CN105646922A - Gel film with curdlan quaternary ammonium salt and polyvinyl alcohol and antibacterial application of gel film - Google Patents

Gel film with curdlan quaternary ammonium salt and polyvinyl alcohol and antibacterial application of gel film Download PDF

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CN105646922A
CN105646922A CN201610204266.7A CN201610204266A CN105646922A CN 105646922 A CN105646922 A CN 105646922A CN 201610204266 A CN201610204266 A CN 201610204266A CN 105646922 A CN105646922 A CN 105646922A
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polyvinyl alcohol
quaternary ammonium
ammonium salt
curdlan quaternary
thin film
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CN105646922B (en
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陈美玲
梁萍萍
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Jiangnan University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00Compositions 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/02Dextran; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/02Dextran; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00Characterised 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

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Abstract

The invention relates to a gel film with curdlan quaternary ammonium salt and polyvinyl alcohol and application of the gel film in the antibacterial aspect. The curdlan quaternary ammonium salt and the polyvinyl alcohol are used as film-forming materials for the gel film. The polyvinyl alcohol is emulsified and hydrophobically modified by the aid of grease substances, and packaging materials comprise components including the 0.02-0.10g/mL H2O polyvinyl alcohol, 0.002-0.020 g/mL H2O total surfactants, the 0.005-0.02 g/mL H2O grease substances and 0.005-0.02 g/mL H2O plasticizers, the components are subjected to reaction, composite emulsification, freezing, thawing and cross-linking in aqueous solution to obtain the packaging materials, and a weight ratio of the curdlan quaternary ammonium salt to the polyvinyl alcohol is 4:1-1:4. Mixed emulsion is subjected to repeated freezing, thawing and cross-linking at the temperatures of -10--40 DEG C after being poured into a container, standing still and being de-foamed, and then is dried at the temperatures of 30-40 DEG C by means of air blowing so as to obtain the gel film. The gel film with the curdlan quaternary ammonium salt and the polyvinyl alcohol and the application have the advantages that the gel film has uniform microstructures and broad-spectrum antibacterial and sterilization performance and is excellent in mechanical property, and antibacterial effects can be realized by the gel film for Escherichia coli, staphylococcus, staphylococcus aureus and mildew; the gel film can be degraded, and the antibacterial effects can be realized by the gel film.

Description

A kind of curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film and antibacterial application thereof
Technical field
The preparation method that the present invention relates to a kind of curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film, the method adopting repeatedly freeze-thaw prepares a kind of curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film with bacteriostatic activity, this gel film have microstructure uniformly, hot property and good mechanical properties, there is broad-spectrum antibacterial performance simultaneously. The invention belongs to field of compound material, be mainly used in the packaging material such as hygienic material such as preservative film, food pack, drug packaging.
Background technology
Along with the decline of the raising of living standards of the people and the enhancing of environmental consciousness and oil, coal reserves, healthy and green concept is increasingly by well-established greatly. Along with people to improving constantly of food quality and safety health demand and advocating of green package theory, people are also more and more higher to the requirement of fresh-keeping packaging material, and at food packing industry, the anti-biotic material demand that can effectively prevent bacterial cross-infection is very big. Exploitation biological degradability, safety, wide spectrum, stable performance natural anticorrosion antibacterial film more and more interested to researchers. The market demand of natural anticorrosion antibacterial film is also inevitable growing. Packaging material for food needs have suitable mechanical performance, water-fast and gas barrier property, heat stability, antibacterial activity and affected by environment low. Such material delays the deterioration of food, and maintains quality and the safety of food. Both at home and abroad still being in the blank stage utilizing curdlan derivant to prepare fresh-keeping packaging material field, the film research of curdlan derivant has great importance for the macromolecule membrane of petroleum replacing chemical raw material synthesis. Because synthetic polymer thin film is inexpensive, it is convenient and highly durable to produce from raw material, is therefore widely used in packaging for foodstuff. But, because they are not biodegradable, so these thin film may result in serious white pollution, from biodegradable biopolymer, therefore find the interest that succedaneum causes people increasing.
Curdlan quaternary ammonium salt is with curdlan for raw material, and deionized water is solvent, with glycidyltrimetiiylammonium ammonium chloride for modifying agent, is prepared by two-step reaction.Wherein curdlan is also known as heat setting glue, condenses polysaccharide, microorganism produces, and with ��-1, the water-insoluble glucan that 3-glycosidic bond is constituted, relative molecular weight is about 50��2,000,000. Curdlan belongs to bio-molecules, this biodegradable polyol of natural polysaccharide macro-molecular shows the character of a series of uniqueness, such as good biodegradable and biocompatibility and the toxic action etc. that nano-carrier is potential can be prevented effectively from or reduce. Thus utilize gel film prepared by polysaccharide-modified product to obtain pay close attention to widely due to its potential biology and application prospect pharmaceutically.
Polyvinyl alcohol is a kind of water solublity synthesising macromolecule copolymer, and structural formula is-CH2CH(OH)n-, it is a kind of white powder or granular water soluble macromolecule resin, by polyvinyl acetate ([CH2CHCOOCH3]n) be hydrolyzed and obtain. Intermolecular exist great amount of hydroxy group, has good water absorption, excellent barrier properties for gases, and its solution has good film property and avirulence, and degradation speed is fast, can is CO by bacterial degradation in soil2And H2The features such as O, solves the plastics difficult degradation pollution problem to environment, good mechanical performance. And polyvinyl alcohol has high-k and insulating properties, therefore polyvinyl alcohol is widely used in packaging industry and electronics industry. Polyvinyl alcohol can be divided into the superelevation degree of polymerization, high polymerization degree, the middle degree of polymerization, low polymerization degree four kinds by the degree of polymerization by molecular weight grade. Generally, superelevation degree of polymerization polyvinyl alcohol molecule amount is 25-30 ten thousand, and polyvinyl alcohol of high degree of polymerization molecular weight is 17-22 ten thousand, and middle degree of polymerization polyvinyl alcohol is 12-15 ten thousand, and polyvinyl alcohol with low degree of polymerization molecular weight is 2.5-3.5 ten thousand. In general, the degree of polymerization increases, and the viscosity of the aqueous solution of same concentrations increases, and intensity and solvent resistance after film forming increase, but the dissolubility in water declines, and the percentage elongation after film forming declines. The dissolubility of polyvinyl alcohol is relevant with alcoholysis degree and the degree of polymerization thereof, and alcoholysis degree and the degree of polymerization are high, then polyvinyl alcohol dissolves slow; Alcoholysis degree and the degree of polymerization are low, and polyvinyl alcohol dissolves fast. Generally, alcoholysis degree on the impact of polyvinyl alcohol solubility more than the degree of polymerization impact on it. Polyvinyl alcohol course of dissolution is: affine moistening, swelling, infinite swelling, dissolves. Polyvinyl alcohol molecule chain contains great amount of hydroxy group (-OH) and hydrogen bond so that it is have good water solublity, it is possible to natural polymer by hydrogen bond crosslinks, compact siro spinning technology. Owing to curdlan quaternary ammonium salt is dissolved in water, and containing substantial amounts of active hydroxyl groups, utilize the method for physical crosslinking to make curdlan quaternary ammonium salt and polyvinyl alcohol cross-link, prepare gel film.
Repetitive freezing thawing method is a kind of physical method preparing macromolecule hydrogel, the hydrogel formed in this way does not introduce the chemical cross-linking agent to organism toxic side effect, and prepare hydrogel moisture content higher, at medical domain, there is extensive use, repeatedly freeze-thaw several times after, so that it may make some of physical property and mechanical performance have greatly improved. This hydrogel has certain mechanical strength and good elasticity, can only by swelling and can not be dissolved in water under room temperature. Gel film will be formed by after hydrogel drying and dehydrating.
Summary of the invention
It is an object of the invention to provide a kind of curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film, curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film that the present invention obtains have microstructure uniformly, good mechanical properties there is broad-spectrum antibacterial performance simultaneously, to colibacillus, staphylococcus, staphylococcus aureus, mycete has bacteriostasis.This gel film both degradables have antibacterial effect simultaneously.
Curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film that the present invention obtains, has the advantage that
1. the curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film prepared has the bacteriostasis property of wide spectrum;
2. the microstructure of the curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film prepared is uniform, good mechanical properties;
3. the curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film prepared has degradability.
4. the steam that vegetable and fruit is breathed out forms water layer rather than water droplet at prepared curdlan quaternary ammonium salt/polyvinyl alcohol gel film surface, and this can prevent water droplet to be dropped on vegetable and fruit compared with commercially available preservative film, it is to avoid pollute.
5. the curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film good emulsion stability prepared.
The technical scheme is that
The preparation method that the invention discloses a kind of curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film, including following preparation process:
(1) taking the mixing of certain polyethylene alcohol and water, stirring and dissolving 2-3h, obtain poly-vinyl alcohol solution, wherein poly-vinyl alcohol solution concentration is 0.02g��0.10g/mLH2O;
(2) being added by a certain percentage by surfactant in (1), stirring and dissolving 0.5-2h at 30��90 DEG C, wherein surfactant adds concentration is 0.001g��0.01g/mLH2O, wherein surfactant can be one or both in sucrose ester S-1570, APG, polyethylene glycol oxide (20) glyceryl monostearate, polyethylene glycol oxide (20) sorbitan monostearate;
(3) being added by a certain percentage in oil substances by surfactant, stir 0.5-1h at 30��80 DEG C, wherein surfactant adds concentration is 0.001g��0.01g/mLH2O, wherein surfactant can be one or both in Span-80, sorbitan fatty acid ester S-60, glyceryl stearate, glyceryl monolaurate, and it is 0.005g��0.02g/mLH that oil substances adds concentration2O, wherein oil substances can be vegetable oil or liquid paraffin;
(4) the oils and fats mixed liquor prepared in (3) is added dropwise to solution prepared in (2), stirring and emulsifying 1-8h under 30��80 DEG C of conditions;
(5) plasticizer adding emulsion by a certain percentage that prepare in (4), stirs 0.5-1h under 30��80 DEG C of conditions, wherein plasticizer adds concentration is 0.005g��0.02g/mLH2O, wherein plasticizer can be one or both in glycerol, stearic acid, glucose, oleic acid, epoxy soybean oil, sorbitol;
(6) curdlan quaternary ammonium salt adds the emulsion prepared in (5) and stirring and dissolving 1-2h by a certain percentage, and wherein curdlan quaternary ammonium salt is 4: 1��1: 4 with the weight ratio of polyvinyl alcohol;
(7) mixed solution prepared in (6) is poured into in film container, pave rear degassed, after container is placed at-10 DEG C��-40 DEG C repeatedly freezing 3��5h, it is placed in 30��40 DEG C of canyons and dries, obtain curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.
The invention also discloses a kind of above-mentioned preparation method and prepare the curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film of gained.
The thickness range of described curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film is 10 ��m��1000 ��m.
Described curdlan quaternary ammonium salt/polyvinyl alcohol gel film surface is smooth, internal porose, and pore diameter range is 125 ��m��600 ��m.
The invention also discloses the application that a kind of above-mentioned preparation method prepares the curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film of gained, colibacillus, staphylococcus, staphylococcus aureus and mycete are had bacteriostasis by this curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film, are applied particularly in medicine, food, daily chemical product as antibiotic packaging material.
Figure of description
Fig. 1 is the field emission scanning electron microscope sectional drawing of embodiment 3 curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.
Antibacterial figure, Fig. 2 (a) that Fig. 2 is embodiment 2 curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film are escherichia coli, and Fig. 2 (b) is staphylococcus.
Detailed description of the invention
The curdlan quaternary ammonium salt adopted in following specific embodiment prepares gained and any one structure that the chemical constitution of the curdlan quaternary ammonium salt adopted is curdlan quaternary ammonium salt described in patent application 201510508036.5 by preparation method described in patent application 201510508036.5; The polyvinyl alcohol adopted in following specific embodiment is the polyvinyl alcohol of any molecular size range, can directly adopt commercial polyethylene alcohol, and carry out the adjustment of molecular size range according to the mechanical requirements of final required curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.
Embodiment 1:(1) take immersion 30min, stirring and dissolving 2h under 4g polyvinyl alcohol 100mL deionized water room temperature, obtain poly-vinyl alcohol solution; (2) take 0.12g sucrose ester S-1570 and join in (1), stirring and dissolving 1h at 30 DEG C; (3) take 0.12gSpan-80 and be added in 0.6g liquid paraffin, at 30 DEG C, stir 0.5h; (4) the paraffin mixed liquor prepared in (3) is instilled the solution prepared in (2), stirring and emulsifying 8h under 30 DEG C of conditions; (5) take 1g epoxy soybean oil by adding the emulsion prepared in (4), at 60 DEG C, stir 0.5h; (6) take 1g curdlan quaternary ammonium salt and add the emulsion prepared in (5), stirring and dissolving 2h; (7) mixed solution prepared in (6) is poured in container, pave rear degassed, freezing 4 hours at container is placed in-10 DEG C, then take out container in thawed at room temperature 3 hours, after being repeatedly performed above-mentioned freeze-thaw process 3 times, it is placed in 30 DEG C of canyons to dry, obtains curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.
Embodiment 2:(1) take immersion 40min, stirring and dissolving 2h under 2.5g polyvinyl alcohol 100mL deionized water room temperature, obtain poly-vinyl alcohol solution; (2) take 0.16g sucrose ester S-1570 and join in (1), stirring and dissolving 1h at 60 DEG C; (3) take 0.16gSpan-80 to be added in 0.8g liquid paraffin at 60 DEG C and stir 0.5h; (4) the paraffin mixed liquor prepared in (3) is instilled the solution prepared in (2), stirring and emulsifying 5h at 60 DEG C; (5) take 0.5g glycerol by adding the emulsion prepared in (4), at 60 DEG C, stir 0.5h; (6) take 2.5g curdlan quaternary ammonium salt and add the emulsion prepared in (5), stirring and dissolving 2h; (7) mixed solution prepared in (6) is poured in container, pave rear degassed, freezing 4 hours at container is placed in-20 DEG C, then take out container in thawed at room temperature 3 hours, after being repeatedly performed above-mentioned freeze-thaw process 5 times, it is placed in 30 DEG C of canyons to dry, obtains curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.
Embodiment 3:(1) take immersion 40min, stirring and dissolving 2h under 3.5g polyvinyl alcohol 100mL deionized water room temperature, obtain poly-vinyl alcohol solution; (2) take 0.20g sucrose ester S-1570 and join in (1), stirring and dissolving 1h at 80 DEG C; (3) take 0.20gSpan-80 to be added in 1.0g liquid paraffin at 80 DEG C and stir 0.5h; (4) the paraffin mixed liquor prepared in (3) is instilled the solution prepared in (2), stirring and emulsifying 2h at 80 DEG C; (5) take 1.5g glycerol by adding the emulsion prepared in (4), at 80 DEG C, stir 0.5h; (6) take 1.5g curdlan quaternary ammonium salt and add the emulsion prepared in (5), stirring and dissolving 2h;(7) mixed solution prepared in (6) is poured in container, pave rear degassed, freezing 4 hours at container is placed in-10 DEG C, then take out container in thawed at room temperature 3 hours, after being repeatedly performed above-mentioned freeze-thaw process 3 times, it is placed in 40 DEG C of canyons to dry, obtains curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.
Fig. 1 is the field emission scanning electron microscope sectional drawing of embodiment 3 curdlans/polyvinyl alcohol gel thin film. The section of curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film is the network structure of porous as can be seen from Figure 1, showing that polyvinyl alcohol and curdlan quaternary ammonium salt have the good compatibility, curdlan quaternary ammonium salt can produce interaction of hydrogen bond by hydroxyl with polyvinyl alcohol and be closely linked.
Embodiment 4:(1) take immersion 30min, stirring and dissolving 2h under 4g polyvinyl alcohol 100mL deionized water room temperature, obtain poly-vinyl alcohol solution; (2) take 0.10g APG and join in (1), stirring and dissolving 1h at 80 DEG C; (3) take 0.10gSpan-80 to be added in 0.5g soybean oil at 80 DEG C and stir 0.5h; (4) the soybean oil mixed liquor prepared in (3) is instilled the solution prepared in (2), stirring and emulsifying 5h at 80 DEG C; (5) take 2.0g glycerol by adding the emulsion prepared in (4), under 80 DEG C of conditions, stir 0.5h; (6) take 1g curdlan quaternary ammonium salt and add the emulsion prepared in (5), stirring and dissolving 2h under 80 DEG C of conditions; (7) mixed solution prepared in (6) is poured in container, stand degassed after paving, freezing 5 hours at container is placed in-25 DEG C, then take out container in thawed at room temperature 3 hours, after being repeatedly performed above-mentioned freeze-thaw process 3 times, it is placed in 35 DEG C of canyons to dry, obtains curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.
Embodiment 5:(1) take immersion 40min, stirring and dissolving 2h under 1g polyvinyl alcohol 100mL deionized water room temperature, obtain poly-vinyl alcohol solution; (2) take 0.40g sucrose ester S-1570 and join in (1), stirring and dissolving 1h at 80 DEG C; (3) take 0.40g glyceryl stearate to be added in 2.0g liquid paraffin at 60 DEG C and stir 0.5h; (4) the paraffin mixed liquor prepared in (3) is instilled the solution prepared in (2), stirring and emulsifying 1h at 80 DEG C; (5) take 1.5g glycerol by adding the emulsion prepared in (4), under 80 DEG C of conditions, stir 0.5h; (6) take 4g curdlan quaternary ammonium salt and add the emulsion prepared in (5), stirring and dissolving 2h under 80 DEG C of conditions; (7) mixed solution prepared in (6) is poured in container, pave standing degassed, container is placed in-40 DEG C of freezings 5 hours, then take out container in thawed at room temperature 3 hours, after being repeatedly performed above-mentioned freeze-thaw process 3 times, it is placed in 40 DEG C of canyons to dry, obtains curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.
Embodiment 6:
Application Example
Select curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film that embodiment 1 obtains, it is carried out Antibacterial Activity: adopt agar plate method that curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film is carried out qualitative antibacterial detection, first 100 microliters of bacteria suspensions are uniformly coated on agar plate, with gram negative bacteria (escherichia coli) and gram-positive bacterium (staphylococcus) for representing antibacterial. The tweezers of the circular membrane sterilizing of the size (6mm) such as sterilized are put it on the agar plate coating bacteria suspension, inhibition zone is observed after cultivating 24h at 37 DEG C, such as (shown in Fig. 2), find out from Fig. 2 (a), escherichia coli are had obvious bacteriostasis by curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film, finding out from Fig. 2 (b), staphylococcus is had obvious bacteriostasis by curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.

Claims (6)

1. the preparation method of curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film, it is characterised in that: include following preparation process:
(1) taking the mixing of certain polyethylene alcohol and water, stirring and dissolving 2-3h, obtain poly-vinyl alcohol solution, wherein poly-vinyl alcohol solution concentration is 0.02g��0.10g/mLH2O;
(2) being added by a certain percentage by surfactant in (1), stirring and dissolving 0.5-2h at 30��90 DEG C, wherein surfactant adds concentration is 0.001g��0.01g/mLH2O, wherein surfactant can be one or both in sucrose ester S-1570, APG, polyethylene glycol oxide (20) glyceryl monostearate, polyethylene glycol oxide (20) sorbitan monostearate;
(3) being added by a certain percentage in oil substances by surfactant, stir 0.5-1h at 30��80 DEG C, wherein surfactant adds concentration is 0.001g��0.01g/mLH2O, wherein surfactant can be one or both in Span-80, sorbitan fatty acid ester S-60, glyceryl stearate, glyceryl monolaurate, and it is 0.005g��0.02g/mLH that oil substances adds concentration2O, wherein oil substances can be vegetable oil or liquid paraffin;
(4) the oils and fats mixed liquor prepared in (3) is added dropwise to solution prepared in (2), stirring and emulsifying 1-8h under 30��80 DEG C of conditions;
(5) plasticizer adding emulsion by a certain percentage that prepare in (4), stirs 0.5-1h under 30��80 DEG C of conditions, wherein plasticizer adds concentration is 0.005g��0.02g/mLH2O, wherein plasticizer can be one or both in glycerol, stearic acid, glucose, oleic acid, epoxy soybean oil, sorbitol;
(6) curdlan quaternary ammonium salt adds the emulsion prepared in (5) and stirring and dissolving 1-2h by a certain percentage, and wherein curdlan quaternary ammonium salt is 4: 1��1: 4 with the weight ratio of polyvinyl alcohol;
(7) mixed solution prepared in (6) is poured into in film container, pave rear degassed, after container is placed at-10 DEG C��-40 DEG C repeatedly freezing 3��5h, it is placed in 30��40 DEG C of canyons and dries, obtain curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.
2. a preparation method according to claim 1 prepares the curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film of gained.
3. curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film according to claim 2, it is characterised in that: the thickness range of described curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film is 10 ��m��1000 ��m.
4. curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film according to claim 2, it is characterised in that: described curdlan quaternary ammonium salt/polyvinyl alcohol gel film surface is smooth, internal porose, and pore diameter range is 125 ��m��600 ��m.
5. preparation method according to claim 1 prepares the application of the curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film of gained, it is characterised in that: colibacillus, staphylococcus, staphylococcus aureus and mycete are had bacteriostasis by described curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film.
6. preparation method according to claim 1 prepares the application of the curdlan quaternary ammonium salt/polyvinyl alcohol gel thin film of gained, it is characterised in that: it is applied in medicine, food, daily chemical product as antibiotic packaging material.
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CN106832701A (en) * 2016-12-20 2017-06-13 江南大学 A kind of antibacterial nano composite membrane of environment-friendly type macromolecule and its antibacterial application
CN107501476A (en) * 2017-09-05 2017-12-22 江南大学 A kind of preparation method of photo-crosslinking antibiotic property composite membrane of polyvinyl alcohol
CN108586828A (en) * 2018-04-10 2018-09-28 南京农业大学 A kind of Compound Edible Coating for Preservation and its preparation method and application
CN112970744A (en) * 2021-03-10 2021-06-18 杭州师范大学钱江学院 Pesticide slow-release gel material and preparation method and application thereof

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