CN101445615B - Soyabean protein/dialdehyde starch/nano silver composite membrane, preparation method and application thereof - Google Patents
Soyabean protein/dialdehyde starch/nano silver composite membrane, preparation method and application thereof Download PDFInfo
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- CN101445615B CN101445615B CN2008102205316A CN200810220531A CN101445615B CN 101445615 B CN101445615 B CN 101445615B CN 2008102205316 A CN2008102205316 A CN 2008102205316A CN 200810220531 A CN200810220531 A CN 200810220531A CN 101445615 B CN101445615 B CN 101445615B
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- dialdehyde starch
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- soybean protein
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- 229920002085 Dialdehyde starch Polymers 0.000 title claims abstract description 74
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000012528 membrane Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 37
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 37
- 235000010469 Glycine max Nutrition 0.000 title claims abstract description 36
- 244000068988 Glycine max Species 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 108010073771 Soybean Proteins Proteins 0.000 claims abstract description 71
- 235000019710 soybean protein Nutrition 0.000 claims abstract description 71
- 235000018102 proteins Nutrition 0.000 claims abstract description 36
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000004332 silver Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims abstract description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000012567 medical material Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 18
- 229920002472 Starch Polymers 0.000 claims description 13
- 235000019698 starch Nutrition 0.000 claims description 13
- 239000008107 starch Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 12
- 235000013305 food Nutrition 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 241000872931 Myoporum sandwicense Species 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004902 Softening Agent Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 11
- 238000004132 cross linking Methods 0.000 abstract description 7
- -1 silver ions Chemical class 0.000 abstract description 7
- 125000003172 aldehyde group Chemical group 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000005003 food packaging material Substances 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 12
- 230000003115 biocidal effect Effects 0.000 description 9
- 230000000845 anti-microbial effect Effects 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- 108060008539 Transglutaminase Proteins 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 102000003601 transglutaminase Human genes 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000009452 anti-microbial packaging Methods 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a soyabean protein/dialdehyde starch/nano silver composite membrane with an anti-bacterial function and a preparation method thereof. The soyabean protein/the dialdehyde starch/the nano silver composite membrane is prepared by the solution casting method, soybean protein and a plasticizer glycerin are dispersed in water, then the soybean protein aqueous solution and dialdehyde starch as well as silver nitrate solution are evenly mixed, cast and baked to form the membrane; a cross-linking reaction occurs between aldehyde groups on the dialdehyde starch and amino groups on the soybean protein during the membrane forming, and the aldehyde groups further reduce silver ions into nano silver ions at the same time. The invention further discloses application of the composite membrane to being used as a food packaging material and a medical material. The soybean protein/the dialdehyde starch/the nano silver composite membrane has excellent mechanical property and anti-bacterial property and can be quickly degraded in the natural environment.
Description
Technical field
The invention belongs to polymer wrapping material field, particularly a kind of is the packing film of matrix with soybean protein and dialdehyde starch---soyabean protein/dialdehyde starch powder/nano silver composite membrane, it has excellent mechanical property and anti-microbial property.
Background technology
The quality of food and safety are the problems that food enterprise and human consumer pay special attention to always.Traditional polyethylene packaging film can only completely cut off the pollution of outside bacterium to food momently, and can't stop the breeding of bacterium in packaging system, simultaneously, polythene material is slow at the degradation rate of occurring in nature, and a large amount of uses also can bring huge pollution to environment.Therefore, the research and development with degradable package film of antibacterial have very important realistic meaning.
With regard to antibiotic mechanism, at present the preparation of antimicrobial packaging film mainly is that some material with antibacterial is directly added in the film forming matrix, and made film can be constantly discharges antimicrobial substance and realize anticorrosion to food to the food surfaces that is in contact with it.Chinese patent ZL01137391.1 adopts in the polyolefine raw material method of blend zinc chloride to prepare the packing film that a class has antibacterial; Chinese patent ZL200720116439.3 adopts the method for blend nano silver particles to prepare a kind of polyethylene antibiotic film of three-decker, between polyethylene film, be mingled with nano silver particles with antibacterial, with respect to other inorganic particulate, nano silver particles has broad spectrum antibacterial, and antibacterial ability is stronger, and the existence of nano silver particles can influence breathing and the eubolism function of bacterium, causes the cell wall rupture of bacterium, thereby killing bacteria reaches the antimicrobial purpose.
Soybean protein is the class natural polymer that separation and Extraction is come out from soybean, has very good film-forming properties, the film of making by soybean protein have edible nontoxic, oxygen transmission rate is low, plurality of advantages such as cheap, and can degrade well at occurring in nature.Owing to contain hydrophilic radicals such as many amino, carboxyl in the soybean protein molecule, to compare with the polyolefins material, simple soybean protein film is still having some deficits aspect intensity and the water tolerance.Cross-linking modified is effective ways that improve the soybean protein material performance.Linking agent commonly used at present has: formaldehyde, acetaldehyde, glutaraldehyde and trans-glutaminases etc.Chinese patent ZL02138823.7 adopts the formaldehyde crosslinking soybean protein, has prepared a class and has had superior ventilation property, chromatic soybean fiber; Chinese patent application CN1676015A adopts trans-glutaminases to carry out cross-linking modified to soybean protein, under the effect of trans-glutaminases, partial peptide bond rupture in the soybean protein molecule generates amino and carboxyl, enzyme can promote amino and carboxyl to form new peptide bond again between protein molecule simultaneously, the generation of peptide bond has strengthened the reactive force between protein molecule, thereby makes the over-all properties of material significantly improve.
Because the toxicity of small molecule aldehyde material is big and volatilization easily, and costing an arm and a leg and being difficult for obtaining in a large number of trans-glutaminases limited the application of albuminous membranae in food product pack and field of medical materials greatly.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide a kind of soyabean protein/dialdehyde starch powder/nano silver composite membrane with antibacterial.The present invention has at first synthesized the starch that has aldehyde radical on a kind of molecular chain---dialdehyde starch.As linking agent soybean protein is carried out cross-linking modifiedly with dialdehyde starch, utilize aldehyde radical on the dialdehyde starch simultaneously Ag
+In-situ reducing becomes nano silver particles, adopts the film forming method of solution-cast, preparation soyabean protein/dialdehyde starch powder/nano silver composite membrane.This composite membrane has excellent mechanical property and anti-microbial property, and can promptly degrade at occurring in nature.
Purpose of the present invention is achieved through the following technical solutions, and a kind of preparation method of soyabean protein/dialdehyde starch powder/nano silver composite membrane comprises the steps:
(1) adopt the sodium periodate oxidation Zulkovsky starch to obtain dialdehyde starch:
The 10g Zulkovsky starch is dissolved in the NaIO that 100mL concentration is 0.2mol/L～0.8mol/L
4In the solution, transferring pH with acid is 2～4, in 0～30 ℃ of following lucifuge reaction 2～6h, that the product acetone precipitation is extremely neutral with deionized water wash more then, obtains dialdehyde starch after the lyophilize.
(2) adopt the film forming method of solution-cast to prepare soyabean protein/dialdehyde starch powder/nano silver composite membrane.
Soybean protein and softening agent glycerol are scattered in the water under 60～90 ℃, obtain the soybean protein aqueous solution, after being cooled to room temperature, dialdehyde starch is dissolved in the soybean protein aqueous solution, under agitation silver nitrate solution is added drop-wise to then in the soybean protein aqueous solution, the consumption of control silver is 0.5%～5% of a soybean protein quality, obtain soybean protein casting liquid, the soybean protein liquid of casting is cast in the mould, after the baking film forming, obtain soyabean protein/dialdehyde starch powder/nano silver composite membrane.
In order to realize the present invention better, in the step (1), described acid is preferably the sulfuric acid of 1mol/L.
In the step (2), described softening agent glycerol is 20～30% of a soybean protein quality; Described dialdehyde starch accounts for 10～30% of soybean protein quality.The concentration of described silver nitrate solution is 0.1mol/L.The solid content of described soybean protein cast-solution is 8%～15%; Described baking film forming is to adopt infrared lamp baking film forming.
The thickness of described soyabean protein/dialdehyde starch powder/nano silver composite membrane is between 0.1～0.25um, and the diameter of silver particles is between 30nm～60nm in the composite membrane, and the consumption of control silver particles is 0.5%～5% of a soybean protein quality.
A kind of soyabean protein/dialdehyde starch powder/nano silver composite membrane forms by method for preparing exactly.
Soyabean protein/dialdehyde starch powder/nano silver composite membrane of the present invention has good antimicrobial property, and colibacillary antibiotic rate about 93%～96%, is suitable for wrapping material and field of medical materials as food.
With the soybean protein is matrix, adopt the film forming method of solution-cast to prepare a series of degradable food packaging films, adopt different aldehyde group content dialdehyde starch to carry out cross-linking modified respectively to soybean protein, the mechanical strength and the water tolerance of modification caudacoria all are significantly improved, and utilize aldehyde radical on the dialdehyde starch with Ag simultaneously
+In-situ reducing becomes silver particles, and scanning electron microscope observation shows diameter (see figure 1) between 30nm～60nm of silver particles.
The present invention compared with prior art has following advantage and beneficial effect:
The present invention adopts that a kind of nonvolatile macromole aldehydes linking agent---dialdehyde starch is carried out cross-linking modified to soybean protein, thereby improves the mechanical property and the water tolerance of albuminous membranae, utilizes aldehyde radical on the dialdehyde starch with Ag simultaneously
+In-situ reducing becomes nano silver particles, and the soybean protein film good antimicrobial property has been given in the existence of nano silver particles, and made soyabean protein/dialdehyde starch powder/nano silver composite membrane has boundless application prospect in food product pack and field of medical materials.
Compare with the method for simple blend nano silver particles, the present invention utilizes aldehyde radical on the dialdehyde starch with Ag
+In-situ reducing becomes nano silver particles, more helps obtaining a kind of homodisperse nano composite material.Simultaneously, compare with the polyolefins packing film, soyabean protein/dialdehyde starch powder/nano silver composite membrane can be degraded well at occurring in nature, can not pollute environment.
The bacterial classification that the soyabean protein/dialdehyde starch powder of the present invention's preparation/test of nano silver composite membrane anti-microbial property is adopted is intestinal bacteria ATCC 8099, antibacterial tests is undertaken by QB/T 2591-2003 " antibiotic plastic---anti-microbial property test method and antibacterial effect ", the antibiotic rate of film shows that soyabean protein/dialdehyde starch powder/nano silver composite membrane has good anti-microbial property about 93%～96%.
Description of drawings
Fig. 1 is the sem photograph of soyabean protein/dialdehyde starch powder of the present invention/nanometer Ag composite membrane section.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) adopt the sodium periodate oxidation Zulkovsky starch to obtain dialdehyde starch.The 10g Zulkovsky starch is dissolved in the NaIO that 100mL concentration is 0.2mol/L
4In the solution, transferring pH with the sulfuric acid of 1mol/L is 2, in 20 ℃ of following lucifuge reaction 4h, that the product acetone precipitation is extremely neutral with deionized water wash more then, obtains dialdehyde starch after the lyophilize, is labeled as DAS1.
(2) with the 10g soybean protein, 3g glycerol and 150mL distilled water join in the reactor, and dispersed with stirring 30min under the room temperature rises to temperature 70 ℃ then, and vigorous stirring is disperseed 30min, obtain the soybean protein aqueous solution of stable homogeneous.Be cooled to room temperature (25 ℃～35 ℃), the dialdehyde starch (DAS1) that will account for soybean protein quality 10% under the vigorous stirring is dissolved in the soybean protein aqueous solution, the silver nitrate solution that with concentration is 0.1mol/L simultaneously is added drop-wise in the reactor, the consumption of control silver is 1% of a soybean protein quality, obtain soybean protein casting liquid, the solid content of soybean protein cast-solution is 8%, the liquid of then soybean protein being cast is cast in the tetrafluoroethylene mould, adopt infrared lamp baking film forming, obtain soyabean protein/dialdehyde starch powder/nano silver composite membrane.The thickness of this composite membrane is 0.15 ± 0.02um, the diameter of silver particles (as shown in Figure 1) between 30nm～60nm in the composite membrane, the tensile strength of composite membrane is 5 ± 0.9MPa, is 93%～96% to colibacillary antibiotic rate, composite membrane landfill in soil can be degraded after 60 days fully.
Embodiment 2
(1) adopt the sodium periodate oxidation Zulkovsky starch to obtain dialdehyde starch.The 10g Zulkovsky starch is dissolved in the NaIO that 100mL concentration is 0.5mol/L
4In the solution, transferring pH with the sulfuric acid of 1mol/L is 3, in 20 ℃ of following lucifuge reaction 4h, that the product acetone precipitation is extremely neutral with deionized water wash more then, obtains dialdehyde starch after the lyophilize, is labeled as DAS2.
(2) with the 10g soybean protein, 3g glycerol and 150mL distilled water join in the reactor, and dispersed with stirring 30min under the room temperature rises to temperature 60 ℃ then, and vigorous stirring is disperseed 30min, obtain the soybean protein aqueous solution of stable homogeneous.Be cooled to room temperature, the dialdehyde starch (DAS2) that will account for soybean protein quality 20% under the vigorous stirring is dissolved in the soybean protein aqueous solution, the silver nitrate solution that with concentration is 0.1mol/L simultaneously is added drop-wise in the reactor, the consumption of control silver is 3% of a soybean protein quality, obtain soybean protein casting liquid, the solid content of soybean protein cast-solution is 15%, the liquid of then soybean protein being cast is cast in the tetrafluoroethylene mould, adopt infrared lamp baking film forming, obtain soyabean protein/dialdehyde starch powder/nano silver composite membrane.The thickness of this composite membrane is 0.2 ± 0.02um, the diameter of silver particles is between 30nm～60nm in the composite membrane, and the tensile strength of composite membrane is 5 ± 0.9MPa, is 93%～96% to colibacillary antibiotic rate, composite membrane landfill in soil can be degraded after 60 days fully.
Embodiment 3
(1) adopt the sodium periodate oxidation Zulkovsky starch to obtain dialdehyde starch.The 10g Zulkovsky starch is dissolved in the NaIO that 100mL concentration is 0.8mol/L
4In the solution, transferring pH with the sulfuric acid of 1mol/L is 2, in 20 ℃ of following lucifuge reaction 4h, that the product acetone precipitation is extremely neutral with deionized water wash more then, obtains dialdehyde starch after the lyophilize, is labeled as DAS3.
(2) with the 10g soybean protein, 3g glycerol and 150mL distilled water join in the reactor, and dispersed with stirring 30min under the room temperature rises to temperature 90 ℃ then, and vigorous stirring is disperseed 30min, obtain the soybean protein aqueous solution of stable homogeneous.Be cooled to room temperature, the dialdehyde starch (DAS3) that will account for soybean protein quality 30% under the vigorous stirring is dissolved in the soybean protein aqueous solution, the silver nitrate solution that with concentration is 0.1mol/L simultaneously is added drop-wise in the reactor, the consumption of control silver is 4% of a soybean protein quality, obtain soybean protein casting liquid, the solid content of soybean protein cast-solution is 10%, the liquid of then soybean protein being cast is cast in the tetrafluoroethylene mould, adopt infrared lamp baking film forming, obtain soyabean protein/dialdehyde starch powder/nano silver composite membrane.The thickness of this composite membrane is 0.2 ± 0.02um, the diameter of silver particles is between 30nm～60nm in the composite membrane, and the tensile strength of composite membrane is 5 ± 0.9MPa, is 93%～96% to colibacillary antibiotic rate, composite membrane landfill in soil can be degraded after 60 days fully.
Embodiment 4
(1) adopt the sodium periodate oxidation Zulkovsky starch to obtain dialdehyde starch.The 10g Zulkovsky starch is dissolved in the NaIO that 100mL concentration is 0.5mol/L
4In the solution, transferring pH with the sulfuric acid of 1mol/L is 3, in 30 ℃ of following lucifuge reaction 2h, that the product acetone precipitation is extremely neutral with deionized water wash more then, obtains dialdehyde starch after the lyophilize, is labeled as DAS2.
(2) with the 10g soybean protein, 2g glycerol and 150mL distilled water join in the reactor, and dispersed with stirring 30min under the room temperature rises to temperature 70 ℃ then, and vigorous stirring is disperseed 30min, obtain the soybean protein aqueous solution of stable homogeneous.Be cooled to room temperature, the dialdehyde starch (DAS2) that will account for soybean protein quality 20% under the vigorous stirring is dissolved in the soybean protein aqueous solution, the silver nitrate solution that with concentration is 0.1mol/L simultaneously is added drop-wise in the reactor, the consumption of control silver is 5% of a soybean protein quality, obtain soybean protein casting liquid, the solid content of soybean protein cast-solution is 12%, the liquid of then soybean protein being cast is cast in the tetrafluoroethylene mould, adopt infrared lamp baking film forming, obtain soyabean protein/dialdehyde starch powder/nano silver composite membrane.The thickness of this composite membrane is 0.15 ± 0.02um, the diameter of silver particles is between 30nm～60nm in the composite membrane, and the tensile strength of composite membrane is 3～6MPa, is 93%～99.5% to colibacillary antibiotic rate, composite membrane landfill in soil can be degraded after 60 days fully.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a soyabean protein/dialdehyde starch powder/nano silver composite membrane is characterized in that comprising the steps:
(1) adopt the sodium periodate oxidation Zulkovsky starch to obtain dialdehyde starch:
The 10g Zulkovsky starch is dissolved in the NaIO that 100mL concentration is 0.2mol/L～0.8mol/L
4In the solution, transferring pH with acid is 2～4, in 0～30 ℃ of following lucifuge reaction 2～6h, that the product acetone precipitation is extremely neutral with deionized water wash more then, obtains dialdehyde starch after the lyophilize;
(2) adopt the film forming method of solution-cast to prepare soyabean protein/dialdehyde starch powder/nano silver composite membrane:
Soybean protein and softening agent glycerol are scattered in the water under 60～90 ℃, obtain the soybean protein aqueous solution, after being cooled to room temperature, dialdehyde starch is dissolved in the soybean protein aqueous solution, under agitation silver nitrate solution is added drop-wise to then in the soybean protein aqueous solution, the consumption of control silver is 0.5%～5% of a soybean protein quality, obtain soybean protein casting liquid, the soybean protein liquid of casting is cast in the mould, after the baking film forming, obtain soyabean protein/dialdehyde starch powder/nano silver composite membrane.
2. the preparation method of a kind of soyabean protein/dialdehyde starch powder/nano silver composite membrane according to claim 1 is characterized in that: in the step (1), described acid is the sulfuric acid of 1mol/L.
3. the preparation method of a kind of soyabean protein/dialdehyde starch powder/nano silver composite membrane according to claim 1 is characterized in that: in the step (2), described softening agent glycerol is 20～30% of a soybean protein quality.
4. the preparation method of a kind of soyabean protein/dialdehyde starch powder/nano silver composite membrane according to claim 1 is characterized in that: in the step (2), described dialdehyde starch accounts for 10～30% of soybean protein quality.
5. the preparation method of a kind of soyabean protein/dialdehyde starch powder/nano silver composite membrane according to claim 1 is characterized in that: in the step (2), the concentration of described silver nitrate solution is 0.1mol/L.
6. the preparation method of a kind of soyabean protein/dialdehyde starch powder/nano silver composite membrane according to claim 1 is characterized in that: in the step (2), the solid content of described soybean protein cast-solution is 8%～15%.
7. the preparation method of a kind of soyabean protein/dialdehyde starch powder/nano silver composite membrane according to claim 1 is characterized in that: in the step (2), described baking film forming is to adopt infrared lamp baking film forming.
8. the preparation method of a kind of soyabean protein/dialdehyde starch powder/nano silver composite membrane according to claim 1, it is characterized in that: the thickness of described soyabean protein/dialdehyde starch powder/nano silver composite membrane is between 0.1～0.25um, and the diameter of silver particles is between 30nm～60nm in the composite membrane.
9. a soyabean protein/dialdehyde starch powder/nano silver composite membrane is prepared from by each described method of claim 1～8 exactly.
10. the described soyabean protein/dialdehyde starch powder/nano silver composite membrane of claim 9 is in the wrapping material of food or the application in the field of medical materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102205316A CN101445615B (en) | 2008-12-29 | 2008-12-29 | Soyabean protein/dialdehyde starch/nano silver composite membrane, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102205316A CN101445615B (en) | 2008-12-29 | 2008-12-29 | Soyabean protein/dialdehyde starch/nano silver composite membrane, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101445615A CN101445615A (en) | 2009-06-03 |
| CN101445615B true CN101445615B (en) | 2011-05-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103146004B (en) * | 2013-02-27 | 2014-10-15 | 江阴摩尔化工新材料有限公司 | Method for improving soybean protein isolate film water resistance through photo-crosslinking |
| CN103665895A (en) * | 2013-11-11 | 2014-03-26 | 青岛佰众化工技术有限公司 | Soybean protein isolate-polyaniline antimicrobial composite film |
| CN103881400B (en) * | 2014-04-09 | 2016-01-20 | 山东金胜粮油集团有限公司 | Edibility nano flower raw albumen composite membrane and preparation technology thereof |
| CN104004209B (en) * | 2014-06-13 | 2017-04-05 | 东华大学 | A kind of preparation method of polycaprolactone keratin composite membrane |
| CN107057128A (en) * | 2017-05-02 | 2017-08-18 | 安徽繁盛禽业有限公司 | A kind of preparation method of the degradable Fresh-keeping Packaging for Fruits and Vegetables film of highly-breathable |
| CN107363946B (en) * | 2017-06-07 | 2019-11-05 | 新沂市金达木业有限公司 | A kind of timber preservative |
| CN113773528B (en) * | 2021-08-23 | 2023-08-18 | 东北农业大学 | Soybean protein isolate or soybean polypeptide hydrogel and preparation method and application thereof |
| CN114307667B (en) * | 2021-12-01 | 2024-03-15 | 苏州科技大学 | Water-soluble aldehyde cyclodextrin-polyethyleneimine coating modified polymer film and preparation method thereof |
| CN114307669B (en) * | 2021-12-01 | 2024-03-15 | 苏州科技大学 | Water-soluble aldehyde starch-polyethyleneimine coating modified polymer film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636259A (en) * | 1983-12-17 | 1987-01-13 | Yoshihara Oil Mill, Ltd. | Soybean protein film |
| CN1678195A (en) * | 2002-09-08 | 2005-10-05 | 阿肯色大学董事会 | Organic acids incorporated edible antimicrobial films |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636259A (en) * | 1983-12-17 | 1987-01-13 | Yoshihara Oil Mill, Ltd. | Soybean protein film |
| CN1678195A (en) * | 2002-09-08 | 2005-10-05 | 阿肯色大学董事会 | Organic acids incorporated edible antimicrobial films |
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