CN102585265B - Preparation method of gelatin/poli vinyl alcohol (PVA) composite films crosslinked with glutaraldehyde solution - Google Patents
Preparation method of gelatin/poli vinyl alcohol (PVA) composite films crosslinked with glutaraldehyde solution Download PDFInfo
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Abstract
The invention provides a preparation method of gelatin/poli vinyl alcohol (PVA) composite films crosslinked with glutaraldehyde solution and relates to the preparation method of the gelatin/PVA composite films. Firstly, pre-prepared PVA solution and gelatin solution are mixed, then, a certain number of plasticizers and glutaraldehyde are added, the low-temperature treatment is carried out for a period of time after the stirring, the uniformly mixed solution is poured into a mold for natural curtain coating, next, the materials are dried at the room temperature, and the gelatin/PVA composite films crosslinked with glutaraldehyde solution are obtained. Compared with the ordinary gelatin/PVA composite films, the gelatin/PVA composite films prepared by the preparation method have the advantages that the comprehensive performance is better, and both the tensile strength and the water resisting performance are improved.
Description
Technical field
The present invention relates to the preparation method of a kind of gelatin/PVA composite membrane, specifically the preparation method of the crosslinked gelatin of a kind of glutaraldehyde solution/PVA composite membrane.
Background technology
At present, the plastics such as the polyethylene of preparation, polypropylene, polyvinyl chloride are seen everywhere in life take oil as raw material, it is greatly convenient that they have brought for people's life, but the simultaneously most stable performances of these plastics, be difficult to biological degradation, after discarded, bring great negative impact to environment, therefore people can satisfy again the material product of service requirements at the new degradable of active research, mostly this kind material product is compounded by different macromolecular materials at present, and gelatin/PVA composite membrane is exactly wherein a kind of.Gelatin is made of and derives from a kind of protein of animal body multiple amino acids, it also is a kind of natural macromolecular material simultaneously, has the advantages such as good biocompatibility, degradability; Polyvinyl alcohol (PVA) is in daily use in the middle of synthesized polymer material, is a kind of nontoxic, non-irritating hydrophilic superpolymer, has the advantages such as good bioaffinity, film-forming properties, fiberizability and cementability, and has preferably mechanical property.So with gelatin and the compound character that has bi-material with the composite membrane of expecting preparation concurrently of PVA bi-material, in the actual fabrication process of gelatin/PVA composite membrane, the performance of film has the several factors impact, wherein add linking agent and can make prepared composite membrane have better mechanical property and water tolerance etc., different linking agents and cross-linking method all can produce certain impact to the performance of prepared film.At present, have and report that the glutaraldehyde vapor crosslinking produces certain influence to the water resistance of gelatin/PVA composite membrane, and it is not described to the improvement situation of other performances of film, and this method operating time is long, inconvenience is carried out.And the present invention carries out crosslinked in film-forming process with the crosslinked method of glutaraldehyde solution, operating procedure is fairly simple, crosslinking time is short, optimizes simultaneously film-forming process, has finally prepared the gelatin better than general gelatin/PVA composite membrane over-all properties/PVA composite membrane.
Summary of the invention
In order to prepare the better gelatin of over-all properties/PVA composite membrane, the invention provides the preparation method of the crosslinked gelatin of a kind of glutaraldehyde solution/PVA composite membrane.
In order to achieve the above object, technical scheme of the present invention is achieved in that the preparation method of the crosslinked gelatin of a kind of glutaraldehyde solution/PVA composite membrane, comprises following step:
(1), the preparation of polyvinyl alcohol solution: the polyvinyl alcohol that takes by weighing the 4-11 weight part adds there-necked flask, the distilled water that measures again the 80-105 weight part adds in the there-necked flask, placing 80-90 ℃ water bath with thermostatic control to be stirred to polyvinyl alcohol in flask dissolves fully, obtain polyvinyl alcohol water solution, i.e. A solution;
(2), the preparation of gelatin solution: the gelatin that takes by weighing the 5-10 weight part adds in the beaker, the distilled water that measures again the 80-100 weight part adds in the beaker, under the room temperature behind the swelling 30min, being stirred to gelatin in 50 ℃ water bath with thermostatic control dissolves fully, remove by filter impurity, namely obtain gelatin solution, i.e. B solution;
(3), the preparation of gelatin/PVA composite membrane: 4:1-7:1 takes by weighing A by weight, two kinds of solution of B join in the there-necked flask, add again softening agent and glutaraldehyde, under 0-10 ℃ of low temperature, preserved 2-5 hour after stirring, then in 30-70 ℃ water bath with thermostatic control, stirred 4 hours, pour the mixed solution that mixes in the mould natural curtain coating, make mixed solution at room temperature dry, namely obtain the gelatin of solution crosslinking/PVA composite membrane.
In the described A solution, the weight ratio of polyvinyl alcohol and water is preferably 1:9, and in the B solution, the weight ratio of gelatin and water is preferably 1:9, and the weight ratio of A, two kinds of solution of B is preferably 4:1.
Described softening agent is ethylene glycol, glycerine or PEG200, and its consumption is 0.6% of A, two kinds of solution gross weights of B.
The consumption of described glutaraldehyde is the 0.01%-0.06% of A, two kinds of solution gross weights of B.
Beneficial effect: the gelatin of the present invention preparation/PVA composite membrane is when having good consistency and certain degradation property, it has better mechanical property than common gelatin/PVA composite membrane, improved tensile strength and the water tolerance of film, the over-all properties of film is better; Especially for some time through subzero treatment is also assisted the mechanical property that has increased film in the inventive method; Product of the present invention can be applied in medical and other article packing fields.
Embodiment
The preparation method of the crosslinked gelatin of a kind of glutaraldehyde solution/PVA composite membrane comprises following step:
(1), the preparation of polyvinyl alcohol solution: the polyvinyl alcohol that takes by weighing the 4-11 weight part adds there-necked flask, the distilled water that measures again the 80-105 weight part adds in the there-necked flask, placing 80-90 ℃ water bath with thermostatic control to be stirred to polyvinyl alcohol in flask dissolves fully, obtain polyvinyl alcohol water solution, i.e. A solution;
(2), the preparation of gelatin solution: the gelatin that takes by weighing the 5-10 weight part adds in the beaker, the distilled water that measures again the 80-100 weight part adds in the beaker, under the room temperature behind the swelling 30min, being stirred to gelatin in 50 ℃ water bath with thermostatic control dissolves fully, remove by filter impurity, namely obtain gelatin solution, i.e. B solution;
(3), the preparation of gelatin/PVA composite membrane: 4:1-7:1 takes by weighing A by weight, two kinds of solution of B join in the there-necked flask, add again softening agent and glutaraldehyde, under 0-10 ℃ of low temperature, preserved 2-5 hour after stirring, then in 30-70 ℃ water bath with thermostatic control, stirred 4 hours, pour the mixed solution that mixes in the mould natural curtain coating, make mixed solution at room temperature dry, namely obtain the gelatin of solution crosslinking/PVA composite membrane.
In the described A solution, the weight ratio of polyvinyl alcohol and water is preferably 1:9, and in the B solution, the weight ratio of gelatin and water is preferably 1:9, and the weight ratio of A, two kinds of solution of B is preferably 4:1.
Described softening agent is ethylene glycol, glycerine or PEG200, and its consumption is 0.6% of A, two kinds of solution gross weights of B.
The consumption of described glutaraldehyde is the 0.01%-0.06% of A, two kinds of solution gross weights of B.
Mechanics Performance Testing: film is cut into inferior prismatic according to GB GB/T1040.3, test behind (the moisture eliminator bottom is saturated KBr solution) balance 60h in the at room temperature moisture eliminator of putting, the test fixture spacing is 25mm, rate of extension 50mm/min, test is at room temperature carried out, test 5～7 samples, get arithmetical av.
Dissolution rate testing method: film is cut into the square of 1cm * 1cm size, at first claims its quality m with its oven dry
1, and then film immersed in the small beaker contain 10mL distilled water soak 60min, suck surface-moisture with filter paper, again film is placed in the baking oven at last and dries, claim its quality m
2, its dissolution rate=(m
1-m
2)/m
1* 100%.
Embodiment 1
Take by weighing the 10g polyvinyl alcohol and place there-necked flask, add 90g distilled water, mechanical stirring is dissolved fully to it in 90 ℃ water bath with thermostatic control, refilters to remove impurity, obtains strength of solution and be 10% polyvinyl alcohol water solution;
Take by weighing the 10g gelatin and place beaker, add 90g distilled water, swelling 30min at room temperature is stirred to it afterwards and dissolves fully in 50 ℃ water bath with thermostatic control first, refilters and removes impurity, namely obtains strength of solution and be 10% gelatin solution;
Above-mentioned polyvinyl alcohol solution and gelatin solution are joined in the 250ml there-necked flask by weight 4:1, add again the softening agent ethylene glycol of two kinds of solution gross weights 0.6% and the glutaraldehyde of two kinds of solution gross weights 0.06%, then under 0 ℃ of environment, store 5 hours, then mechanical stirring was reacted 4 hours in 50 ℃ water bath with thermostatic control, pour the mixed solution that mixes in the mould natural curtain coating, make mixed solution at room temperature dry, can obtain gelatin/PVA composite membrane.Composite membrane is carried out Mechanics Performance Testing, and its result is: tensile strength is 27.6MPa, and elongation at break is 658%; The dissolution rate test result is 18.5%.
Embodiment 2
Take by weighing the 10g polyvinyl alcohol and place there-necked flask, add 90g distilled water, mechanical stirring is dissolved fully to it in 90 ℃ water bath with thermostatic control, refilters to remove impurity, obtains strength of solution and be 10% polyvinyl alcohol water solution;
Take by weighing the 10g gelatin and place beaker, add 90g distilled water, swelling 30min at room temperature is stirred to it afterwards and dissolves fully in 50 ℃ water bath with thermostatic control first, refilters and removes impurity, namely obtains strength of solution and be 10% gelatin solution;
Above-mentioned polyvinyl alcohol solution and gelatin solution are joined in the 250ml there-necked flask by weight 4:1, add again the softening agent glycerine of two kinds of solution gross weights 0.6% and the glutaraldehyde of two kinds of solution gross weights 0.03%, then under 10 ℃ of environment, store 4 hours, then mechanical stirring was reacted 4 hours in 50 ℃ water bath with thermostatic control, pour the mixed solution that mixes in the mould natural curtain coating, make mixed solution at room temperature dry, can obtain gelatin/PVA composite membrane.Composite membrane is carried out Mechanics Performance Testing, and its result is: tensile strength is 26.3MPa, and elongation at break is 595%; The dissolution rate test result is 22.6%.
Embodiment 3
Take by weighing the 10g polyvinyl alcohol and place there-necked flask, add 90g distilled water, mechanical stirring is dissolved fully to it in 90 ℃ water bath with thermostatic control, refilters to remove impurity, obtains strength of solution and be 10% polyvinyl alcohol water solution;
Take by weighing the 10g gelatin and place beaker, add 90g distilled water, swelling 30min at room temperature is stirred to it afterwards and dissolves fully in 50 ℃ water bath with thermostatic control first, refilters and removes impurity, namely obtains strength of solution and be 10% gelatin solution;
Above-mentioned polyvinyl alcohol solution and gelatin solution are joined in the 250ml there-necked flask by weight 4:1, add again the plasticizer P EG200 of two kinds of solution gross weights 0.6% and the glutaraldehyde of two kinds of solution gross weights 0.01%, then under 5 ℃ of environment, store 2 hours, then mechanical stirring was reacted 4 hours in 30 ℃ water bath with thermostatic control, pour the mixed solution that mixes in the mould natural curtain coating, make mixed solution at room temperature dry, can obtain gelatin/PVA composite membrane.Composite membrane is carried out Mechanics Performance Testing, and its result is: tensile strength is 24.6MPa, and elongation at break is 630%; The dissolution rate test result is 29.8%.
Embodiment 4
Take by weighing the 10g polyvinyl alcohol and place there-necked flask, add 90g distilled water, mechanical stirring is dissolved fully to it in 90 ℃ water bath with thermostatic control, refilters to remove impurity, obtains strength of solution and be 10% polyvinyl alcohol water solution;
Take by weighing the 10g gelatin and place beaker, add 90g distilled water, swelling 30min at room temperature is stirred to it afterwards and dissolves fully in 50 ℃ water bath with thermostatic control first, refilters and removes impurity, namely obtains strength of solution and be 10% gelatin solution;
Above-mentioned polyvinyl alcohol solution and gelatin solution are joined in the 250ml there-necked flask by weight 5:1, add again the softening agent ethylene glycol of two kinds of solution gross weights 0.6% and the glutaraldehyde of two kinds of solution gross weights 0.06%, then under 0 ℃ of environment, store 5 hours, then mechanical stirring was reacted 4 hours in 50 ℃ water bath with thermostatic control, pour the mixed solution that mixes in the mould natural curtain coating, make mixed solution at room temperature dry, can obtain gelatin/PVA composite membrane.Composite membrane is carried out Mechanics Performance Testing, and its result is: tensile strength is 28.5MPa, and elongation at break is 596%; The dissolution rate test result is 15.6%.
Embodiment 5
Take by weighing the 10g polyvinyl alcohol and place there-necked flask, add 90g distilled water, mechanical stirring is dissolved fully to it in 90 ℃ water bath with thermostatic control, refilters to remove impurity, obtains strength of solution and be 10% polyvinyl alcohol water solution;
Take by weighing the 10g gelatin and place beaker, add 90g distilled water, swelling 30min at room temperature is stirred to it afterwards and dissolves fully in 50 ℃ water bath with thermostatic control first, refilters and removes impurity, namely obtains strength of solution and be 10% gelatin solution;
Above-mentioned polyvinyl alcohol solution and gelatin solution are joined in the 250ml there-necked flask by weight 7:1, add again the softening agent ethylene glycol of two kinds of solution gross weights 0.6% and the glutaraldehyde of two kinds of solution gross weights 0.06%, then under 10 ℃ of environment, store 4 hours, then mechanical stirring was reacted 4 hours in 70 ℃ water bath with thermostatic control, pour the mixed solution that mixes in the mould natural curtain coating, make mixed solution at room temperature dry, can obtain gelatin/PVA composite membrane.Composite membrane is carried out Mechanics Performance Testing, and its result is: tensile strength is 30.1MPa, and elongation at break is 628%; The dissolution rate test result is 12.9%.
Comparative Examples 1
Do not add glutaraldehyde, other operates with embodiment 1.
Composite membrane is carried out Mechanics Performance Testing, and its result is: tensile strength is 19.8MPa, and elongation at break is 610%; The dissolution rate test result is 32.9%.
Comparison by Comparative Examples and embodiment, also can find out, gelatin and PVA are when same ratio in composite membrane, and tensile strength and the elongation at break of composite membrane all are improved after the adding glutaraldehyde, and dissolution rate has also descended after the adding glutaraldehyde, and this has improved the water tolerance of film simultaneously.
Claims (2)
1. the preparation method of the crosslinked gelatin of a glutaraldehyde solution/PVA composite membrane is characterized in that: comprise the steps:
(1), the preparation of polyvinyl alcohol solution:
The polyvinyl alcohol that takes by weighing the 4-11 weight part places there-necked flask, adds the distilled water of 80-105 weight part again, is stirred to polyvinyl alcohol and dissolves fully in 80-90 ℃ water bath with thermostatic control, obtains polyvinyl alcohol water solution, i.e. PVA solution;
(2), the preparation of gelatin solution:
The gelatin that takes by weighing the 5-10 weight part places beaker, adds the distilled water of 80-100 weight part again, and first swelling 30min at room temperature is stirred to gelatin afterwards and dissolves fully in 50 ℃ water bath with thermostatic control, remove by filter impurity after, obtain gelatin solution;
(3), the preparation of gelatin/PVA composite membrane:
Above-mentioned PVA solution and gelatin solution are joined in the container by weight 4:1-7:1, add again softening agent and glutaraldehyde, under 0-10 ℃ of low temperature, preserved 2-5 hour after stirring, then in 30-70 ℃ water bath with thermostatic control, stirred 4 hours, pour the mixed solution that mixes in the mould natural curtain coating, make mixed solution at room temperature dry, namely obtain the crosslinked gelatin of glutaraldehyde solution/PVA composite membrane;
The consumption of described softening agent is 0.6% of PVA solution and gelatin solution gross weight; The consumption of described glutaraldehyde is the 0.01%-0.06% of PVA solution and gelatin solution gross weight.
2. the preparation method of the crosslinked gelatin of a kind of glutaraldehyde solution as claimed in claim 1/PVA composite membrane, it is characterized in that: described softening agent is ethylene glycol, glycerine or PEG200.
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| CN108070262A (en) * | 2017-12-29 | 2018-05-25 | 常州市阿曼特化工有限公司 | A kind of preparation method of tensile type gelatin film |
| CN109078616B (en) * | 2018-09-14 | 2021-06-18 | 河南科技大学 | Tannin modified graphene/gelatin porous composite material and preparation method and application thereof |
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| CN112143148A (en) * | 2020-09-25 | 2020-12-29 | 湖南安翔科技有限公司 | Polyvinyl alcohol film and preparation method thereof |
| CN115895154A (en) * | 2022-11-29 | 2023-04-04 | 无锡学院 | Degradable high-barrier film and preparation method thereof |
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