CN102585265A - 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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- CN102585265A CN102585265A CN2012100184063A CN201210018406A CN102585265A CN 102585265 A CN102585265 A CN 102585265A CN 2012100184063 A CN2012100184063 A CN 2012100184063A CN 201210018406 A CN201210018406 A CN 201210018406A CN 102585265 A CN102585265 A CN 102585265A
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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 package, specifically is the preparation method of the crosslinked gelatin of a kind of glutaraldehyde solution/PVA composite package.
Background technology
At present; The plastics such as Vilaterm, Vestolen PP 7052, SE that with the oil are feedstock production are seen everywhere in life; It is greatly convenient that they have brought for people's life, but most stable performances of these plastics simultaneously are difficult to biological degradation; Bring great negative impact in discarded back to environment; Therefore people can satisfy the material product of request for utilization again at the new degradable of active research, and mostly this kind material product is compounded by different macromolecular materials at present, and gelatin/PVA composite package is exactly wherein a kind of.A kind of protein of animal body is made up of and is derived to gelatin multiple amino acids, it also is a kind of natural macromolecular material simultaneously, has advantages such as excellent biological compatibility, degradability; Z 150PH (PVA) is in daily use in the middle of synthesized polymer material, is a kind of nontoxic, non-irritating hydrophilic superpolymer, has advantages such as good bioaffinity, film-forming properties, fiberizability and cementability, and has mechanical property preferably.So with gelatin and the compound character that has two kinds of materials with the composite package of expecting preparation concurrently of two kinds of materials of PVA; In the actual fabrication process of gelatin/PVA composite package; The performance of film has the several factors influence; Wherein add linking agent and can make the prepared composite film have excellent mechanical property and water tolerance etc. more, different linking agents and cross-linking method all can produce certain influence to the performance of prepared film.At present, have and report that the LUTARALDEHYDE vapor crosslinking produces certain influence to the water resistance of gelatin/PVA composite package, and its improvement situation to other performances of film is not described, and this method running 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 film-forming process simultaneously, has finally prepared the gelatin better than general gelatin/PVA composite package over-all properties/PVA composite package.
Summary of the invention
In order to prepare the better gelatin of over-all properties/PVA composite package, the present invention provides the preparation method of the crosslinked gelatin of a kind of glutaraldehyde solution/PVA composite package.
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 package, comprises following step:
(1), the preparation of polyvinyl alcohol solution: the Z 150PH that takes by weighing the 4-11 weight part adds there-necked flask; The zero(ppm) water of measuring the 80-105 weight part again adds in the there-necked flask; Placing 80-90 ℃ water bath with thermostatic control to be stirred to Z 150PH 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 zero(ppm) water of measuring the 80-100 weight part again adds in the beaker; Behind the swelling 30min, in 50 ℃ water bath with thermostatic control, be stirred to gelatin and dissolve fully under the room temperature, remove by filter impurity; Promptly obtain gelatin solution, i.e. B solution;
(3), the preparation of gelatin/PVA composite package: by weight 4:1-7:1 take by weighing A, two kinds of solution of B join in the there-necked flask; Add softening agent and LUTARALDEHYDE again; Stir the back and under 0-10 ℃ of low temperature, preserved 2-5 hour, in 30-70 ℃ water bath with thermostatic control, stirred 4 hours then, pour the mixed solution that mixes in the mould natural curtain coating; Make mixed solution at room temperature dry, promptly obtain the gelatin/PVA composite package of solution crosslinking.
In the described A solution, the weight ratio of Z 150PH 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 terepthaloyl moietie, glycerine or PEG200, and its consumption is 0.6% of A, two kinds of solution gross weights of B.
The consumption of described LUTARALDEHYDE is the 0.01%-0.06% of A, two kinds of solution gross weights of B.
Beneficial effect: the gelatin/PVA composite package of the present invention preparation is when having good consistency and certain degradation property; It has better mechanical property than common gelatin/PVA composite package; Improved the tensile strength and the water tolerance of film, the over-all properties of film is better; Especially also assist the mechanical property that has increased film through for some time of subzero treatment in the inventive method; Product of the present invention can be applied in medical and other article packing fields.
Embodiment
The preparation method of gelatin/PVA composite package that a kind of glutaraldehyde solution is crosslinked comprises following step:
(1), the preparation of polyvinyl alcohol solution: the Z 150PH that takes by weighing the 4-11 weight part adds there-necked flask; The zero(ppm) water of measuring the 80-105 weight part again adds in the there-necked flask; Placing 80-90 ℃ water bath with thermostatic control to be stirred to Z 150PH 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 zero(ppm) water of measuring the 80-100 weight part again adds in the beaker; Behind the swelling 30min, in 50 ℃ water bath with thermostatic control, be stirred to gelatin and dissolve fully under the room temperature, remove by filter impurity; Promptly obtain gelatin solution, i.e. B solution;
(3), the preparation of gelatin/PVA composite package: by weight 4:1-7:1 take by weighing A, two kinds of solution of B join in the there-necked flask; Add softening agent and LUTARALDEHYDE again; Stir the back and under 0-10 ℃ of low temperature, preserved 2-5 hour, in 30-70 ℃ water bath with thermostatic control, stirred 4 hours then, pour the mixed solution that mixes in the mould natural curtain coating; Make mixed solution at room temperature dry, promptly obtain the gelatin/PVA composite package of solution crosslinking.
In the described A solution, the weight ratio of Z 150PH 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 terepthaloyl moietie, glycerine or PEG200, and its consumption is 0.6% of A, two kinds of solution gross weights of B.
The consumption of described LUTARALDEHYDE 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 moisture eliminator of putting at room temperature; The test fixture spacing is 25mm, rate of extension 50mm/min, and test is at room temperature carried out; Test 5～7 samples, get arithmetical av.
Dissolution rate testing method: film is cut into the big or small square of 1cm * 1cm, at first claims its quality m with its oven dry
1, and then film immersed in the small beaker contain 10mL zero(ppm) water soak 60min, inhale with filter paper and remove surface-moisture, again film is presented 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 Z 150PH and place there-necked flask, add 90g zero(ppm) water, mechanical stirring is dissolved to it fully 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 zero(ppm) water, swelling 30min at room temperature earlier, the back is stirred to it and dissolves fully in 50 ℃ water bath with thermostatic control, refilter and remove impurity, promptly 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 the softening agent terepthaloyl moietie of two kinds of solution gross weights 0.6% and the LUTARALDEHYDE of two kinds of solution gross weights 0.06% again; Under 0 ℃ of environment, store 5 hours then, mechanical stirring was reacted 4 hours in 50 ℃ water bath with thermostatic control then, poured the mixed solution that mixes in the mould natural curtain coating; Make mixed solution at room temperature dry, can obtain gelatin/PVA composite package.Composite package 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 Z 150PH and place there-necked flask, add 90g zero(ppm) water, mechanical stirring is dissolved to it fully 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 zero(ppm) water, swelling 30min at room temperature earlier, the back is stirred to it and dissolves fully in 50 ℃ water bath with thermostatic control, refilter and remove impurity, promptly 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 the softening agent glycerine of two kinds of solution gross weights 0.6% and the LUTARALDEHYDE of two kinds of solution gross weights 0.03% again; Under 10 ℃ of environment, store 4 hours then, mechanical stirring was reacted 4 hours in 50 ℃ water bath with thermostatic control then, poured the mixed solution that mixes in the mould natural curtain coating; Make mixed solution at room temperature dry, can obtain gelatin/PVA composite package.Composite package 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 Z 150PH and place there-necked flask, add 90g zero(ppm) water, mechanical stirring is dissolved to it fully 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 zero(ppm) water, swelling 30min at room temperature earlier, the back is stirred to it and dissolves fully in 50 ℃ water bath with thermostatic control, refilter and remove impurity, promptly 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 the plasticizer P EG200 of two kinds of solution gross weights 0.6% and the LUTARALDEHYDE of two kinds of solution gross weights 0.01% again; Under 5 ℃ of environment, store 2 hours then, mechanical stirring was reacted 4 hours in 30 ℃ water bath with thermostatic control then, poured the mixed solution that mixes in the mould natural curtain coating; Make mixed solution at room temperature dry, can obtain gelatin/PVA composite package.Composite package 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 Z 150PH and place there-necked flask, add 90g zero(ppm) water, mechanical stirring is dissolved to it fully 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 zero(ppm) water, swelling 30min at room temperature earlier, the back is stirred to it and dissolves fully in 50 ℃ water bath with thermostatic control, refilter and remove impurity, promptly 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 the softening agent terepthaloyl moietie of two kinds of solution gross weights 0.6% and the LUTARALDEHYDE of two kinds of solution gross weights 0.06% again; Under 0 ℃ of environment, store 5 hours then, mechanical stirring was reacted 4 hours in 50 ℃ water bath with thermostatic control then, poured the mixed solution that mixes in the mould natural curtain coating; Make mixed solution at room temperature dry, can obtain gelatin/PVA composite package.Composite package 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 Z 150PH and place there-necked flask, add 90g zero(ppm) water, mechanical stirring is dissolved to it fully 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 zero(ppm) water, swelling 30min at room temperature earlier, the back is stirred to it and dissolves fully in 50 ℃ water bath with thermostatic control, refilter and remove impurity, promptly 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 the softening agent terepthaloyl moietie of two kinds of solution gross weights 0.6% and the LUTARALDEHYDE of two kinds of solution gross weights 0.06% again; Under 10 ℃ of environment, store 4 hours then, mechanical stirring was reacted 4 hours in 70 ℃ water bath with thermostatic control then, poured the mixed solution that mixes in the mould natural curtain coating; Make mixed solution at room temperature dry, can obtain gelatin/PVA composite package.Composite package 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 LUTARALDEHYDE, other is operated with embodiment 1.
Composite package 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 through Comparative Examples and embodiment; Can find out that also gelatin and PVA are when same ratio in composite package, the tensile strength and the elongation at break of composite package all have raising behind the adding LUTARALDEHYDE; And dissolution rate has also descended behind the adding LUTARALDEHYDE, and this has improved the water tolerance of film simultaneously.
Claims (3)
1. the preparation method of the crosslinked gelatin/PVA composite package of a glutaraldehyde solution is characterized in that: comprise the steps:
(1), the preparation of polyvinyl alcohol solution:
The Z 150PH that takes by weighing the 4-11 weight part places there-necked flask, adds the zero(ppm) water of 80-105 weight part again, in 80-90 ℃ water bath with thermostatic control, is stirred to Z 150PH and dissolves fully, 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 zero(ppm) water of 80-100 weight part again, first swelling 30min at room temperature, the back is stirred to gelatin 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 package:
Above-mentioned PVA solution and gelatin solution are joined in the container by weight 4:1-7:1; Add softening agent and LUTARALDEHYDE again; Stir the back and under 0-10 ℃ of low temperature, preserved 2-5 hour, in 30-70 ℃ water bath with thermostatic control, stirred 4 hours then, pour the mixed solution that mixes in the mould natural curtain coating; Make mixed solution at room temperature dry, promptly obtain the crosslinked gelatin of glutaraldehyde solution/PVA composite package.
2. the preparation method of gelatin/PVA composite package that a kind of glutaraldehyde solution as claimed in claim 1 is crosslinked is characterized in that: described softening agent is terepthaloyl moietie, glycerine or PEG200, and its consumption is 0.6% of PVA solution and a gelatin solution gross weight.
3. the preparation method of gelatin/PVA composite package that a kind of glutaraldehyde solution as claimed in claim 1 is crosslinked is characterized in that: the consumption of described LUTARALDEHYDE is the 0.01%-0.06% of PVA solution and gelatin solution gross weight.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107673657A (en) * | 2017-09-07 | 2018-02-09 | 芜湖林电子科技有限公司 | A kind of material of construction industry 3D printing |
| 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 |
| CN109078616A (en) * | 2018-09-14 | 2018-12-25 | 河南科技大学 | A kind of tannic acid modified graphene/gelatin porous composite material and preparation method, application |
| CN110523388A (en) * | 2019-05-20 | 2019-12-03 | 北京化工大学 | A kind of gelatin/nano-attapulgite clay compounded adsorbed film and preparation method thereof |
| 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 |
-
2012
- 2012-01-20 CN CN 201210018406 patent/CN102585265B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 《Food Hydrocolloids》 20111031 Priscila M.A.Alves et al. "Development of films based on blends of gelatin and poly(vinyl alcohol) cross linked with glutaraldehyde" 第1751～1757页 1－3 第25卷, 第7期 * |
| PRISCILA M.A.ALVES ET AL.: ""Development of films based on blends of gelatin and poly(vinyl alcohol) cross linked with glutaraldehyde"", 《FOOD HYDROCOLLOIDS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107673657A (en) * | 2017-09-07 | 2018-02-09 | 芜湖林电子科技有限公司 | A kind of material of construction industry 3D printing |
| 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 |
| CN109078616A (en) * | 2018-09-14 | 2018-12-25 | 河南科技大学 | A kind of tannic acid modified graphene/gelatin porous composite material and preparation method, application |
| 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 |
| CN110523388A (en) * | 2019-05-20 | 2019-12-03 | 北京化工大学 | A kind of gelatin/nano-attapulgite clay compounded adsorbed film and preparation method thereof |
| CN110523388B (en) * | 2019-05-20 | 2021-06-29 | 北京化工大学 | Gelatin/nano-attapulgite composite adsorption film and preparation method thereof |
| 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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