CN110527147A - A kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane - Google Patents
A kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane Download PDFInfo
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- 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
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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
- 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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- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
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- 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
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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
- 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
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
Abstract
The present invention relates to technology of composite film preparation fields, specially a kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane, the metal salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate are added into the chitosan solution prepared, influence of the part acetato- to chitosan can be effectively eliminated, and the anion in metal salt can form ionomer with the amino of chitosan, enhance the interaction strength of chitosan molecule interchain.Preparation-obtained chitosan film is after contact wetting, and due to the effect of metal salt, the protonated amino of chitosan weakens, so that the degree of swelling of chitosan film be greatly reduced, it is made still to keep good mechanical performance in aqueous solution.
Description
Technical field
The present invention relates to technology of composite film preparation field, specially a kind of system of multipurpose water-resistant type multidimensional crosslinked composite membrane
Preparation Method.
Background technique
Chitosan is a kind of water-insoluble polysaccharide extracted from the shellfish such as discarded shrimp, crab, chitosan
Contain a large amount of amino on strand, there is good biological degradability, biocompatibility.Chitosan is a kind of excellent at membrane material
Material is widely used in fields such as food packaging, water pollution processing, electrochemical electrode preparation and wound dressings.However, without appointing
The chitosan film of what modification has very strong hydrophily and swellability, and as the degree of swelling increases, mechanical strength
It will be greatly reduced, become frangible, lose toughness, this significantly limits the practical application of chitosan film.Chitosan film
Swelling behavior influenced by pH, in acid condition, protonated amino causes hydrone to easily enter inside film, and with
PH increases, and degree of swelling is reduced.Therefore, chitosan film is after the preparation usually using naoh treatment, to eliminate inside it
Remaining acetic acid, to enhance the water resistance of chitosan film.But alkaline solution facture must first be prepared chitosan film
It completes, then film is immersed in alkaline solution again, it is suitable in terms of improving chitosan film water resistance which has limited this methods
The property used.
In order to improve the mechanical performance of chitosan film, chitosan is usually compound with other high molecular materials or nano material
It uses, this can effectively improve the mechanical strength of chitosan film and reduce its degree of swelling.Chitosan and other materials are answered
It is smaller to chitosan film performance increase rate with ratio and its important, a small amount of addition other materials, and the improvement to water resistance
Degree is lower.However, other a large amount of compound high molecular materials will lose the characteristic of chitosan itself, and the additive amount of nano material
It is excessively high that Assembling Behavior can occur, lead to the degradation of film.Therefore, it is carried out using bifunctional reagents such as Geniposide and glutaraldehydes
It is chemical crosslinking modified to become another thinking for improving chitosan film performance.Chemical crosslinking can be such that the performance of chitosan film has
Certain amplitude improves, and increasing crosslinking degree can make the degree of swelling of chitosan film lower and lower.But this method
There are obvious drawbacks, i.e., as the increase of the degree of cross linking, the rigidity of chitosan film increase, toughness is reduced, or even becomes fragile, easily broken
It splits.Therefore, chitosan and a small amount of other materials are used in combination and the machine of chitosan film can be improved in lower chemical crosslinking
Tool performance but still has the disadvantage of water resistance deficiency.
Summary of the invention
The object of the present invention is to provide a kind of preparation sides of multiduty water resistant metal salt chitosan multidimensional crosslinked composite membrane
Method, this method have the chitosan complex film of preparation good by metal Salt treatment, the lower chemical crosslinking of degree of cooperation
Water resistance still has very high intensity and toughness in aqueous solution, can be applied to the food packaging of high-moisture, sewage
Processing, electrochemical electrode preparation and wound dressing etc..
To achieve the above object, the preparation method of a kind of multipurpose water-resistant type multidimensional crosslinked composite membrane provided by the invention,
The following steps are included:
(1) it dissolves the chitosan in acetic acid solution, the complex material A and 0.5-3% that content is 1-30% is then added
Glycerol, be made chitosan content be 1-5% mixed solution A；
(2) metal salt solution that concentration is 0.02-0.5mol/L is added in mixed solution A, obtains pH in 5.5-
Mixed solution B in 6.8 ranges；
(3) complex material B solution is added in mixed solution B and obtains mixed solution C, wherein the content of complex material B
For the 5-40% of chitosan mass；
(4) crosslinking agent is added in mixed solution C according to the ratio of the 0.01-4% of chitosan mass, after mixing evenly
It removes bubble in solution, then in a mold by solution, or is coated in food surface, after evaporation drying to obtain the final product.
Preferably, the volumetric concentration of the acetic acid solution is 0.1-2%.
Preferably, the complex material A is nano silica, nano-titanium dioxide, nano-graphene, carbon nanometer
One of pipe, montmorillonite are a variety of.
Preferably, the metal salt is sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, disodium hydrogen phosphate, phosphoric acid
Hydrogen dipotassium, one of β phosphoglycerol disodium or a variety of.
Preferably, the complex material B is that polyvinyl alcohol, konjaku glucomannan, carboxymethyl cellulose, Propiram are more
One of sugar, sodium alginate, gelatin are a variety of；The mass concentration of the complex material B solution is 0.5-10%.
Preferably, the crosslinking agent is one of Geniposide, glutaraldehyde, dialdehyde starch or a variety of.
The present invention further requests a kind of preparation method of above-mentioned multipurpose water-resistant type multidimensional crosslinked composite membrane to be prepared into
A kind of microorganism fertilizer arrived.
Compared with prior art, the beneficial effects of the present invention are:
1, the metal salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate are added into the chitosan solution prepared, it can be effective
Influence of the part acetato- to chitosan is eliminated, and the anion in metal salt can form ion with the amino of chitosan
Crosslinking enhances the interaction strength of chitosan molecule interchain.Preparation-obtained chitosan film is after contact wetting, due to gold
Belong to the effect of salt, the protonated amino of chitosan weakens, so that the degree of swelling of chitosan film be greatly reduced, make its
Good mechanical performance is still kept in aqueous solution.
2, complex material nano-titanium dioxide, nano-graphene, carbon nanotube, montmorillonite, mesh are added into chitosan film
Be in order to by nanomaterial-filled between chitosan molecule chain, with chitosan molecule formed interaction of hydrogen bond, further
Enhance the mechanical strength of chitosan film.
3, it is more that complex material polyvinyl alcohol, konjaku glucomannan, carboxymethyl cellulose, Propiram are added into chitosan film
Sugar, sodium alginate, gelatin, in order to allow the above macromolecular to form physics with chitosan molecule chain and tangle, enhance chitosan
The mechanical performance of film especially increases the toughness of chitosan film.
4, carrying out chemical crosslinking to chitosan complex film is its mechanical strength in order to further increase, while being chemically crosslinked anti-
Part amino should be consumed, the degree of swelling of chitosan complex film is further reduced, makes composite membrane that there is better water resistance.This
The mechanical strength of the prepared water-resistant type metal salt chitosan multidimensional crosslinked composite membrane of invention is compared traditional chitosan film and is improved
250%, after especially sufficiently impregnating in aqueous solution, mechanical strength still maintains the 90% of drying regime.
5, the low swelling ratio of the chitosan complex film prepared by the present invention in aqueous solution, makes it in the ring of high moisture content
It is applied under border, good mechanical performance can still be maintained, be not in occur damaged because of water suction.Therefore, should
Food packaging of the chitosan complex film in high-moisture, sewage treatment, the fields such as electrochemical electrode preparation and Wound healing and bone regeneration are answered
In, excellent service performance can be kept.
Detailed description of the invention
Fig. 1 is the surface sweeping electron microscope of chitosan film prepared by embodiment 1；
Fig. 2 is the surface sweeping electron microscope of chitosan film prepared by embodiment 2；
Fig. 3 is the surface sweeping electron microscope of chitosan film prepared by embodiment 3；
Fig. 4 is the surface sweeping electron microscope of chitosan film prepared by embodiment 4.
Specific embodiment
It is clearly and completely described below in conjunction with the technical solution in the embodiment of the present invention, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without making creative work belongs to what the present invention protected
Range.
Embodiment 1
1) preparation of mixed solution A:
It accurately weighs 1.5g chitosan to be added in 100mL acetic acid solution (concentration 0.5%, v/v), stir complete to chitosan
Dissolution is then added 1g glycerol and 0.5g nano silica stirs evenly, filtering removal insoluble substance, for use.
2) preparation of mixed solution B:
It accurately weighs disodium hydrogen phosphate to be dissolved in distilled water, the metal salt solution that concentration is 0.15mol/L is prepared.
Metal salt solution is added drop-wise in mixed solution A under stirring conditions then, makes the final pH 6.5 of solution, for use.
3) preparation of mixed solution C:
It accurately weighs polyvinyl alcohol 2g to be dissolved in 100mL distilled water, takes 20mL poly-vinyl alcohol solution that 80mL mixing is added molten
In liquid B, it is stand-by that bubble is eliminated after mixing evenly.
A certain amount of mixed solution C is taken, is added Geniposide according to 0.01% of chitosan mass contained by it, after stirring and dissolving,
Solution is poured in masking mould, so that it is prolonged stream and is unfolded, it is dry under static conditions, film is taken off after film forming.
Embodiment 2
1) preparation of mixed solution A:
It accurately weighs 1.6g chitosan to be added in 100mL acetic acid solution (concentration 1%, v/v), stir completely molten to chitosan
Solution is then added 1.1g glycerol and 0.4g nano-titanium dioxide stirs evenly, filtering removal insoluble substance, for use.
2) preparation of mixed solution B:
It accurately weighs dipotassium hydrogen phosphate to be dissolved in distilled water, the metal salt solution that concentration is 0.15mol/L is prepared.With
Metal salt solution is added drop-wise in mixed solution A under stirring conditions afterwards, makes the final pH 6.25 of solution, for use.
3) preparation of mixed solution C:
It accurately weighs konjaku glucomannan 3g to be dissolved in 100mL distilled water, 25mL konjak portuguese gansu polyose sugar juice is taken to be added
In 75mL mixed solution B, it is stand-by that bubble is eliminated after mixing evenly.
A certain amount of mixed solution C is taken, is added Geniposide according to 0.02% of chitosan mass contained by it, after stirring and dissolving,
Solution is poured in masking mould, so that it is prolonged stream and is unfolded, it is dry under static conditions, film is taken off after film forming.
Embodiment 3
1) preparation of mixed solution A:
It accurately weighs 2g chitosan to be added in 100mL acetic acid solution (concentration 1%, v/v), stir completely molten to chitosan
Solution is then added 1.2g glycerol and 0.6g nano-graphene stirs evenly, filtering removal insoluble substance, for use.
2) preparation of mixed solution B:
It accurately weighs β phosphoglycerol disodium to be dissolved in distilled water, the solution that concentration is 0.2mol/L is prepared.Then will
Two sodium solution of β phosphoglycerol is added drop-wise in mixed solution A under stirring conditions, makes the final pH 6.0 of solution, for use.
3) preparation of mixed solution C:
It accurately weighs carboxymethyl cellulose 3.5g to be dissolved in 100mL distilled water, 30mL konjak portuguese gansu polyose sugar juice is taken to be added
In 70mL mixed solution B, it is stand-by that bubble is eliminated after mixing evenly.
A certain amount of mixed solution C is taken, is added Geniposide according to 0.04% of chitosan mass contained by it, after stirring and dissolving,
Solution is poured in masking mould, so that it is prolonged stream and is unfolded, it is dry under static conditions, film is taken off after film forming.
Embodiment 4
1) preparation of mixed solution A:
It accurately weighs 2g chitosan to be added in 100mL acetic acid solution (concentration 1%, v/v), stir completely molten to chitosan
Solution is then added 1.3g glycerol and 0.7g nano-graphene stirs evenly, filtering removal insoluble substance, for use.
2) preparation of mixed solution B:
It accurately weighs sodium bicarbonate to be dissolved in distilled water, the solution that concentration is 0.25mol/L is prepared.Then by carbonic acid
Hydrogen sodium solution is added drop-wise in mixed solution A under stirring conditions, makes the final pH 5.8 of solution, for use.
3) preparation of mixed solution C:
It accurately weighs pulullan polysaccharide 4g to be dissolved in 100mL distilled water, takes 30mL pulullan polysaccharide solution that 70mL is added mixed
It closes in solution B, it is stand-by to eliminate bubble after mixing evenly.
A certain amount of mixed solution C is taken, is added Geniposide according to 0.05% of chitosan mass contained by it, after stirring and dissolving,
Solution is poured in masking mould, so that it is prolonged stream and is unfolded, it is dry under static conditions, film is taken off after film forming.
It is the identification method explanation to the embodiment of the present invention 1 to embodiment 4 below:
1, swelling ratio:
Film is cut into certain size, weigh and is recorded, is subsequently dipped in distilled water, is taken out afterwards for 24 hours carefully with filter
Paper dries surface moisture, is weighed and is recorded with assay balance, so measures the swelling ratio of different moments sample.The calculating of swelling ratio
Formula is as follows:
In formula: Wt--- weight of the sample in the t time；
W0--- the initial weight of sample.
Table 2 illustrates the swelling ratio of traditional chitosan film and embodiment 1-4.From result it is recognised that traditional chitosan film
There is very high swellbility in aqueous solution, this is very unfavorable to the application of chitosan film.And shell prepared by embodiment 1-4 is poly-
For the swelling ratio of sugared multidimensional crosslinked composite membrane only between 28.54%-36.15%, this illustrates that the composite membrane of this method preparation has
Good water-resistant type can effectively prevent chitosan film in aqueous solution because mechanical performance declines caused by swelling.It is real
It applies the lower one side reason of composite membrane degree of swelling prepared by a 1-4 and is that the addition of metal salt has neutralized part acetic acid,
Make the reduction of amino of chitosan protonation.On the other hand, the anion in metal salt is as a kind of ion crosslinking agent, in addition after
The addition of continuous chemical crosslinking and a variety of composite materials, collective effect make the composite membrane have extremely strong water-resistant capacity.
The swelling ratio of 1. embodiment 1-4 of table
| Traditional chitosan film | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Swelling ratio (%) | 250 | 28.54 | 34.26 | 36.15 | 31.72 |
2, the mechanical performance under drying regime and solvent swelling state:
Film is placed in the drying box that relative humidity is 53% ± 5%, balances 48h in 25 DEG C of environment.Film is cut into
The strip of 10mm × 50mm.The thickness of film takes 5 points at random on film, is measured and is made even with digital display spiral micrometer (0.01mm)
Mean value.Using the mechanical performance of Texture instrument test film, upper and lower clamp distance is 30mm, and rate of extension is set as 1mm/s, each sample
It surveys 5 times.
The tensile strength of film is calculated by formula (1):
In formula: F --- maximum stretching force (N)；
The width (mm) of a --- film；
The thickness (mm) of b --- film.
The strain of film is calculated by formula (2):
In formula: L --- the length (mm) when film stretching is broken；
L1--- the length (mm) before film stretching.
Table 2 illustrates the fracturing machine performance of traditional chitosan film and embodiment 1-4 under drying regime.It can be obtained from result
Out, for compared to traditional chitosan film, the fracture strength of chitosan complex film prepared by embodiment 1-4 is increased substantially,
Fracture strength compares traditional chitosan film and increases 533.6%-588.9%, and its strain property is also compared and increased
218.7%-250.5%.This is mainly due to there are a variety of cross-linked forms and a variety of multiple in the composite membrane prepared by this method
Condensation material, this significantly increases the tightness degree between chitosan molecule chain, so that its mechanical performance be made to greatly improve.
Table 3 illustrates the fracturing machine performance of traditional chitosan film and embodiment 1-4 under solvent swelling state.It is poly- for traditional shell
For sugared film, after swelling, mechanical performance sharply declines, almost broken at a touch, can not carry out measuring mechanical property.Review reality
Chitosan complex film prepared by a 1-4 is applied, after swelling, fracture strength still maintains the 83.7%- of drying regime
92.3%, and its strain property still maintains the 88.4%-91.5% of drying regime.This illustrates chitosan prepared by the present invention
Multidimensional crosslinked composite membrane still is able to have good mechanical performance in aqueous solution, can satisfy in aqueous solution or high humility
Under the conditions of application request.
The mechanical performance of traditional chitosan film and embodiment 1-4 under 2. drying regime of table
The mechanical performance of traditional chitosan film and embodiment 1-4 under 3. solvent swelling state of table
3, fresh meat is packed:
Chitosan complex film prepared by Example 1-4 packs the fresh meat of certain mass, with unpacked fresh
Meat as control, after being placed 8 days under the conditions of 4 DEG C, according to national standard method measurement fresh meat total remission rate content and
Thiobarbituric acid reaction object content evaluates application effect of this chitosan complex film in fresh meat is fresh-keeping with this.It can from table 4
To know, the fresh meat of blank control group is after placing 8 days, TVB-N content and thiobarbituric acid reaction object content
Sample packaged by significantly larger than embodiment 1-4 illustrates that metal salt chitosan multidimensional crosslinked composite membrane prepared by the present invention exists
There is excellent application effect in food packaging, and will not be influenced by the high-moisture of food.
Application of the 4. embodiment 1-4 of table in fresh meat packaging
4, sewage treatment is tested:
Chitosan complex film prepared by the embodiment 1-4 of same quality is taken to inhale certain density methyl orange solution
Attached experiment removes chitosan complex film after handling 2h from solution, is commented by remaining methyl orange content in measurement solution
The wastewater treatment efficiency of valence chitosan complex film.The results are shown in Table 5, chitosan complex film prepared by embodiment 1-4 compared with
In the short time, there is very high adsorbance to anionic dye methyl orange, this illustrates that chitosan prepared by this method is multiple
Sewage treatment can be advantageously applied to by closing film.
Adsorption effect of the 5. embodiment 1-4 of table to methyl orange
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Adsorbance (mg/g) | 564.73 | 528.97 | 632.55 | 605.42 |
5, bacteriostatic experiment:
Chitosan complex film prepared by Example 1-4 (round, diameter 6mm) carries out high pressure sterilization, while by 100 μ L
Concentration is that the Escherichia coli of 107CFU/mL and bacillus subtilis bacteria suspension are mixed in agar medium for use.After sterilizing
Chitosan complex film be placed on media surface, carried out at 37 DEG C culture 2 days after, calculate inhibition zone size.Knot from table 6
Fruit is it is found that chitosan complex film prepared by embodiment 1-4 (removes from office blue Escherichia coli (Gram-negative) and bacillus subtilis
Family name is positive) all have good fungistatic effect.This shows that metal salt chitosan multidimensional crosslinked composite membrane can prepared by the present invention
With the field for for food packaging and Wound healing and bone regeneration etc. needing that there is bacteria resistance function.Especially in Wound healing and bone regeneration, the present invention
The mechanical performance of prepared chitosan complex film not will receive tissue fluid exudation influence, can digital preservation wound, play
Bacteriostasis.
Fungistatic effect of the 6. embodiment 1-4 of table to Escherichia coli and bacillus subtilis
6, microstructure observing:
Fig. 1-4 is please referred to, it can be seen from the figure that prepared film is all very fine and close neat, apparent phase does not occur
Separation and material aggregation, this illustrates that each nano material is well dispersed inside composite membrane prepared by this method, macromolecular material phase
It mutually tangles, forms fine and close composite membrane.
Although hereinbefore invention has been described by reference to embodiment, the scope of the present invention is not being departed from
In the case where, various improvement can be carried out to it and can replace component therein with equivalent.Especially, as long as being not present
Structural conflict, the various features in presently disclosed embodiment can be combined with each other use by any way, In
The description for not carrying out exhaustive to the case where these combinations in this specification is examined merely for the sake of omission length with what is economized on resources
Consider.Therefore, the invention is not limited to specific embodiments disclosed herein, but the institute including falling within the scope of the appended claims
There is technical solution.
Claims (6)
1. a kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane, which comprises the following steps:
(1) it dissolves the chitosan in acetic acid solution, the sweet of the complex material A and 0.5-3% that content is 1-30% is then added
The mixed solution A that chitosan content is 1-5% is made in oil；
(2) metal salt solution that concentration is 0.02-0.5mol/L is added in mixed solution A, obtains pH in 5.5-6.8 range
Interior mixed solution B；
(3) complex material B solution is added in mixed solution B and obtains mixed solution C, wherein the content of complex material B is shell
The 5-40% of glycan quality；
(4) crosslinking agent is added in mixed solution C according to the ratio of the 0.01-4% of chitosan mass, is removed after mixing evenly
Bubble in solution then in a mold by solution, or is coated in food surface, after evaporation drying to obtain the final product.
2. a kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane according to claim 1, it is characterised in that:
The volumetric concentration of the acetic acid solution is 0.1-2%.
3. a kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane according to claim 1, it is characterised in that:
The complex material A is one of nano silica, nano-titanium dioxide, nano-graphene, carbon nanotube, montmorillonite
Or it is a variety of.
4. a kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane according to claim 1, it is characterised in that:
The metal salt is sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, disodium hydrogen phosphate, dipotassium hydrogen phosphate, β phosphoglycerol
One of disodium is a variety of.
5. a kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane according to claim 1, it is characterised in that:
The complex material B is polyvinyl alcohol, konjaku glucomannan, carboxymethyl cellulose, pulullan polysaccharide, sodium alginate, gelatin
One of or it is a variety of；The mass concentration of the complex material B solution is 0.5-10%.
6. a kind of preparation method of multipurpose water-resistant type multidimensional crosslinked composite membrane according to claim 1, it is characterised in that:
The crosslinking agent is one of Geniposide, glutaraldehyde, dialdehyde starch or a variety of.
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