CN108610502A - The preparation method of transparent self-supporting packing film based on polylactic acid Visible Light Induced Photocatalytic - Google Patents
The preparation method of transparent self-supporting packing film based on polylactic acid Visible Light Induced Photocatalytic Download PDFInfo
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- CN108610502A CN108610502A CN201810378531.2A CN201810378531A CN108610502A CN 108610502 A CN108610502 A CN 108610502A CN 201810378531 A CN201810378531 A CN 201810378531A CN 108610502 A CN108610502 A CN 108610502A
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- polylactic acid
- film
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- molybdenum disulfide
- visible light
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 74
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 72
- 238000012856 packing Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 23
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 71
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229920001661 Chitosan Polymers 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000003851 corona treatment Methods 0.000 claims abstract description 23
- 239000002135 nanosheet Substances 0.000 claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 235000019253 formic acid Nutrition 0.000 claims abstract description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000005191 phase separation Methods 0.000 claims abstract description 10
- 230000004907 flux Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- ZZASRJYLQUPYFI-UHFFFAOYSA-N chloroform;n,n-dimethylformamide Chemical compound ClC(Cl)Cl.CN(C)C=O ZZASRJYLQUPYFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 241000446313 Lamella Species 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000009182 swimming Effects 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 79
- 239000000463 material Substances 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 abstract 1
- 230000000258 photobiological effect Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 239000005022 packaging material Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 210000000481 breast Anatomy 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241000233866 Fungi Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000009416 shuttering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- 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
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
- Wrappers (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The preparation method of the invention discloses a kind of transparent self-supporting packing film based on polylactic acid Visible Light Induced Photocatalytic, this method are the materials based on polylactic acid (PLA), and chitosan (CS) is modified material, molybdenum disulfide (MoS2) it is decorative material, steps are as follows：First by N, N dimethylformamides obtain polylactic acid chitosan blend solution as the intermediate flux of chloroform and formic acid, the blend solution is dropped in water again, a strata chitosan lactate self-supporting film is formed by phase separation method, corona treatment is carried out to the composite membrane later, molybdenum disulfide nano sheet layer is finally modified on film, obtains the transparent self-supporting laminated film of polylactic acid chitosan molybdenum disulfide；The film has good transparency, preparation method is simple, photocatalytic degradation can occur under visible light illumination, and it can achieve the effect that regulate and control photodegradable speed by adjusting the content of molybdenum disulfide, it can adapt to different external environment of degrading, it is a kind of ideal photo-biological double degradable package thin-film material convenient for industrialization production and commercial applications.
Description
Technical field
The preparation method of the present invention relates to a kind of transparent self-supporting packing film based on polylactic acid Visible Light Induced Photocatalytic belongs to
In the biomedical packaging material such as the agricultural product packagings such as food fresh keeping Material Field and tissue engineering bracket field.
Background technology
Packaging material in the biomedical sectors such as the agricultural product such as food fresh keeping and tissue engineering bracket is typically due to not
It is degradable to cause a large amount of environmental pollution and problem of energy crisis.In face of these problems, it is petroleum-based degradable to prepare replacement
The necessity and emergency of packaging material are come into being.
Polylactic acid (PLA) and chitosan (CS) are typical biodegradation materials, have outstanding biodegradability and
Biocompatibility.Meanwhile polylactic acid itself has good glossiness and transparency, gas permeability, fungus resistance and outstanding physics
Performance has obtained the approval of United States food and drag administration (FDA), therefore selects master of the polylactic acid as degradable films
Want ingredient.Chitosan itself has excellent anti-microbial property, and the hydrophily that chitosan has can improve polylactic acid membrane
Hydrophobicity, positive charge can neutralize the lactic acid generated when polylactic acid degradation, inhibit Delayed onset foreign matter inflammatory reaction, therefore use
Altered contents of the chitosan as polylactic acid.The polylactic acid-chitose composite membrane obtained in summary disclosure satisfy that as packaging
Transparency, antibiotic property required by material and degradability, it can however not denying, same degradation material cannot fit
The external environment condition of Various Complex, such as simple polylactic acid-chitose packing film is answered to be discarded in non-microorganism item
Under part, still it is difficult to degrade, to bring problem of environmental pollution.Therefore, it is necessary to carry out work(to polylactic acid-chitose packaging material
Energyization is modified, and makes it not only can be biodegradable, moreover it is possible to light degradation, to faster and better apply to food and medicine field.
Functional modification is carried out to which the method for developing into photo-degradable and bio-degradable material includes mainly to biodegradation material
Two kinds.One is high molecular molecular structure is changed, suitable photosensitive group (such as carboxylic is imported in the macromolecular structure of material
Base, carbonyl and double bond etc.), make this high molecular material itself that there is photosensitivity, light degradation can occur.Another kind is to change
The composition of high molecular material, adds photosensitizing agents in the material, and after light irradiates, photosensitizing agents absorb luminous energy and generate free radicals,
Polymer molecule is transferred energy to, promotes high molecular material that photocatalytic degradation reaction occurs.In comparison, the latter operates more
It is at low cost to be simple, it is more suitable for industrialization promotion.In numerous photosensitizing agents, the present invention selects molybdenum disulfide (MoS2) conduct
The decorative material of polylactic acid-chitose is because molybdenum disulfide is provided simultaneously with transient metal sulfide and two-dimensional layer nanometer material
The peculiar property of material has good biocompatibility, mechanical performance and photoelectric properties, can effectively absorb luminous energy, be ground extensively
Study carefully for biomedical and photoelectric field.
The present invention is packed thin by transparent self-supporting of the phase separation method preparation based on polylactic acid Visible Light Induced Photocatalytic
Film.This method does not only need large scale equipment, but also does not need high-temperature and high-pressure conditions and shuttering supporting, can control production cost,
Improve processing safety.Molybdenum disulfide can improve response of the film to visible light, under visible light illumination, curing simultaneously
Molybdenum absorbs luminous energy, generates free radicals, transfers energy to polylactic acid-chitose-molybdenum disulfide composite membrane, promote the film visible
Light issues third contact of a total solar or lunar eclipse catalytic degradation reaction so that the Materials become a kind of new photo-degradable and bio-degradable material.In addition, this is multiple
Close film degradation speed under visible light illumination be it is controllable, can by adjusting molybdenum disulfide content to artificially control light
The speed of degradation.
Invention content
Technical problem：The present invention is intended to provide it is a kind of can occur under visible light illumination controlled degradation based on polylactic acid
Transparent self-supporting packing film preparation method, illustrate the mechanism between surface modification and membrane structure performance, make it is suitable for
Industrialization production and commercial applications.
Technical solution：A kind of preparation side of transparent self-supporting packing film based on polylactic acid Visible Light Induced Photocatalytic of the present invention
Method obtains polylactic acid-chitose blend solution using n,N-Dimethylformamide as the intermediate flux of chloroform and formic acid first, then
The blend solution is dropped in water, one layer of polylactic acid-chitose self-supporting laminated film is formed by phase separation method,
Corona treatment is carried out to the laminated film later, molybdenum disulfide nano sheet layer is finally modified on laminated film, is gathered
The transparent self-supporting laminated film of lactic acid-chitosan-molybdenum disulfide.The film has good transparency, and preparation method is simple, energy
It is enough that photocatalytic degradation occurs under visible light illumination, and regulation and control photodegradable speed can be reached by adjusting the content of molybdenum disulfide
Effect can adapt to different external environment of degrading, be convenient for industrialization production and commercial applications, be a kind of ideal light-life
Object double degradable package thin-film material.
Wherein：
It is described using n,N-Dimethylformamide as chloroform and the intermediate flux of formic acid obtain polylactic acid-chitose be blended it is molten
The detailed process of liquid is：The speed that the chitosan solution that mass volume ratio is 5mg/ml-12.5mg/ml is dropped into 5 drops with per second 3
It is added dropwise in the PLA solution that mass volume ratio is 10mg/ml-25mg/ml, wherein heating temperature is 55 DEG C -65 DEG C, stirring
Speed is 750rpm-850rpm, and it is 5min-10min, the volume ratio of PLA solution and chitosan solution to be stirred the time
For 3/1-8/1.
The solvent of the chitosan solution is formic acid.
The solvent of the PLA solution is chloroform-n,N-Dimethylformamide that isometric ratio is blended.
It is described to drop to polylactic acid-chitose blend solution in water, strata breast is formed by phase separation method
The detailed process of acid-chitosan self-supporting film is：The speed that polylactic acid-chitose solution is dropped to 5 drops with per second 3 is added dropwise to
In water, after standing 5min-10min, the adrift self-supporting film of layer of transparent on the water surface drags for the film swum on the water surface
It rises, places dry in baking oven.
The dry time is 1h-5h in the placement baking oven, and temperature is 50 DEG C -65 DEG C.
Molybdenum disulfide nano sheet is modified on film after the progress corona treatment by polylactic acid-chitose composite membrane
Layer, the detailed process for obtaining the transparent self-supporting laminated film of polylactic acid-chitose-molybdenum disulfide are：By the polylactic acid-after drying
Chitosan film is with after corona treatment 3min-10min, and by being ultrasonically treated, the molybdenum disulfide nano sheet layer after 30min-1h is molten
Drop adds on the polylactic acid-chitose film after corona treatment, will obtained film place it is dry in baking oven, you can
To the polylactic acid-chitose-molybdenum disulfide packing film for the transparent self-supporting for capableing of Visible Light Induced Photocatalytic.
The film places the time dry in baking oven as 1h-5h, and temperature is 50 DEG C -65 DEG C.
The mass volume ratio of the molybdenum disulfide nano sheet layer solution is 18mg/ml, and solvent is what isometric ratio was blended
Alcohol-water.
The weight fraction ratio of the molybdenum disulfide and polylactic acid that wherein add is 2%-40%.
Advantageous effect：Compared with prior art, the present invention haing the following advantages：
1, the innovation in terms of preparation method rarely has be capable of Visible Light Induced Photocatalytic using the preparation of phase separation method at present
The research of transparent self-supporting packing film based on polylactic acid, this method is simple and effective, and device is simple, at low cost, is not necessarily to substrate,
It can rapidly and efficiently be prepared on a large scale.
2, in terms of product, polylactic acid-chitose-molybdenum disulfide composite membrane of preparation has good transparency (to visible
The transmitance of light>And controllable light degradation rate 75%).
3, have a wide range of application, polylactic acid-chitose-molybdenum disulfide composite membrane of preparation can adapt to the more complicated external world
Degradation environment, may be used as the packaging material of the biomedical sectors such as the agricultural product such as food fresh keeping and tissue engineering bracket, can be big
Amplitude reduces environmental pollution, alleviating energy crisis.
Description of the drawings
Fig. 1 is polylactic acid-chitose composite membrane and the polylactic acid-chitose-drop of molybdenum disulfide composite membrane under visible light
Solve effect contrast figure.PLA/CS/MoS in figure2- 2%, PLA/CS/MoS2- 5%, PLA/CS/MoS2- 10%, PLA/CS/MoS2-
20% and PLA/CS/MoS2- 40% weight fraction ratio for referring respectively to molybdenum disulfide and polylactic acid is 2%, 5%, 10%,
20% and 40% polylactic acid-chitose-molybdenum disulfide composite membrane.
Fig. 2 is the transparency interaction pair of polylactic acid-chitose composite membrane and polylactic acid-chitose-molybdenum disulfide composite membrane
Than figure.Angle of wherein sitting down is respectively polylactic acid-chitose composite membrane (left side) and polylactic acid-chitose-molybdenum disulfide composite membrane
The pictorial diagram on (right side).
Specific implementation mode
A kind of preparation method of transparent self-supporting packing film based on polylactic acid Visible Light Induced Photocatalytic of the present invention is：First
Polylactic acid-chitose blend solution is obtained using n,N-Dimethylformamide as the intermediate flux of chloroform and formic acid, then this is total to
Miscible fluid drops in water, and one layer of polylactic acid-chitose self-supporting film is formed by phase separation method, multiple to this later
It closes film and carries out corona treatment, molybdenum disulfide nano sheet layer is finally modified on film, obtains-two sulphur of polylactic acid-chitose
Change the transparent self-supporting laminated film of molybdenum.
Wherein：
It is described using n,N-Dimethylformamide as chloroform and the intermediate flux of formic acid obtain polylactic acid-chitose be blended it is molten
The detailed process of liquid is：The speed that the chitosan solution that mass volume ratio is 5mg/ml-12.5mg/ml is dropped into 5 drops with per second 3
It is added dropwise in the PLA solution that mass volume ratio is 10mg/ml-25mg/ml, wherein heating temperature is 55 DEG C -65 DEG C, stirring
Speed is 750rpm-850rpm, and it is 5min-10min, the volume ratio of PLA solution and chitosan solution to be stirred the time
For 3/1-8/1.
The solvent of the chitosan solution is formic acid.
The solvent of the PLA solution is chloroform-n,N-Dimethylformamide that isometric ratio is blended.
It is described to drop to polylactic acid-chitose blend solution in water, strata breast is formed by phase separation method
The detailed process of acid-chitosan self-supporting film is：The speed that polylactic acid-chitose solution is dropped to 5 drops with per second 3 is added dropwise to
In water, after standing 5min-10min, the adrift self-supporting film of layer of transparent on the water surface drags for the film swum on the water surface
It rises, places dry in baking oven.
The dry time is 1h-5h in the placement baking oven, and temperature is 50 DEG C -65 DEG C.
Molybdenum disulfide nano sheet is modified on film after the progress corona treatment by polylactic acid-chitose composite membrane
Layer, the detailed process for obtaining the transparent self-supporting laminated film of polylactic acid-chitose-molybdenum disulfide are：By the polylactic acid-after drying
Chitosan film is with after corona treatment 3min-10min, and by being ultrasonically treated, the molybdenum disulfide nano sheet layer after 30min-1h is molten
Drop adds on the polylactic acid-chitose film after corona treatment, will obtained film place it is dry in baking oven, you can
To the polylactic acid-chitose-molybdenum disulfide packing film for the transparent self-supporting for capableing of Visible Light Induced Photocatalytic.
The film places the time dry in baking oven as 1h-5h, and temperature is 50 DEG C -65 DEG C.
The mass volume ratio of the molybdenum disulfide nano sheet layer solution is 18mg/ml, and solvent is what isometric ratio was blended
Alcohol-water.
The weight fraction ratio of the molybdenum disulfide and polylactic acid that wherein add is 2%-40%.
This film material based on polylactic acid PLA, chitosan CS are modified material, molybdenum disulfide MoS2To modify material
Material, is prepared by phase separation method.The film has good transparency, and preparation method is simple, can be can
Light-exposed irradiation issues third contact of a total solar or lunar eclipse catalytic degradation, and can achieve the effect that regulate and control photodegradable speed by adjusting the content of molybdenum disulfide,
Different external environment of degrading is can adapt to, is convenient for industrialization production and commercial applications, is that a kind of ideal light-biology is double down
Solution packaging thin-film material.
The present invention is done with reference to embodiment and is further explained, the following example is merely to illustrate the present invention, but
It is not used to limit the practical range of the present invention.
A kind of preparation method of the transparent self-supporting packing film based on polylactic acid Visible Light Induced Photocatalytic includes the following steps：
Step 1: configuration quality volume ratio is the PLA solution of 10mg/ml-25mg/ml, 5mg/ml-12.5mg/ml
The molybdenum disulfide nano sheet layer solution of chitosan solution and 18mg/ml, the wherein solvent of PLA solution are total for isometric ratio
The solvent of mixed chloroform-n,N-Dimethylformamide, chitosan solution is formic acid, and the solvent of molybdenum disulfide nano sheet layer solution is
The alcohol-water that isometric ratio is blended；
Step 2: the speed that chitosan solution is dropped to 5 drops with per second 3 is added dropwise in PLA solution, wherein heating temperature
Degree is 55 DEG C -65 DEG C, mixing speed 750rpm-850rpm, and it is 5min-10min, PLA solution and shell to be stirred the time
The volume ratio of glycan solution is 3/1-8/1.Molybdenum disulfide solution is ultrasonically treated 30min-1h simultaneously；
Step 3: the speed that polylactic acid-chitose solution is dropped to 5 drops with per second 3 is added dropwise in water, 5min- is stood
After 10min, the adrift self-supporting polylactic acid-chitose laminated film of layer of transparent on the water surface；
Step 4: the film swum on the water surface is picked up, dry 1h-5h in baking oven is placed, temperature is 50 DEG C -65 DEG C；
Step 5: the polylactic acid-chitose film after drying is taken out, with corona treatment 3min-10min；
Step 6: the molybdenum disulfide nano sheet layer solution after supersound process to be added dropwise to the poly- breast after corona treatment
Acid-chitosan film, wherein the weight fraction ratio of the molybdenum disulfide and polylactic acid that add is 2%-40%；
Step 7: the film that upper step is obtained places dry 1h-5h in baking oven, temperature is 50 DEG C -65 DEG C, you can is obtained
It is capable of polylactic acid-chitose-molybdenum disulfide packing film of the transparent self-supporting of Visible Light Induced Photocatalytic.
Embodiment 1
1) configuration quality volume ratio be the PLA solution of 10mg/ml, the chitosan solution of 5mg/ml and 18mg/ml two
Molybdenum sulfide nanoscale twins solution, the wherein solvent of PLA solution are chloroform-N, N- the dimethyl formyl that isometric ratio is blended
The solvent of amine, chitosan solution is formic acid, and the solvent of molybdenum disulfide nano sheet layer solution is the ethyl alcohol-that isometric ratio is blended
Water；
2) chitosan solution is added dropwise to the speed of 3 drop per second in PLA solution, wherein heating temperature is 55 DEG C, is stirred
It is 750rpm to mix speed, is stirred the time as 5min, the volume ratio of PLA solution and chitosan solution is 6/1.Simultaneously
Molybdenum disulfide solution is ultrasonically treated 1h；
3) polylactic acid-chitose solution is added dropwise to the speed of 3 drop per second in water, after standing 10min, is floated on the water surface
The self-supporting polylactic acid-chitose laminated film of layer of transparent；
4) film swum on the water surface is picked up, places dry 5h in baking oven, temperature is 50 DEG C；
5) the polylactic acid-chitose film after drying is taken out, with corona treatment 5min；
6) the molybdenum disulfide nano sheet layer solution after supersound process is added dropwise to polylactic acid-shell after corona treatment to gather
Sugared film, wherein the weight fraction ratio of the molybdenum disulfide and polylactic acid that add is 5%；
7) film for obtaining upper step places dry 5h in baking oven, and temperature is 50 DEG C, you can obtaining being capable of visible light drop
Polylactic acid-chitose-molybdenum disulfide packing film of the transparent self-supporting of solution.
Embodiment 2
1) configuration quality volume ratio be the PLA solution of 10mg/ml, the chitosan solution of 5mg/ml and 18mg/ml two
Molybdenum sulfide nanoscale twins solution, the wherein solvent of PLA solution are chloroform-N, N- the dimethyl formyl that isometric ratio is blended
The solvent of amine, chitosan solution is formic acid, and the solvent of molybdenum disulfide nano sheet layer solution is the ethyl alcohol-that isometric ratio is blended
Water；
2) chitosan solution is added dropwise to the speed of 3 drop per second in PLA solution, wherein heating temperature is 55 DEG C, is stirred
It is 750rpm to mix speed, is stirred the time as 5min, the volume ratio of PLA solution and chitosan solution is 6/1.Simultaneously
Molybdenum disulfide solution is ultrasonically treated 1h；
3) polylactic acid-chitose solution is added dropwise to the speed of 3 drop per second in water, after standing 10min, is floated on the water surface
The self-supporting polylactic acid-chitose laminated film of layer of transparent；
4) film swum on the water surface is picked up, places dry 5h in baking oven, temperature is 50 DEG C；
5) the polylactic acid-chitose film after drying is taken out, with corona treatment 5min；
6) the molybdenum disulfide nano sheet layer solution after supersound process is added dropwise to polylactic acid-shell after corona treatment to gather
Sugared film, wherein the weight fraction ratio of the molybdenum disulfide and polylactic acid that add is 10%；
7) film for obtaining upper step places dry 5h in baking oven, and temperature is 50 DEG C, you can obtaining being capable of visible light drop
Polylactic acid-chitose-molybdenum disulfide packing film of the transparent self-supporting of solution.
Embodiment 3
1) configuration quality volume ratio be the PLA solution of 10mg/ml, the chitosan solution of 5mg/ml and 18mg/ml two
Molybdenum sulfide nanoscale twins solution, the wherein solvent of PLA solution are chloroform-N, N- the dimethyl formyl that isometric ratio is blended
The solvent of amine, chitosan solution is formic acid, and the solvent of molybdenum disulfide nano sheet layer solution is the ethyl alcohol-that isometric ratio is blended
Water；
2) chitosan solution is added dropwise to the speed of 3 drop per second in PLA solution, wherein heating temperature is 55 DEG C, is stirred
It is 750rpm to mix speed, is stirred the time as 5min, the volume ratio of PLA solution and chitosan solution is 6/1.Simultaneously
Molybdenum disulfide solution is ultrasonically treated 1h；
3) polylactic acid-chitose solution is added dropwise to the speed of 3 drop per second in water, after standing 10min, is floated on the water surface
The self-supporting polylactic acid-chitose laminated film of layer of transparent；
4) film swum on the water surface is picked up, places dry 5h in baking oven, temperature is 50 DEG C；
5) the polylactic acid-chitose film after drying is taken out, with corona treatment 5min；
6) the molybdenum disulfide nano sheet layer solution after supersound process is added dropwise to polylactic acid-shell after corona treatment to gather
Sugared film, wherein the weight fraction ratio of the molybdenum disulfide and polylactic acid that add is 20%；
7) film for obtaining upper step places dry 5h in baking oven, and temperature is 50 DEG C, you can obtaining being capable of visible light drop
Polylactic acid-chitose-molybdenum disulfide packing film of the transparent self-supporting of solution.
Embodiment 4
1) configuration quality volume ratio be the PLA solution of 10mg/ml, the chitosan solution of 5mg/ml and 18mg/ml two
Molybdenum sulfide nanoscale twins solution, the wherein solvent of PLA solution are chloroform-N, N- the dimethyl formyl that isometric ratio is blended
The solvent of amine, chitosan solution is formic acid, and the solvent of molybdenum disulfide nano sheet layer solution is the ethyl alcohol-that isometric ratio is blended
Water；
2) chitosan solution is added dropwise to the speed of 3 drop per second in PLA solution, wherein heating temperature is 55 DEG C, is stirred
It is 750rpm to mix speed, is stirred the time as 5min, the volume ratio of PLA solution and chitosan solution is 6/1.Simultaneously
Molybdenum disulfide solution is ultrasonically treated 1h；
3) polylactic acid-chitose solution is added dropwise to the speed of 3 drop per second in water, after standing 10min, is floated on the water surface
The self-supporting polylactic acid-chitose laminated film of layer of transparent；
4) film swum on the water surface is picked up, places dry 5h in baking oven, temperature is 50 DEG C；
5) the polylactic acid-chitose film after drying is taken out, with corona treatment 5min；
6) the molybdenum disulfide nano sheet layer solution after supersound process is added dropwise to polylactic acid-shell after corona treatment to gather
Sugared film, wherein the weight fraction ratio of the molybdenum disulfide and polylactic acid that add is 40%；
7) film for obtaining upper step places dry 5h in baking oven, and temperature is 50 DEG C, you can obtaining being capable of visible light drop
Polylactic acid-chitose-molybdenum disulfide packing film of the transparent self-supporting of solution.
Claims (10)
1. a kind of preparation method of the transparent self-supporting packing film based on polylactic acid Visible Light Induced Photocatalytic, it is characterised in that：First
Polylactic acid-chitose blend solution is obtained using n,N-Dimethylformamide as the intermediate flux of chloroform and formic acid, then this is total to
Miscible fluid drops in water, and one layer of polylactic acid-chitose self-supporting laminated film is formed by phase separation method, right later
The laminated film carries out corona treatment, and molybdenum disulfide nano sheet layer is finally modified on laminated film, obtains polylactic acid-shell
The transparent self-supporting laminated film of glycan-molybdenum disulfide.
2. the preparation method of the transparent self-supporting packing film according to claim 1 based on polylactic acid Visible Light Induced Photocatalytic,
It is characterized in that：It is described n,N-Dimethylformamide is obtained into polylactic acid-chitose as the intermediate flux of chloroform and formic acid to be total to
The detailed process of miscible fluid is：The chitosan solution that mass volume ratio is 5mg/ml-12.5mg/ml is dropped into 5 drops with per second 3
Speed is added dropwise in the PLA solution that mass volume ratio is 10mg/ml-25mg/ml, and wherein heating temperature is 55 DEG C -65 DEG C,
Mixing speed is 750rpm-850rpm, and it is 5min-10min, the volume of PLA solution and chitosan solution to be stirred the time
Ratio is 3/1-8/1.
3. the preparation method of the transparent self-supporting packing film according to claim 2 based on polylactic acid Visible Light Induced Photocatalytic,
It is characterized in that：The solvent of the chitosan solution is formic acid.
4. the preparation method of the transparent self-supporting packing film according to claim 2 based on polylactic acid Visible Light Induced Photocatalytic,
It is characterized in that：The solvent of the PLA solution is chloroform-n,N-Dimethylformamide that isometric ratio is blended.
5. the preparation side of the transparent self-supporting packing film of the Visible Light Induced Photocatalytic according to claim 1 based on polylactic acid
Method, it is characterised in that it is described to drop to polylactic acid-chitose blend solution in water, form one layer by phase separation method
The detailed process of polylactic acid-chitose self-supporting film is：The speed that polylactic acid-chitose solution is dropped to 5 drops with per second 3 is dripped
It adds in water, after standing 5min-10min, the adrift self-supporting film of layer of transparent on the water surface is thin on the water surface by swimming in
Film picks up, and places dry in baking oven.
6. the preparation method of the transparent self-supporting packing film according to claim 5 based on polylactic acid Visible Light Induced Photocatalytic,
It is characterized in that described place the time dry in baking oven as 1h-5h, temperature is 50 DEG C -65 DEG C.
7. the preparation method of the transparent self-supporting packing film according to claim 1 based on polylactic acid Visible Light Induced Photocatalytic,
It is characterized in that：Molybdenum disulfide is modified after the progress corona treatment by polylactic acid-chitose composite membrane on film to receive
Rice lamella, the detailed process for obtaining the transparent self-supporting laminated film of polylactic acid-chitose-molybdenum disulfide are：It will be poly- after drying
Lactic acid-chitosan film will be ultrasonically treated the molybdenum disulfide nano after 30min-1h with after corona treatment 3min-10min
Lamella solution is added dropwise on the polylactic acid-chitose film after corona treatment, will obtained film place it is dry in baking oven,
It can be obtained the polylactic acid-chitose-molybdenum disulfide packing film for the transparent self-supporting for capableing of Visible Light Induced Photocatalytic.
8. the preparation method of the transparent self-supporting packing film according to claim 1 based on polylactic acid Visible Light Induced Photocatalytic,
It is characterized in that：The film places the time dry in baking oven as 1h-5h, and temperature is 50 DEG C -65 DEG C.
9. the preparation method of the transparent self-supporting packing film according to claim 1 based on polylactic acid Visible Light Induced Photocatalytic,
It is characterized in that the mass volume ratio of the molybdenum disulfide nano sheet layer solution is 18mg/ml, solvent is blended for isometric ratio
Alcohol-water.
10. the preparation method of the transparent self-supporting packing film according to claim 7 based on polylactic acid Visible Light Induced Photocatalytic,
It is characterized in that the weight fraction ratio of the molybdenum disulfide and polylactic acid that wherein add is 2%-40%.
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| CN109794266A (en) * | 2019-02-20 | 2019-05-24 | 清华大学 | A kind of inorganic catalytic membrane and its preparation method and application |
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