CN102558589A - Preparation method of formaldehyde cross-linked gelatin/polyvinyl alcohol(PVA) composite membrane - Google Patents
Preparation method of formaldehyde cross-linked gelatin/polyvinyl alcohol(PVA) composite membrane Download PDFInfo
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- CN102558589A CN102558589A CN2012100184129A CN201210018412A CN102558589A CN 102558589 A CN102558589 A CN 102558589A CN 2012100184129 A CN2012100184129 A CN 2012100184129A CN 201210018412 A CN201210018412 A CN 201210018412A CN 102558589 A CN102558589 A CN 102558589A
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Abstract
The invention relates to a preparation method of a formaldehyde cross-linked gelatin / polyvinyl alcohol(PVA) composite membrane, in particular to a preparation method of a gelatin/PVA composite membrane. The preparation method comprises the following steps of: mixing a polyvinyl alcohol aqueous solution with a gelatin aqueous solution, adding a certain amount of plasticizer and formaldehyde into the mixture, storing the mixture for 2-5 hours at 0-10 DEG C, uniformly stirring the mixture in thermostatic waterbath, pouring the uniformly mixed solution into a mold for naturally flowing, and drying the mixed solution at room temperature, so as to obtain the formaldehyde cross-linked gelatin/PVA composite membrane. The product prepared by the invention has good biocompatibility, good degradation property and better mechanical property than the general gelatin/PVA composite membrane.
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 a kind of formaldehyde crosslinking gelatin/PVA composite package.
Background technology
In the last few years, People more and more was recognized because the serious harm that the white pollution that a large amount of uses of SE based packaging material cause brings to environment.Also the begin one's study matrix material of increasing novel degradable of people; Mostly this type matrix material is favorable mechanical performance and the mechanical property by the degradability of natural macromolecular material and synthesized polymer material, processes the matrix material of comprehensive two types of material advantages thereby different natural polymers and synthetic macromolecule be combined with each other.This type of matrix material kind has many, 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 is a kind of polymer natural materials; Have excellent biological compatibility, degradability; Z 150PH (PVA) is a kind of nontoxic, non-irritating hydrophilic superpolymer, has good bioaffinity, film-forming properties and mechanical property preferably.Common gelatin/PVA composite package that present prior art makes; Ratio through two components in the controlling diaphragm can be controlled problems such as its consistency preferably; But the mechanical property of film, solvability aspect often do not reach higher request for utilization; And the present invention passes through in film-forming process, to add linking agent formaldehyde and softening agent, and improves other processing condition, finally makes the gelatin/PVA composite package that makes have better mechanical property than common film.
Summary of the invention
In order to improve the mechanical property of common gelatin/PVA composite package, the present invention provides the preparation method of a kind of formaldehyde crosslinking gelatin/PVA composite package.
For achieving the above object, technical scheme of the present invention is achieved in that the preparation method of a kind of formaldehyde crosslinking gelatin/PVA composite package, comprises following step:
(1) preparation of Z 150PH (PVA) 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) 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) preparation of gelatin/PVA composite package: by weight 3:1-5:1 take by weighing A, two kinds of solution of B join in the there-necked flask; Add softening agent and formaldehyde again; Stir the back and preserved 2-5 hour down, in 30-70 ℃ water bath with thermostatic control, stirred 4 hours then, pour the mixed solution that mixes in the mould natural curtain coating at low temperature 0-10 ℃; Make mixed solution at room temperature dry, promptly obtain gelatin/PVA composite package.
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 formaldehyde is the 0.03%-0.08% 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, and it has mechanical property better than normal film, has improved the tensile strength and the water tolerance of composite package; 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 agricultural mulching and other article packing fields.
Embodiment
The preparation method of a kind of formaldehyde crosslinking gelatin/PVA composite package comprises following step:
(1) 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) 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) preparation of gelatin/PVA composite package: by weight 3:1-5:1 take by weighing A, two kinds of solution of B join in the there-necked flask; Add softening agent and formaldehyde again; Stir the back and preserved 2-5 hour down, in 30-70 ℃ water bath with thermostatic control, stirred 4 hours then, pour the mixed solution that mixes in the mould natural curtain coating at low temperature 0-10 ℃; Make mixed solution at room temperature dry, promptly obtain formaldehyde crosslinking gelatin/PVA composite package.
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 formaldehyde is the 0.03%-0.08% 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 formaldehyde of two kinds of solution gross weights 0.08% 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.
The Mechanics Performance Testing result of composite package is: tensile strength is 38.3MPa, and elongation at break is 501%, and the dissolution rate test result of film is 11.8%.
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 formaldehyde of two kinds of solution gross weights 0.03% again; Under 10 ℃ 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.
The Mechanics Performance Testing result of composite package is: tensile strength is 30.3MPa, and elongation at break is 539%, and the dissolution rate test result of film is: 17.6%.
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 3:1; Add the plasticizer P EG200 of two kinds of solution gross weights 0.6% and the formaldehyde of two kinds of solution gross weights 0.06% again; Under 10 ℃ of environment, store 2 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.
The Mechanics Performance Testing result of composite package is: tensile strength is 33.6MPa, and elongation at break is 535%, and the dissolution rate test result of film is: 16.1%.
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 formaldehyde of two kinds of solution gross weights 0.08% again; Under 5 ℃ 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.
The Mechanics Performance Testing result of composite package is: tensile strength is 36.5MPa, and elongation at break is 531%, and the dissolution rate test result of film is: 9.6%.
Comparative Examples 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; The softening agent terepthaloyl moietie that adds two kinds of solution gross weights 0.6%; 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.
The Mechanics Performance Testing result of composite package is: tensile strength is 19.8MPa, and elongation at break is 610%, and the dissolution rate test result of film is: 32.9%.
Through the comparison between Comparative Examples and the embodiment; Also can find out; Gelatin and PVA are when same ratio in composite package, and the elongation at break of composite package descends to some extent behind the adding formaldehyde, but the tensile strength of composite package is significantly improved; The dissolution rate that adds the formaldehyde caudacoria simultaneously descends to some extent, can strengthen its water tolerance.
Claims (3)
1. the preparation method of formaldehyde crosslinking gelatin/PVA composite package is characterized in that: comprise following step:
(1) 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 that adds the 80-105 weight part again; Place 80-90 ℃ water bath with thermostatic control to be stirred to Z 150PH in flask and dissolve fully, obtain polyvinyl alcohol water solution, be i.e. PVA solution;
(2) preparation of gelatin solution: the gelatin that takes by weighing the 5-10 weight part adds in the beaker; The zero(ppm) water that adds the 80-100 weight part again behind the swelling 30min, is stirred to gelatin and dissolves fully under the room temperature in 50 ℃ water bath with thermostatic control; After removing by filter impurity, promptly obtain gelatin solution;
(3) preparation of gelatin/PVA composite package: above-mentioned PVA solution and gelatin solution are joined in the there-necked flask by weight 3:1-5:1; Add softening agent and formaldehyde 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 gelatin/PVA composite package.
2. the preparation method of a kind of formaldehyde crosslinking gelatin as claimed in claim 1/PVA composite package, it is characterized in that: described softening agent is terepthaloyl moietie, glycerine or PEG200, its consumption is 0.6% of PVA solution and a gelatin solution gross weight.
3. the preparation method of a kind of formaldehyde crosslinking gelatin as claimed in claim 1/PVA composite package, it is characterized in that: the consumption of described formaldehyde is the 0.03%-0.08% of PVA solution and gelatin solution gross weight.
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| CN 201210018412 CN102558589B (en) | 2012-01-20 | 2012-01-20 | Preparation method of formaldehyde cross-linked gelatin/polyvinyl alcohol(PVA) composite membrane |
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| CN 201210018412 CN102558589B (en) | 2012-01-20 | 2012-01-20 | Preparation method of formaldehyde cross-linked gelatin/polyvinyl alcohol(PVA) composite membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674562A (en) * | 2016-12-29 | 2017-05-17 | 同济大学 | Loose-structure polyvinyl alcohol (PVA) film and preparation method thereof |
| CN108428905A (en) * | 2018-04-04 | 2018-08-21 | 江苏新亿源环保科技有限公司 | A kind of preparation method of fuel cell electrode catalyst material |
| CN112852172A (en) * | 2021-01-12 | 2021-05-28 | 陕西科技大学 | Full-biodegradable multi-crosslinked gelatin-based agricultural mulching 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104656A (en) * | 1993-12-31 | 1995-07-05 | 中国科学院兰州化学物理研究所 | Biodegradable films and their production |
| CN101993558A (en) * | 2009-08-09 | 2011-03-30 | 陈天云 | Thin film produced by using starch fiber waste plastic |
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2012
- 2012-01-20 CN CN 201210018412 patent/CN102558589B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104656A (en) * | 1993-12-31 | 1995-07-05 | 中国科学院兰州化学物理研究所 | Biodegradable films and their production |
| CN101993558A (en) * | 2009-08-09 | 2011-03-30 | 陈天云 | Thin film produced by using starch fiber waste plastic |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674562A (en) * | 2016-12-29 | 2017-05-17 | 同济大学 | Loose-structure polyvinyl alcohol (PVA) film and preparation method thereof |
| CN106674562B (en) * | 2016-12-29 | 2019-10-18 | 同济大学 | A kind of polyvinyl alcohol film and preparation method thereof with open structure |
| CN108428905A (en) * | 2018-04-04 | 2018-08-21 | 江苏新亿源环保科技有限公司 | A kind of preparation method of fuel cell electrode catalyst material |
| CN112852172A (en) * | 2021-01-12 | 2021-05-28 | 陕西科技大学 | Full-biodegradable multi-crosslinked gelatin-based agricultural mulching film and preparation method thereof |
| CN112852172B (en) * | 2021-01-12 | 2022-04-26 | 陕西科技大学 | Full-biodegradable multi-crosslinked gelatin-based agricultural mulching 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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| CN102558589B (en) | 2013-11-06 |
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