CN109134897A - Nano-chitosan/polyvinyl alcohol compound film preparation method and its laminated film obtained and application - Google Patents
Nano-chitosan/polyvinyl alcohol compound film preparation method and its laminated film obtained and application Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/42—Applications of coated or impregnated materials
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a kind of preparation method of nano-chitosan/polyvinyl alcohol compound film and its laminated film obtained and applications, are related to packaging material field.Nano-chitosan/polyvinyl alcohol compound film preparation method, comprising the following steps: nano-chitosan film is put into poly-vinyl alcohol solution, after taking-up after drying and heat treatment, obtains nano-chitosan/polyvinyl alcohol compound film；Nano-chitosan film is obtained after nano-chitosan suspension plastic film mulch solidifies；Heat treatment is that 110~120 DEG C are heated under saturated steam environment.The preparation method has many advantages, such as that simple process, raw material sources are extensive, preparation cost is low and environmentally protective, can also efficiently utilize marine industries waste, improve its use value.Nano-chitosan/polyvinyl alcohol compound film of preparation method preparation has many advantages, such as good barrier property, biological degradability, the transparency, tensile strength, thermal stability, antibiotic property and nontoxic, can be used as antibacterial environment protection packaging material.
Description
Technical field
The present invention relates to packaging material fields, in particular to a kind of nano-chitosan/polyvinyl alcohol compound film
Preparation method and its laminated film obtained and application.
Background technique
With the continuous development of industry, " white pollution " is increasingly serious, in such circumstances, degradable environment-friendly package material
By favor.Biodegradable material, be one kind can the regular hour and under the conditions of, can be by the Institute of Micro-biology of nature
The material of decomposition, the final product of degradation are the small-molecule substance of carbon dioxide, water and some environmental sounds.
Miniaturization is the persistent trend of current materials science field, original to be promoted by reducing the size of material structure
Performance, nanofiber are successfully prepared via different synthetic polymer or natural polymer.So-called nanofiber refers to straight
Diameter is less than 100nm, and aspect ratio is greater than 100, with high axial strength and elasticity close to perfect crystal, almost without lacking
It falls into.Had the advantages that by nano material prepared by natural resources significant such as biological degradability, reproducibility and sustainability.
Chitin is the high molecular weight natural polyethylene alcohol abundant of nature second, is only second to cellulose.As threadiness
Crystalline material, there are three types of crystal forms for chitin: α-chitin, β-chitin and γ-chitin, wherein α-chitin mainly sinks
Product is in the ectoskeleton shell of crab, shrimp and lobster.In the food industry, the usual abandoned of the shell of these seafood products.In order to return
Them are received, a kind of effective method is the nano-chitosan (ChWs) that manufacture has high-mechanical property.ChWs can be added to respectively
In kind synthesizing polyethylene alcohol matrix, for manufacturing enhancing composite membrane.Ideal ChWs/ polyvinyl alcohol composite material film, which has, to be changed
Kind intensity and elasticity, and other valuable performances, such as transparency and flexibility will not be damaged.Patent
CN103342825A discloses a kind of preparation method of chitin nano fiber/composite membrane of polyvinyl alcohol, but the patent is prepared
Composite membrane water resistant ability it is poor, packaging material field can not be applied to.
Currently, the preparation process of existing major part nano-chitosan/composite membrane of polyvinyl alcohol is complicated, energy consumption is high, is made
Composite membrane water resistant ability it is poor, packaging material field can not be applied to.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of nano-chitosan/polyvinyl alcohol compound film, hot
Processing makes the strand of polyvinyl alcohol carry out warm-up movement, changes its molecular structure, enhances the hydrophobicity of polyvinyl alcohol, enhances
The water barrier property of laminated film；Meanwhile heat treatment makes have more objects between chitin and polyvinyl alcohol in laminated film
Crosslinking points are managed, the properties of laminated film are improved.In addition, the preparation method has simple process, raw material sources are extensive, system
For the advantages that at low cost, environmentally protective, marine industries waste can be also efficiently utilized, its use value is improved.
The second object of the present invention is to provide a kind of nano-chitosan/polyvinyl alcohol compound film, and the nano-chitosan/
Polyvinyl alcohol compound film is prepared into using the preparation method of nano-chitosan/polyvinyl alcohol compound film provided by the invention
It arrives.The laminated film has good water barrier property, biological degradability, the transparency, tensile strength, thermal stability, antibiotic property
And the advantages that nontoxic, it can be used as antibacterial environment protection packaging material.
The third object of the present invention is to provide nano-chitosan/polyvinyl alcohol compound film in preparing packaging material
Using.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
In a first aspect, the present invention provides a kind of preparation methods of nano-chitosan/polyvinyl alcohol compound film, including with
Lower step:
Nano-chitosan film is put into poly-vinyl alcohol solution, after taking-up after drying and heat treatment, obtains a nanometer crust
Element/polyvinyl alcohol compound film；
Nano-chitosan film is obtained after nano-chitosan suspension plastic film mulch solidifies；
Heat treatment is that 110~120 DEG C are heated under saturated steam environment.
Further, on the basis of technical solution provided by the invention, nano-chitosan/polyvinyl alcohol compound film thickness
Degree is 20~70 μm, preferably 30~60 μm, further preferably 35~55 μm.
Further, on the basis of technical solution provided by the invention, the mass concentration of poly-vinyl alcohol solution is 2%~
10%, preferably 4%~10%, further preferably 6%~10%.
Further, on the basis of technical solution provided by the invention, the mass concentration of nano-chitosan suspension is
0.1%~2%, preferably 1%~2%, further preferably 1.5%~2%.
Further, on the basis of technical solution provided by the invention, nano-chitosan suspension is made by the following method
It is standby to obtain: pretreated chitin raw material being put into lye, carries out deacetylated processing, then solution is tuned into acid with Bronsted acid
Property obtains nano-chitosan suspension after homogeneous.
Further, on the basis of technical solution provided by the invention, pretreatment includes deproteinized, removes minerals and bleaching
The step of.
Further, on the basis of technical solution provided by the invention, the time of heat treatment is 3~15min；
Preferably, the time of heat treatment is 5~10min.
Further, on the basis of technical solution provided by the invention, plastic film mulch solidification includes by nano-chitosan suspension
10~15h film forming, then the step of being dried are stood after coating to mold；
Preferably, nano-chitosan film is put into the time in poly-vinyl alcohol solution as 12~20h, preferably 12~15h.
Second aspect, the present invention provides a kind of nano-chitosan/polyvinyl alcohol compound film, using nano-chitosan/
The preparation method of polyvinyl alcohol compound film is prepared.
The third aspect, the present invention provides nano-chitosan/polyvinyl alcohol compound films to prepare answering in packaging material
With；
Preferably, the packaging material is packaging material for food.
Compared with prior art, the invention has the benefit that
(1) preparation method of nano-chitosan/polyvinyl alcohol compound film provided by the invention, nano-chitosan is suspended
Liquid elder generation plastic film mulch film-forming, places into poly-vinyl alcohol solution, and nano-chitosan and polyvinyl alcohol can be physical crosslinking at this time
Reaction, forms hydrogen bond between the amino of nano-chitosan and the hydroxyl of polyvinyl alcohol, enhances the mechanical performance of laminated film；Heat
Processing makes the strand of polyvinyl alcohol carry out warm-up movement, changes its molecular structure, enhances the hydrophobicity of polyvinyl alcohol, enhances
The water barrier property of laminated film；Meanwhile heat treatment makes have more objects between chitin and polyvinyl alcohol in laminated film
Crosslinking points are managed, the properties of laminated film are improved.The nano-chitosan that preparation method is prepared through the invention/poly- second
Enol laminated film has good water barrier property, biological degradability, the transparency, tensile strength, thermal stability, antibiotic property and nothing
The advantages that malicious, can be used as antibacterial environment protection packaging material.
(2) preparation method of nano-chitosan/polyvinyl alcohol compound film provided by the invention, the preparation used, reaction,
Drying equipment is simply common, does not need addition expensive equipment, therefore can be achieved at low cost preparation process；Used chitin
The utilization again of raw material sources Yu Haiyang waste, it is cheap, and prepare without any toxic chemical in raw material, it is green
Colour circle is protected, and operating process is easy.So the preparation method of nano-chitosan/polyvinyl alcohol compound film provided by the invention has
Have simple process, raw material sources are extensive, and preparation cost is low, it is environmentally protective the advantages that, can also efficiently utilize marine industries waste,
Improve its use value.
(3) nano-chitosan/polyvinyl alcohol compound film provided by the invention, Young's modulus are answered up to 6.46GPa, stretching
Power maximum value load is up to 301Mpa, and moisture-vapor transmission minimum is up to 2.26 × 10-10(g/Pams), antibacterial circle diameter is reachable
6.24mm。
Detailed description of the invention
Fig. 1 is nano-chitosan/polyvinyl alcohol compound film electron microscope prepared by the embodiment of the present invention 6；
Fig. 2 is the nanometer of nano-chitosan/polyvinyl alcohol compound film of the preparation of the embodiment of the present invention 6, the preparation of comparative example 1
Nano-chitosan/the polyvinyl alcohol compound film and crust of pure PVA film, the preparation of comparative example 3 prepared by chitin film, comparative example 2
The thermal stability results figure of plain powder；
Fig. 3 is the nanometer of nano-chitosan/polyvinyl alcohol compound film of the preparation of the embodiment of the present invention 6, the preparation of comparative example 1
The transparency results figure of chitin film, pure PVA film prepared by comparative example 2 and chitin powder.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, a kind of preparation side of nano-chitosan/polyvinyl alcohol compound film is provided
Method, comprising the following steps:
Nano-chitosan film is put into poly-vinyl alcohol solution, after taking-up after drying and heat treatment, obtains a nanometer crust
Element/polyvinyl alcohol compound film；
Nano-chitosan film is obtained after nano-chitosan suspension plastic film mulch solidifies；
Heat treatment is that 110~120 DEG C are heated under saturated steam environment.
"/" in nano-chitosan/polyvinyl alcohol compound film is the meaning of sum.
It is the environment of same temperature that saturated steam environment, which refers to the temperature of steam and generates the temperature of the water of steam,；At heat
A kind of preferred embodiment of reason is that 110~120 DEG C are heated in high-temperature sterilizing chambers.
The typical but non-limiting temperature of heat treatment is, for example, 110 DEG C, 111 DEG C, 112 DEG C, 113 DEG C, 114 DEG C, 115
DEG C, 116 DEG C, 117 DEG C, 118 DEG C, 119 DEG C or 120 DEG C.
Nano-chitosan have high mechanical strength, high-aspect-ratio, density is low, surface area is big, source is wide, it is nontoxic, antibacterial, can
The advantages that regeneration, biodegradable and bio-compatible, therefore nano-chitosan can be used for many fields, and it is compound such as to prepare polymer
Material, Cosmetic Manufacture, food additives, food packaging, water process, drug are carried with organizational project etc..
Polyvinyl alcohol preferably 1799 types, polyvinyl alcohol (PVA) they are a kind of environmentally protective packaging materials haveing excellent performance, due to
It is and wide with performances such as good filming performance, mechanical performance, antistatic property, chemical resistance and biodegradabilities
It is general to apply in food packaging applications.But the strongly hydrophilic of polyvinyl alcohol will lead to film and excessively be swollen in the case where contacting wet environment,
It even dissolves, which greatly limits its applications.
By nano-chitosan suspension elder generation plastic film mulch film-forming, place into poly-vinyl alcohol solution, at this time nano-chitosan
Physical crosslinking reaction can occur with polyvinyl alcohol, form hydrogen bond between the amino of nano-chitosan and the hydroxyl of polyvinyl alcohol, increase
The strong mechanical performance of laminated film；Heat treatment makes the strand of polyvinyl alcohol carry out warm-up movement, changes its molecular structure, increases
The strong hydrophobicity of polyvinyl alcohol, enhances the water barrier property of laminated film；Meanwhile heat treatment make chitin and polyvinyl alcohol it
Between have more physical crosslinking points, improve the properties of laminated film.
Nano-chitosan/polyvinyl alcohol compound film that preparation method is prepared through the invention has good water resistance
Every property, biological degradability, the transparency, tensile strength, thermal stability, antibiotic property and it is nontoxic the advantages that, can be used as antibacterial environment protection packet
Package material.
The preparation method of nano-chitosan/polyvinyl alcohol compound film provided by the invention, the preparation used, are done reaction
Dry equipment is simply common, does not need addition expensive equipment, therefore can be achieved at low cost preparation process；Used chitin is former
Material derives from the utilization again of sea leave, cheap, and prepares in raw material without any toxic chemical, green
Environmental protection, operating process are easy.So the preparation method of nano-chitosan/polyvinyl alcohol compound film provided by the invention has
The advantages that simple process, raw material sources are extensive, and preparation cost is low, environmentally protective can also efficiently utilize marine industries waste, mention
Its high use value.
In a preferred embodiment, nano-chitosan/polyvinyl alcohol compound film is excellent with a thickness of 20~70 μm
It is selected as 30~60 μm, further preferably 35~55 μm.
Typical but non-limiting nano-chitosan/polyvinyl alcohol compound film thickness is, for example, 20 μm, 30 μm, 40 μ
M, 50 μm, 60 μm or 70 μm.
Nano-chitosan/polyvinyl alcohol compound film thickness and its mechanical property and the transparency are closely related, nanometer first
Shell element/polyvinyl alcohol compound film thickness it is excessive and it is too small can all directly affect its mechanical property, made to be unfavorable for it
Application in standby packaging material.By limiting the thickness with preferred nano-chitosan/polyvinyl alcohol compound film, can make to prepare
Obtained laminated film has good mechanical property, is conducive to it and is preparing the application in packaging material.
In a preferred embodiment, the mass concentration of poly-vinyl alcohol solution be 2%~10%, preferably 4%~
10%, further preferably 6%~10%.
The mass concentration of poly-vinyl alcohol solution it is typical but non-limiting be, for example, 2%, 3%, 4%, 5%, 6%, 7%,
8%, 9% or 10%.
The mass concentration of poly-vinyl alcohol solution and the close phase of nano-chitosan/polyvinyl alcohol compound film mechanical performance
It closes, the excessively high and too low physics friendship that can all influence poly-vinyl alcohol solution and nano-chitosan film of the mass concentration of poly-vinyl alcohol solution
Join reaction result, declines the mechanical performance of laminated film.It, can be with by limiting and the mass concentration of preferred poly-vinyl alcohol solution
Keep the nano-chitosan/polyvinyl alcohol compound film mechanical performance being prepared more preferable.
In a preferred embodiment, the mass concentration of nano-chitosan suspension is 0.1%~2%, preferably
1%~2%, further preferably 1.5%~2%.
The mass concentration of nano-chitosan suspension it is typical but non-limiting be, for example, 0.1%, 0.3%, 0.5%,
0.8%, 1.0%, 1.3%, 1.5%, 1.8% or 2%.
The mass concentration of nano-chitosan suspension and the close phase of nano-chitosan/polyvinyl alcohol compound film performance
It closes, also can further influence the physical crosslinking reaction result of nano-chitosan film and poly-vinyl alcohol solution.Nano-chitosan suspends
The mass concentration of liquid is high, and hydrogen bond distance is close, and the film of formation is closer, and the film mechanical performance of formation is more preferable.But nano-chitosan is outstanding
Supernatant liquid mass concentration is excessively high to will increase preparation cost, is unfavorable for being applied to packaging material；Nano-chitosan suspension quality concentration
It is too low to will affect nano-chitosan/polyvinyl alcohol compound film mechanical performance.
By limiting and the mass concentration of preferred nano-chitosan suspension can make the nano-chitosan being prepared/poly-
Vinyl alcohol laminated film has good mechanical performance, is conducive to it and is preparing the application in packaging material.
In a preferred embodiment, nano-chitosan suspension is prepared by the following method to obtain: will pre-process
Chitin raw material afterwards is put into lye, is carried out deacetylated processing, then solution is tuned into acidity with Bronsted acid, is received after homogeneous
Rice chitin suspension；
Preferably, the chitin raw material derives from least one of shrimp shell or crab shell.
Chitin raw material derives from the utilization again of sea leave, cheap, from a wealth of sources, and prepares in raw material
It is environmentally protective without any toxic chemical.
In a preferred embodiment, lye includes that sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide are molten
One of liquid is a variety of；
Preferably, the mass concentration of lye is 20%~50%；
Preferably, it is 70~90 DEG C that the reaction condition of deacetylated processing, which includes: temperature, and the time is 1~3h.
Pretreated chitin raw material is put into deacetylated processing in lye, chitin knot can be made under alkaline condition
N- acetyl group on structure unit C2 hydrolyzes, and exposes amino, prepares for protonation in next step.
The mass concentration of lye it is typical but non-limiting be, for example, 20%, 25%, 28%, 30%, 35%, 38%,
40%, 45% or 50%；The typical but non-limiting reaction temperature of deacetylated processing is, for example, 70 DEG C, 73 DEG C, 76 DEG C, 79
DEG C, 82 DEG C, 85 DEG C, 88 DEG C or 90 DEG C；The reaction time of deacetylated processing typical but non-limiting for example, 1h, 1.3h,
1.6h, 1.9h, 2.1h, 2.4h, 2.6h, 2.8h or 3h.
By limit and preferred deacetylated processing used in lye, the mass concentration of lye and deacetylated processing temperature,
Time can make the effect of deacetylated processing more preferable, keep the concentration that nano-chitosan suspension is prepared higher.
In a preferred embodiment, Bronsted acid includes acetic acid, folic acid, gluconic acid, oxalic acid, lysine, flax
Acid, citric acid, aspartic acid, nucleotide, itaconic acid, malonic acid or coloured glaze clap one of acid or a variety of.
The pH value of solution is adjusted to 3~4 with Bronsted acid, it is, for example, 3 that pH value is typical but non-limiting, 3.1,3.2,3.3,
3.4,3.5,3.6,3.7,3.8,3.9 or 4.By limiting the pH value with preferred Bronsted acid and adjusting, make that a nanometer first is prepared
Shell element suspension concentration is higher, is convenient for subsequent homogenization process.
In a preferred embodiment, the homogenization time is 2~5h.
It is preferred that high pressure homogenizer carries out homogeneous, the stable nanometer of available homogeneous transparent after high pressure homogenizer homogeneous
Chitin suspension facilitates the solid content of measurement nano-chitosan suspension.Homogenization time typical but non-limiting example
For example 2h, 2.5h, 3h, 3.5h, 4h or 5h.
It can make the uniform, transparent of the nano-chitosan suspension being prepared with the preferred homogenization time by limiting
It is more prominent with stable advantage, be conducive to subsequent use nano-chitosan suspension and prepare nano-chitosan film.
In a preferred embodiment, pretreatment includes the steps that deproteinized, removes minerals and bleaching.
Chitin raw material pretreatment can effectively be removed into the impurity components such as albumen, minerals and color in raw material, with
Exempt to influence the subsequent nano-chitosan/polyvinyl alcohol compound film performance being prepared.
In a preferred embodiment, the deproteinized is that chitin raw material is mixed to the remaining egg of removal with aqueous slkali
It is white, then it is washed to neutrality；
Preferably, the aqueous slkali includes one of sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution
Or it is a variety of；
Preferably, the concentration of the aqueous slkali is 0.5~1mol/L.
It is preferred that water is deionized water, avoid introducing foreign ion.The concentration of aqueous slkali is typical but non-limiting to be, for example,
0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L.
Deproteinized can remove the residual protein in chitin raw material, in order to avoid continuously preparing nano crust after residual protein influence
Element/polyvinyl alcohol compound film is conducive to going on smoothly for subsequent preparation process, greatly reduces protein impurities content in product.
In a preferred embodiment, it is described go minerals be chitin raw material is mixed with inorganic acid removal mineral
Matter, then it is washed to neutrality；
Preferably, the inorganic acid includes one of hydrochloric acid, sulfuric acid or acetic acid or a variety of；
Preferably, the concentration of the inorganic acid is 0.5~1mol/L.
It is preferred that water is deionized water, in order to avoid introduce foreign ion.The concentration of inorganic acid is typical but non-limiting to be, for example,
0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L.
Go minerals that can remove the minerals in chitin raw material, in order to avoid continuously preparing nano crust after minerals influence
Element/polyvinyl alcohol compound film is conducive to going on smoothly for subsequent preparation process, greatly reduces containing for product mineral impurity
Amount.
In a preferred embodiment, the bleaching is that chitin raw material is mixed 1~3h with bleaching agent to float
It is white；
Preferably, the bleaching agent includes at least one of sodium chlorite or calcium chlorite；
Preferably, the concentration of the bleaching agent is 0.5~1mol/L.
It is preferred that water is deionized water, in order to avoid introduce foreign ion.The typical but non-limiting for example, 1h of bleaching time,
1.3h, 1.5h, 1.8h, 2h, 2.3h, 2.5h, 2.8h or 3h；The concentration of bleaching agent is typical but non-limiting to be, for example,
0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L.
The step of bleaching, can effectively remove the color of chitin raw material, in order to avoid continuously preparing nano first after the Color influences of raw material
Shell element/polyvinyl alcohol compound film color and the transparency, are conducive to going on smoothly for subsequent preparation process.
In a preferred embodiment, the time of heat treatment is 3~15min；
Preferably, the time of heat treatment is 5~10min.
The time of heat treatment it is typical but non-limiting be, for example, 3min, 4min, 5min, 6min, 7min, 8min, 9min,
10min, 11min, 12min, 13min, 14min or 15min.
The time of heat treatment is too short to fall flat, and the overlong time of heat treatment can make laminated film be hardened, shadow
Ring its mechanical performance.By limiting and preferred heat treatment time, the function and effect of heat treatment can be made more preferable, make to be prepared
Nano-chitosan // polyvinyl alcohol compound film water barrier property and all other performances are more preferable.
In a preferred embodiment, plastic film mulch solidification includes standing after coating nano-chitosan suspension to mold
10~15h film forming, then the step of being dried；
Preferably, the coating method includes one of the tape casting, spin coating method, spray coating method or brushing method.
Nano-chitosan suspension obtained is coated to smooth mold, 10~15h is stood and removes bubble, transfer to temperature
It is dried in 45~60 DEG C of climatic chambers of degree, obtains nano-chitosan film.Time of repose is typical but non-limiting for example
For 10h, 11h, 12h, 13h, 14h or 15h；Drying temperature it is typical but non-limiting be, for example, 45 DEG C, 48 DEG C, 50 DEG C, 53 DEG C,
55 DEG C, 58 DEG C or 60 DEG C.By limit and preferred plastic film mulch solidify in reaction condition, can be more efficient prepare nano-chitosan
Film, and keep the nano-chitosan film properties being prepared more preferable.
In a preferred embodiment, nano-chitosan film be put into the time in poly-vinyl alcohol solution be 12~20h,
Preferably 12~15h.
It is preferably carried out in mode, by nano-chitosan film immersion obtained into poly-vinyl alcohol solution, is placed under room temperature
12~20h.The typical but non-limiting time is, for example, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h.
By limit and preferred nano-chitosan film be put into the time in poly-vinyl alcohol solution, can make nano-chitosan and
Polyvinyl alcohol occurs physical crosslinking and reacts more abundant, makes the nano-chitosan/polyvinyl alcohol compound film biology being prepared
Degradability, the transparency, tensile strength, thermal stability, antibiotic property and it is nontoxic the advantages that it is more prominent.
Preferably, a kind of preparation method of typical nano-chitosan/polyvinyl alcohol compound film, comprising the following steps:
(1) chitin raw material is subjected to deproteinized, goes dry after the pretreatment of minerals and bleaching, then carried out deacetylated
Then processing is added proton acid for adjusting pH, obtains chitin suspension；
(2) by chitin suspension obtained after homogeneous, nano-chitosan suspension is obtained, measures nano-chitosan
The solid content of suspension is placed in 2~8 DEG C and is sealed；
(3) nano-chitosan suspension flow obtained is extended down to smooth mold, stands 10~15h and remove bubble, is transferred to
8~12h is dried in 45~60 DEG C of climatic chambers of temperature, obtains nano-chitosan film；
(4) by nano-chitosan film immersion obtained into poly-vinyl alcohol solution, 12~20h is placed under room temperature；
(5) the resulting nano-chitosan film for impregnating poly-vinyl alcohol solution is subjected to suspension 10~30min of processing, with stream
The poly-vinyl alcohol solution that most surface is not immersed, obtains nano-chitosan/polyvinyl alcohol wet film；
(6) nano-chitosan/polyvinyl alcohol wet film is transferred in 45~60 DEG C of climatic chambers of temperature and is dried, obtained
To nano-chitosan/polyvinyl alcohol compound film；
(7) nano-chitosan/polyvinyl alcohol compound film is placed in high-temperature sterilizing chambers, is heated to 110~120 DEG C,
5~10min is kept, is taken out.
The preparation method of the typical nano-chitosan/polyvinyl alcohol compound film, the step of defining preparation method and
Condition shortens the time of preparation method, reduces cost, makes the nano-chitosan/polyvinyl alcohol compound film being prepared
Performance it is more preferable.
According to the second aspect of the invention, a kind of nano-chitosan/polyvinyl alcohol compound film, this nanometer of first are provided
Shell element/polyvinyl alcohol compound film is the preparation method using nano-chitosan/polyvinyl alcohol compound film provided by the invention
It is prepared.
Nano-chitosan/the polyvinyl alcohol compound film has good water barrier property, biological degradability, the transparency, resists
Tensile strength, thermal stability, antibiotic property and it is nontoxic the advantages that, can be used as antibacterial environment protection packaging material.
According to the third aspect of the present invention, offer nano-chitosan/polyvinyl alcohol compound film is provided to wrap in preparation
Application in package material；
Preferably, the packaging material is packaging material for food.
In order to further appreciate that the present invention, the method for the present invention and effect are done further in detail combined with specific embodiments below
Explanation.Each raw material of the present invention can pass through commercially available acquisition.
Polyvinyl alcohol used in embodiment and comparative example is 1799 types；High pressure homogenizer is U.S. Nano DeBEE type
Number；Climatic chamber is Jiangsu favour section LHS-150HC model；High-temperature sterilizing chambers are three Shengong department YX280B model of Shanghai.
Embodiment 1
A kind of preparation method of nano-chitosan suspension, comprising the following steps:
(1) the 20g shrimp shell discarded is immersed in the sodium hydroxide solution of 1mol/L and removes residual protein, then spend from
Son is washed to neutrality, obtains the shrimp shell of deproteinized；
(2) shrimp shell of deproteinized is immersed in the hydrochloric acid of 1mol/L and is demineralized, then be washed with deionized water to neutrality,
Obtain the shrimp shell of minerals；
(3) shrimp shell of minerals will be gone to be immersed in the sodium chlorite solution of 0.1mol/L and bleaches 2h, shrimp is dried after bleaching
Shell；
(4) shrimp shell after drying is immersed in the sodium hydroxide solution of 44wt%, while 5g sodium borohydride is added, 90
Magnetic agitation 3h carries out deacetylation under DEG C oil bath, and acetic acid is added after the reaction was completed and adjusts pH value of solution to 3.5, obtains chitin
Suspension；
(5) chitin suspension obtained is obtained into nano-chitosan suspension by high pressure homogenizer homogeneous 3h, measured
The solid content of nano-chitosan suspension at this time is placed at 4 DEG C and is sealed.
Embodiment 2
(1) ultrapure water is added to be configured to concentration by nano-chitosan suspension prepared by embodiment 1 is 0.1wt%, room temperature
Under stir, then carry out ultrasound 30min；
(2) the smooth mold of polytetrafluoroethylene (PTFE) that nano-chitosan suspension flow obtained is extended down to diameter 6cm stands 12h
Bubble is removed, is transferred in temperature 50 C climatic chamber and 10h is dried, obtain nano-chitosan film；
(3) nano-chitosan film immersion obtained is placed into 15h under room temperature into 10Wt% poly-vinyl alcohol solution；
(4) the resulting nano-chitosan film for impregnating poly-vinyl alcohol solution is subjected to suspension processing 30min, to flow to end table
The poly-vinyl alcohol solution that face is not immersed obtains nano-chitosan/polyvinyl alcohol wet film；
(5) nano-chitosan/polyvinyl alcohol wet film is transferred in temperature 50 C climatic chamber and is dried, received
Rice chitin/polyvinyl alcohol laminated film；
(6) nano-chitosan/polyvinyl alcohol compound film is placed in high-temperature sterilizing chambers, 120 DEG C of processing 10min take
Nanometer chitin/polyvinyl alcohol laminated film out.
Wherein, nano-chitosan/polyvinyl alcohol compound film thickness is about 45 μm.
Embodiment 3
(1) ultrapure water is added to be configured to concentration by nano-chitosan suspension prepared by embodiment 1 is 0.5wt%, room temperature
Under stir, then carry out ultrasound 30min；
(2) the smooth mold of polytetrafluoroethylene (PTFE) that nano-chitosan suspension flow obtained is extended down to diameter 6cm stands 12h
Bubble is removed, is transferred in temperature 50 C climatic chamber and 10h is dried, obtain nano-chitosan film；
(3) nano-chitosan film immersion obtained is placed into 15h under room temperature into 10Wt% poly-vinyl alcohol solution；
(4) the resulting nano-chitosan film for impregnating poly-vinyl alcohol solution is subjected to suspension processing 30min, to flow to end table
The poly-vinyl alcohol solution that face is not immersed obtains nano-chitosan/polyvinyl alcohol wet film；
(5) nano-chitosan/polyvinyl alcohol wet film is transferred in temperature 50 C climatic chamber and is dried, received
Rice chitin/polyvinyl alcohol laminated film；
(6) nano-chitosan/polyvinyl alcohol compound film is placed in high-temperature sterilizing chambers, 120 DEG C of processing 10min take
Nanometer chitin/polyvinyl alcohol laminated film out.
Wherein, nano-chitosan/polyvinyl alcohol compound film thickness is about 45 μm.
Embodiment 4
(1) ultrapure water is added to be configured to concentration by nano-chitosan suspension prepared by embodiment 1 is 1.0wt%, room temperature
Under stir, then carry out ultrasound 30min；
(2) the smooth mold of polytetrafluoroethylene (PTFE) that nano-chitosan suspension flow obtained is extended down to diameter 6cm stands 12h
Bubble is removed, is transferred in temperature 50 C climatic chamber and 10h is dried, obtain nano-chitosan film；
(3) nano-chitosan film immersion obtained is placed into 15h under room temperature into 10Wt% poly-vinyl alcohol solution；
(4) the resulting nano-chitosan film for impregnating poly-vinyl alcohol solution is subjected to suspension processing 30min, to flow to end table
The poly-vinyl alcohol solution that face is not immersed obtains nano-chitosan/polyvinyl alcohol wet film；
(5) nano-chitosan/polyvinyl alcohol wet film is transferred in temperature 50 C climatic chamber and is dried, received
Rice chitin/polyvinyl alcohol laminated film；
(6) nano-chitosan/polyvinyl alcohol compound film is placed in high-temperature sterilizing chambers, 120 DEG C of processing 10min take
Nanometer chitin/polyvinyl alcohol laminated film out.
Wherein, nano-chitosan/polyvinyl alcohol compound film thickness is about 45 μm.
Embodiment 5
(1) ultrapure water is added to be configured to concentration by nano-chitosan suspension prepared by embodiment 1 is 1.5wt%, room temperature
Under stir, then carry out ultrasound 30min；
(2) the smooth mold of polytetrafluoroethylene (PTFE) that nano-chitosan suspension flow obtained is extended down to diameter 6cm stands 12h
Bubble is removed, is transferred in temperature 50 C climatic chamber and 10h is dried, obtain nano-chitosan film；
(3) nano-chitosan film immersion obtained is placed into 15h under room temperature into 10Wt% poly-vinyl alcohol solution；
(4) the resulting nano-chitosan film for impregnating poly-vinyl alcohol solution is subjected to suspension processing 30min, to flow to end table
The poly-vinyl alcohol solution that face is not immersed obtains nano-chitosan/polyvinyl alcohol wet film；
(5) nano-chitosan/polyvinyl alcohol wet film is transferred in temperature 50 C climatic chamber and is dried, received
Rice chitin/polyvinyl alcohol laminated film；
(6) nano-chitosan/polyvinyl alcohol compound film is placed in high-temperature sterilizing chambers, 120 DEG C of processing 10min take
Nanometer chitin/polyvinyl alcohol laminated film out.
Wherein, nano-chitosan/polyvinyl alcohol compound film thickness is about 45 μm.
Embodiment 6
(1) ultrapure water is added in nano-chitosan suspension prepared by embodiment 1 and is configured to concentration for 2wt%, under room temperature
It stirs, then carries out ultrasound 30min；
(2) the smooth mold of polytetrafluoroethylene (PTFE) that nano-chitosan suspension flow obtained is extended down to diameter 6cm stands 12h
Bubble is removed, is transferred in temperature 50 C climatic chamber and 10h is dried, obtain nano-chitosan film；
(3) nano-chitosan film immersion obtained is placed into 15h under room temperature into 10Wt% poly-vinyl alcohol solution；
(4) the resulting nano-chitosan film for impregnating poly-vinyl alcohol solution is subjected to suspension processing 30min, to flow to end table
The poly-vinyl alcohol solution that face is not immersed obtains nano-chitosan/polyvinyl alcohol wet film；
(5) nano-chitosan/polyvinyl alcohol wet film is transferred in temperature 50 C climatic chamber and is dried, received
Rice chitin/polyvinyl alcohol laminated film；
(6) nano-chitosan/polyvinyl alcohol compound film is placed in high-temperature sterilizing chambers, 120 DEG C of processing 10min take
Nanometer chitin/polyvinyl alcohol laminated film out.
Wherein, nano-chitosan/polyvinyl alcohol compound film thickness is about 45 μm.
Embodiment 7
The difference of the present embodiment and embodiment 4 is that the concentration of poly-vinyl alcohol solution is 2.0wt%.
Embodiment 8
The difference of the present embodiment and embodiment 4 is that the concentration of poly-vinyl alcohol solution is 4.0wt%.
Embodiment 9
The difference of the present embodiment and embodiment 4 is that the concentration of poly-vinyl alcohol solution is 6.0wt%.
Embodiment 10
The difference of the present embodiment and embodiment 4 is that the concentration of poly-vinyl alcohol solution is 8.0wt%.
Embodiment 11
The difference of the present embodiment and embodiment 6 is that nano-chitosan/polyvinyl alcohol compound film thickness is about 20 μm.
Embodiment 12
The difference of the present embodiment and embodiment 6 is that nano-chitosan/polyvinyl alcohol compound film thickness is about 70 μm.
Comparative example 1
(1) ultrapure water is added in nano-chitosan suspension prepared by embodiment 1 and is configured to concentration for 2wt%, under room temperature
It stirs, then carries out ultrasound 30min；
(2) the smooth mold of polytetrafluoroethylene (PTFE) that nano-chitosan suspension flow obtained is extended down to diameter 6cm stands 12h
Bubble is removed, is transferred in temperature 50 C climatic chamber and 10h is dried, obtain nano-chitosan film.
Wherein, the thickness of nano-chitosan film is about 45 μm.
Comparative example 2
The smooth mold of the polytetrafluoroethylene (PTFE) that 10wt% polyvinyl alcohol is cast to diameter 6cm stands 12h and removes bubble, turns
It moves in temperature 50 C climatic chamber and 10h is dried, obtain pure polyvinyl alcohol (PVA) film.
Wherein, the thickness of pure polyvinyl alcohol (PVA) film is about 45 μm.
Comparative example 3
The difference of this comparative example and embodiment 6 is to remove the heat treatment process of step (6).
Comparative example 4
CN103342825A embodiment 5 and embodiment 9, comprising the following steps:
(1) the chitin powder for accurately weighing 60 mesh of 10g handles chitin with the HCl of 7% concentration under room temperature environment
Powder for 24 hours, removes remaining calcium carbonate in chitin, is washed with deionized water later to neutrality；
(2) under room temperature environment, chitin suspension 12h is handled with the NaOH of 5% concentration, is removed remaining in chitin
Protein is washed till neutrality with a large amount of deionized water later；It is repeated four times to ensure sufficiently to remove isolating protein；
(3) under room temperature environment, with the alcohol treatment of 50% concentration suspension 12h, pigment composition is removed, later with big
Amount deionized water is washed till neutrality；
(4) chitin powder is dried into 6h in a vacuum drying oven, is then dissolved in the deionized water of 1000mL, is configured to
The chitin suspension of 1wt% concentration；
(5) obtained chitin suspension is made into the solution of 0.2wt%, is handled by grinder, grinder rotating speed is
1500rpm, scale are adjusted to -1.5, grind 10 times, ultrasound 30min after grinding respectively, then homogeneous 10 times, obtain chitin Nanowire
Tie up solution；
(6) make to pour into after chitin fiber is uniformly dispersed in the chitin suspension of 0.2wt% with glass bar hand operated mixing
In Buchner funnel, the filter paper of two layers of 9mm diameter is first padded before filter membrane in Buchner funnel, then the miillpore filter of same diameter is attached to
Surface is soaked with deionized water and filter paper and squeezes out the bubble below filter membrane, make its it is smooth be laid in Buchner funnel, open
Vacuum pump is filtered；
(7) filter drained completely to deionized water after terminate, close vacuum pump, by chitin nano fiber film be fitted in
Filter paper and miillpore filter together takes out from Buchner funnel together, and gently outermost tunica fibrosa is removed from filter membrane with hand
It comes, obtains wet chitin nano fiber film；
(8) the wet chitin nano fiber film is sandwiched among the new filter paper of two panels, be together placed in two pieces of glass plates or
In iron plate, it is put into about 55 DEG C of electric heating constant-temperature blowing drying box and dries 24~48 hours；It is taken after fiber membrane is dried completely
Out, chitin nano fiber film is made；
(9) suitable 10wt% polyvinyl alcohol water solution is taken to pour into culture dish, the chitin nanometer that will be prepared in advance
Tunica fibrosa immerses in poly-vinyl alcohol solution, and stirs film and keep its smooth and be dipped into polyvinyl alcohol completely.Air in order to prevent
In dust etc. pollute the solution, one layer of preservative film is covered on culture dish, by tunica fibrosa after impregnating at room temperature about 12 hours
It takes out, is hung on sample in the electric heating constant-temperature blowing drying box that temperature is 55 DEG C about 12 hours or so with suspension method, to film
It is taken out after drying, obtains chitin nano fiber/composite membrane of polyvinyl alcohol.
Comparative example 5
CN107286547A embodiment 3, comprising the following steps:
(1) by the mixed liquor of 7g polyethylene glycol and glycerine, (mass ratio of polyethylene glycol and glycerine is 4:1, wherein gathering
The molecular weight of ethylene glycol is that the 400 and 0.5g concentrated sulfuric acid is uniformly mixed in three-necked flask, and 1g chitin is added, and stirring is placed in
90min is reacted at 160 DEG C, obtains 8g chitin liquefaction products；
(2) 16g polyvinyl alcohol and 400g deionized water are placed at 90 DEG C and heat 2h, and by filtering, standing and defoaming is gathered
Glycohol solution；
(3) 8g chitin liquefaction products are mixed at 65 DEG C with 416g poly-vinyl alcohol solution, continues to stir 3h, will mixes
Liquid is poured on glass plate model, using the tape casting plastic film mulch, solidifies for 24 hours at room temperature, the blend film after solidification is placed in ethyl alcohol
It is proposed after middle rinsing, natural airing, obtains chitin liquefaction products/polyvinyl alcohol blending film.
Experimental example 1
The film that embodiment 2-12 and comparative example 1-5 are prepared carries out performance data test, and test Young's modulus stretches
The results are shown in Table 1 in the load of maximum value, moisture-vapor transmission and antibacterial circle diameter for stress.
Table 1
As shown in Table 1, nano-chitosan/polyvinyl alcohol compound film Young mould that embodiment 2-12 preparation method obtains
Amount, tensile stress are significantly better than that comparative example 4 in the performance data of the load of maximum value, moisture-vapor transmission and antibacterial circle diameter
The chitin liquefaction that the chitin nano fiber/composite membrane of polyvinyl alcohol and 5 preparation method of comparative example that preparation method obtains obtain
Product/polyvinyl alcohol blending film.It is good that this shows that nano-chitosan/polyvinyl alcohol compound film that the present invention is prepared has
Barrier property, tensile strength and the advantages that antibiotic property, suitable for preparing antibacterial environment protection packaging material.
In embodiment 2-6, the concentration of nano-chitosan suspension is gradually increased, and the concentration of poly-vinyl alcohol solution is constant.From
Data in table 1 can be seen that nano-chitosan/polyvinyl alcohol compound film performance in embodiment 2-6 and gradually become more preferable,
This shows that the concentration of nano-chitosan suspension and nano-chitosan/polyvinyl alcohol compound film performance are closely related.Implement
Compared with Example 6, the main distinction is that the thickness of film is different, the nanometer crust that embodiment 6 is prepared for example 11, embodiment 12
Element/polyvinyl alcohol compound film performance is better than embodiment 11 and embodiment 12, this shows that nano-chitosan/polyvinyl alcohol is compound
The thickness of film can also have an impact its properties.
Nano-chitosan film has been prepared in comparative example 1, and pure polyvinyl alcohol (PVA) film has been prepared in comparative example 2.Comparison
Compared with Example 6, the properties data that table 1 measures are all poorer than embodiment 6, this shows nano-chitosan/polyethylene for example 1,2
Alcohol laminated film is more preferable than the performance of nano-chitosan film and pure polyvinyl alcohol (PVA) film.
The polyvinyl alcohol as the result is shown (PVA) of Fig. 1 has been impregnated into the inside of nano-chitosan film, shows preparation side of the invention
Nano-chitosan/polyvinyl alcohol compound film has been prepared in method really.Fig. 2 as the result is shown within the scope of 200 DEG C, embodiment
Nano-chitosan/polyvinyl alcohol compound film thermal stability through Overheating Treatment of 6 preparations is apparently higher than the preparation of comparative example 1
Nano-chitosan film, comparative example 2 prepare pure PVA film, comparative example 3 prepare nano-chitosan/polyvinyl alcohol compound film and
The thermal stability of chitin powder.When the wavelength as the result is shown of Fig. 3 is greater than 600nm, the receiving through Overheating Treatment of the preparation of embodiment 6
Rice chitin/polyvinyl alcohol laminated film transparency prepared with comparative example 1 nano-chitosan film, comparative example 2 preparation it is pure
The transparency of PVA film and chitin powder does not have significant difference.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of nano-chitosan/polyvinyl alcohol compound film, which comprises the following steps:
Nano-chitosan film is put into poly-vinyl alcohol solution, after taking-up after drying and heat treatment, obtains nano-chitosan/poly-
Vinyl alcohol laminated film；
Nano-chitosan film is obtained after nano-chitosan suspension plastic film mulch solidifies；
Heat treatment is that 110~120 DEG C are heated under saturated steam environment.
2. the preparation method of nano-chitosan/polyvinyl alcohol compound film described in accordance with the claim 1, which is characterized in that institute
Nano-chitosan/polyvinyl alcohol compound film is stated with a thickness of 20~70 μm, preferably 30~60 μm, further preferably 35~
55μm。
3. the preparation method of nano-chitosan/polyvinyl alcohol compound film described in accordance with the claim 1, which is characterized in that institute
The mass concentration for stating poly-vinyl alcohol solution is 2%~10%, preferably 4%~10%, further preferably 6%~10%.
4. the preparation method of nano-chitosan/polyvinyl alcohol compound film described in accordance with the claim 1, which is characterized in that institute
State nano-chitosan suspension mass concentration be 0.1%~2%, preferably 1%~2%, further preferably 1.5%~
2%.
5. according to the preparation method of the described in any item nano-chitosan/polyvinyl alcohol compound films of claim 1-4, feature
It is, the nano-chitosan suspension is prepared by the following method to obtain:
Pretreated chitin raw material is put into lye, carries out deacetylated processing, then solution is tuned into acidity with Bronsted acid,
Nano-chitosan suspension is obtained after homogeneous；
Preferably, the chitin raw material derives from least one of shrimp shell or crab shell；
Preferably, the lye includes one of sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution or a variety of；
Preferably, the mass concentration of the lye is 20%~50%；
Preferably, it is 70~90 DEG C that the reaction condition of the deacetylated processing, which includes: reaction temperature, and the reaction time is 1~3h；
Preferably, the Bronsted acid includes acetic acid, folic acid, gluconic acid, oxalic acid, lysine, linolenic acid, citric acid, asparagus fern ammonia
Acid, nucleotide, itaconic acid, malonic acid or coloured glaze clap one of acid or a variety of；
Preferably, the homogenization time is 2~5h.
6. nano-chitosan/polyvinyl alcohol compound film preparation method according to claim 5, which is characterized in that institute
Pretreatment is stated to include the steps that deproteinized, remove minerals and bleaching；
Preferably, the deproteinized is chitin raw material to be mixed to removal residual protein with aqueous slkali, then be washed to neutrality；
Preferably, the aqueous slkali includes one of sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution or more
Kind；
Preferably, the concentration of the aqueous slkali is 0.5~1mol/L；
It is preferably, described that remove minerals be to mix chitin raw material with inorganic acid to demineralize, then be washed to neutrality；
Preferably, the inorganic acid includes one of hydrochloric acid, sulfuric acid or acetic acid or a variety of；
Preferably, the concentration of the inorganic acid is 0.5~1mol/L；
Preferably, the bleaching is that chitin raw material is mixed 1~3h with bleaching agent to bleach；
Preferably, the bleaching agent includes at least one of sodium chlorite or calcium chlorite；
Preferably, the concentration of the bleaching agent is 0.5~1mol/L.
7. according to the preparation method of the described in any item nano-chitosan/polyvinyl alcohol compound films of claim 1-4, feature
It is, the time of the heat treatment is 3~15min；
Preferably, the time of heat treatment is 5~10min.
8. according to the preparation method of the described in any item nano-chitosan/polyvinyl alcohol compound films of claim 1-4, feature
It is, the plastic film mulch solidification includes 10~15h film forming being stood after coating nano-chitosan suspension to mold, then be dried
The step of；
Preferably, the coating method includes one of the tape casting, spin coating method, spray coating method or brushing method；
Preferably, the nano-chitosan film is put into the time in poly-vinyl alcohol solution as 12~20h, preferably 12~15h.
9. a kind of nano-chitosan/polyvinyl alcohol compound film, which is characterized in that described in any item using claim 1-8
Nano-chitosan/polyvinyl alcohol compound film preparation method is prepared.
10. made from a kind of preparation method of the described in any item nano-chitosan/polyvinyl alcohol compound films of claim 1-8
Nano-chitosan/polyvinyl alcohol compound film is preparing the application in packaging material；
Preferably, the packaging material is packaging material for food.
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| CN111925551A (en) * | 2020-08-17 | 2020-11-13 | 四川大学 | Natural polysaccharide composite material with brick-mud structure, preparation method and application |
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| CN113845678B (en) * | 2021-11-30 | 2023-06-09 | 安徽理工大学 | Preparation method of high-transparency flame-retardant polyvinyl alcohol film |
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Application publication date: 20190104 |