
10. An antibacterial environmentally friendly film prepared by the method for preparing an antibacterial environmentally friendly film according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010093827.7A CN111205607A (en) | 2020-02-14 | 2020-02-14 | Antibacterial environment-friendly film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010093827.7A CN111205607A (en) | 2020-02-14 | 2020-02-14 | Antibacterial environment-friendly film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111205607A true CN111205607A (en) | 2020-05-29 |
Family
ID=70786880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010093827.7A Withdrawn CN111205607A (en) | 2020-02-14 | 2020-02-14 | Antibacterial environment-friendly film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111205607A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116080112A (en) * | 2022-10-10 | 2023-05-09 | 江阴市申美包装材料有限公司 | Antibacterial composite film for medical instrument and preparation method thereof |
-
2020
- 2020-02-14 CN CN202010093827.7A patent/CN111205607A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116080112A (en) * | 2022-10-10 | 2023-05-09 | 江阴市申美包装材料有限公司 | Antibacterial composite film for medical instrument and preparation method thereof |
| CN116080112B (en) * | 2022-10-10 | 2023-09-29 | 江阴市申美包装材料有限公司 | Antibacterial composite film for medical instrument and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE102007041722A1 (en) | Process for the preparation of conductive polymers | |
| EP2238194A1 (en) | Method for the production of conductive<i></i>polymers | |
| CN101177479A (en) | Method for preparing self-emulsification aqueous epoxy resin emulsion | |
| JP5589354B2 (en) | Cellulose fiber, molded body and display element substrate | |
| CN111617641A (en) | Imidazole functionalized ionic liquid copolymer synthesis and alloy ultrafiltration membrane preparation method | |
| CN111205607A (en) | Antibacterial environment-friendly film and preparation method thereof | |
| CN111978772A (en) | Antibacterial and antivirus powder coating and preparation process thereof | |
| Zhou et al. | Effect of metal ions with reducing properties on hydrogels containing catechol groups | |
| CN110358437B (en) | High-performance environment-friendly water-based paint and preparation method thereof | |
| CN112094378B (en) | Hyperbranched polyester, preparation method thereof and water-based paint prepared from hyperbranched polyester | |
| KR102311273B1 (en) | Conductive copper powder based oil paste for improved long term stability and manufacturing method thereof | |
| CN109294176A (en) | A kind of antibacterial flame-retardant PET composite material and preparation method thereof | |
| CN102093717B (en) | Sulfonated polyethersulfone/TiO2 nano composite material and preparation method thereof | |
| CN107286547B (en) | Preparation method of chitin liquefied product/polyvinyl alcohol blending film | |
| CN107189083B (en) | Conductive polymer PEDOT organic dispersion system and preparation method thereof | |
| CN110863261B (en) | Phase-change temperature-regulating composite fiber with chitosan as matrix and preparation method thereof | |
| CN106811034A (en) | A kind of water-based insulating paint material and preparation method thereof | |
| CN105542480A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and P(CPP-SA)-polyethylene glycol | |
| CN115490926A (en) | High-transparency low-temperature-processable cellulose acetate film and preparation method thereof | |
| KR101577911B1 (en) | A method for preparing polyvinyl alcohol films by the heterogeneous surface saponification of polyvinyl acetate films | |
| CN102585263B (en) | Preparation method of organic montmorillonite-modified gelatin/PVA (polyvinyl acetate) composite film | |
| CN114349874A (en) | Preparation method of hydrophobically modified sodium carboxymethyl starch | |
| CN109467631B (en) | Solid anti-mud ultra-slow release type polycarboxylic slump retaining agent and preparation method thereof | |
| CN112239629A (en) | Alkali-resistant mildew-proof water-based black paint and preparation method thereof | |
| KR100671122B1 (en) | High Conductive Coating Composition for Electromagnetic Interference Shielding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200529 |