CN116410496B - Barrier green active starch-based film and preparation method thereof - Google Patents
Barrier green active starch-based film and preparation method thereof Download PDFInfo
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- CN116410496B CN116410496B CN202310149794.7A CN202310149794A CN116410496B CN 116410496 B CN116410496 B CN 116410496B CN 202310149794 A CN202310149794 A CN 202310149794A CN 116410496 B CN116410496 B CN 116410496B
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- starch
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- 229920002472 Starch Polymers 0.000 title claims abstract description 139
- 239000008107 starch Substances 0.000 title claims abstract description 138
- 235000019698 starch Nutrition 0.000 title claims abstract description 138
- 230000004888 barrier function Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 210000003278 egg shell Anatomy 0.000 claims abstract description 191
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 179
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 179
- 239000000843 powder Substances 0.000 claims abstract description 135
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002699 waste material Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 16
- 235000013305 food Nutrition 0.000 claims abstract description 14
- 239000005022 packaging material Substances 0.000 claims abstract description 8
- 239000003814 drug Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 62
- 239000013543 active substance Substances 0.000 claims description 44
- 239000006185 dispersion Substances 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 34
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
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- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
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- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 3
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims description 3
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- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001263 FEMA 3042 Substances 0.000 claims description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 2
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- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- 235000015523 tannic acid Nutrition 0.000 claims description 2
- 229920002258 tannic acid Polymers 0.000 claims description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 2
- 229940033123 tannic acid Drugs 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 abstract description 34
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- 230000000844 anti-bacterial effect Effects 0.000 abstract description 24
- 239000002131 composite material Substances 0.000 abstract description 20
- 238000010345 tape casting Methods 0.000 abstract description 11
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- 238000012545 processing Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 150000002433 hydrophilic molecules Chemical class 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 41
- 241000196324 Embryophyta Species 0.000 description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 27
- 230000005540 biological transmission Effects 0.000 description 25
- 238000003756 stirring Methods 0.000 description 15
- 238000005303 weighing Methods 0.000 description 14
- -1 three methods Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- WMBWREPUVVBILR-WIYYLYMNSA-N (-)-Epigallocatechin-3-o-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-WIYYLYMNSA-N 0.000 description 6
- WMBWREPUVVBILR-UHFFFAOYSA-N GCG Natural products C=1C(O)=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-UHFFFAOYSA-N 0.000 description 6
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- 230000007613 environmental effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000003385 bacteriostatic effect Effects 0.000 description 3
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- 238000013329 compounding Methods 0.000 description 3
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- 229920006280 packaging film Polymers 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 244000198134 Agave sisalana Species 0.000 description 1
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000004252 protein component Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a barrier green active starch-based film and a preparation method thereof, and belongs to the technical field of packaging material processing. The method comprises the steps of washing and crushing waste eggshells to obtain eggshell powder, modifying hydrophilic compounds on the surfaces of the eggshell powder by utilizing the coordination action of metal ions, and further utilizing porous structures rich in the surfaces of the eggshell powder to adsorb natural active ingredients of plants to form an active eggshell powder compound; and mixing the solution of the active eggshell powder compound with gelatinized starch solution, and preparing the green active starch-based film with barrier property by adopting a tape casting method. The composite starch-based film is complete and continuous, the water vapor barrier property can be improved by 7%, and the oxygen barrier property can be improved by 28%; the antibacterial performance of the composition can be improved by 37%; has excellent water vapor and oxygen barrier property and good antibacterial activity, and can be used in the fields of food, medicine, medical appliances and agricultural product packaging.
Description
Technical Field
The invention relates to a barrier green active starch-based film and a preparation method thereof, belonging to the technical field of packaging material processing.
Background
For most food products, an increase in moisture and oxygen content within the package is an important factor in accelerating the change in texture of the food product, even spoilage. Controlling the water vapor content and oxygen concentration within the package is an effective way to improve this result. The active food package with barrier property is a novel packaging material, and the packaging material can effectively block the diffusion of water vapor and oxygen in the environment into the food package and actively interact with the internal and external environments of the food package, so that the microbial growth is limited to the greatest extent, the oxidation and spoilage speeds of the food are reduced, and the shelf life of the food is prolonged and the quality of the food is maintained.
Starch films have been used in large quantities as fully degradable emerging food packaging materials, however, the low barrier, easy-to-stain performance drawbacks limit their wider range of use, and currently, to achieve barrier enhancement of starch-based packaging materials, three methods, starch modification, multi-layer film compounding and inorganic material compounding, are commonly employed. However, in practical application, starch modification is often accompanied by chemical residue, modification steps are complex, modification degree is difficult to control, and thus the cost of materials is high, and the use safety is doubtful; the multi-layer film is compounded to improve the overall barrier property of the starch film by compounding high-barrier plastic or aluminum foil, but the packaging material has high cost, poor degradability and even partial non-degradability, and high environmental risk. The inorganic material is used as a filler to be mixed in a natural polymer, so that the preparation is simple and effective, however, the existing inorganic filler comprises graphene, clay and other substances, has poor dispersibility in the natural polymer, high cost and dark color, and does not have antibacterial effect. Although zinc oxide nanoparticles have bacteriostatic action, their use is limited by the high cost.
There are some reports of preparing barrier antibacterial packaging films. For example, CN201810191378.2 discloses a degradable packaging film made from food waste, the invention uses eggshells and starch as main raw materials, and various auxiliary agents are added, so that the prepared packaging film has strong physical and mechanical properties, selective permeability, antibacterial and antioxidant effects, and the selected raw materials are easy to degrade, thereby avoiding white pollution and protecting ecological environment. The principle of the invention is to realize the improvement of barrier property by mixing expensive fumed silica, nano-grade calcium carbonate and purified protein, and the invention has the following defects: the components are complex, and more than 16 raw materials are needed to be used in total; (2) The process is complex, wherein the film forming liquid can be mixed only by adjusting the temperature for a plurality of times due to different properties of a plurality of auxiliary agents; (3) The protein components attached to the inside of the eggshells are required to be obtained through complex extraction and purification processes to be used as film-forming raw materials, the eggshells are still abandoned, the steps are complex, the energy consumption is high, and the cost of the extractant is high; (4) Up to 14 auxiliary agents are used, eggshell waste is generated, the environmental pollution risk is high, and the use safety risk is high; (5) There is no data or theory supporting the existence of bacteriostatic and antioxidative properties.
Therefore, development of an active degradable starch-based film which has few auxiliary agents, simple operation process, excellent barrier property, low cost, environmental protection and antibacterial property is needed, and the active degradable starch-based film has important economic value and social significance for expanding the application range of the starch-based film, prolonging the shelf life of food and solving the problem of food safety and quality.
Disclosure of Invention
[ technical problem ]
The existing method for improving the barrier property of the starch-based film has the problems of high cost, complex process, limited improvement degree, environmental protection, incapability of having antibacterial activity and the like.
Technical scheme
In order to solve at least one of the problems, the invention adopts eggshell waste with specific size to carry out hydrophilic modification, and prepares the green active starch-based film with high-efficiency barrier property by a method of porous adsorption of plant active substances. The method is simple, has extremely low cost, is green, pollution-free and low in energy consumption. The composite starch-based film prepared by the invention has good water vapor and oxygen barrier property, and compared with a pure starch film, the water vapor barrier property is improved by 4 to 7 percent, and the oxygen barrier property is improved by 16 to 28 percent; has certain antibacterial performance, and the antibacterial performance is improved by 18 to 37 percent.
The first object of the present invention is to provide a method for preparing a green active starch-based film having high barrier property, comprising washing eggshells, pulverizing to obtain eggshell powder of 200-400 mesh, then hydrophilically modifying the eggshell powder, and drying to disperse the eggshell powder to adsorb plant active substances to obtain eggshell powder adsorbing plant active substances; and then evenly mixing the starch pasting solution to obtain film forming solution, and preparing the film to obtain the green active starch-based film with barrier property.
In one embodiment, the method comprises the steps of:
(1) Eggshell washing:
washing the waste eggshell fragments with alkaline aqueous solution to remove proteins and impurities, and drying to obtain eggshell fragments
(2) Obtaining eggshell powder:
pulverizing eggshell fragments, and sieving to obtain 200-400 mesh eggshell powder;
(3) Eggshell powder modification
Placing eggshell powder into a modifying solution with a certain pH value for hydrophilic modification, filtering and drying to obtain modified eggshell powder;
(4) The dispersion modified eggshell powder adsorbs plant active substances:
dispersing the modified eggshell powder to obtain eggshell powder dispersion liquid, adding a plant active substance solution, rotating in a dark place to perform self-adsorption, and centrifuging to obtain eggshell powder for adsorbing plant active substances;
(5) Preparing a film forming liquid:
dispersing eggshell powder adsorbing plant active substances in water to obtain dispersion liquid; then uniformly mixing the dispersion liquid and the starch gelatinization solution to obtain film forming liquid;
(6) And (3) film preparation:
and (3) preparing a film from the film forming liquid to obtain the green active starch base film with barrier property.
In one embodiment, the waste eggshell fragments in step (1) include one or more of eggshells of birds such as eggshells and duck eggshells.
In one embodiment, the aqueous alkaline solution of step (1) has a pH of 8 to 10; optionally, the drying temperature is 50-100 ℃ and the drying time is 4-24 h.
In one embodiment, the mass to volume ratio of the waste eggshell fragments described in step (1) to the alkaline aqueous solution is 1:5 to 1:50.
in one embodiment, step (2) employs a pulverizer to perform the high speed pulverizer; the high-speed pulverizer has a pulverizing rotation speed of 10000-50000rpm, a pulverizing time of 1min-5 min/time, and pulverizing repetition times of 2-5 times.
In one embodiment, the screen used in the step (2) is an ultrafine stainless steel screen, and the mesh number of the screen is 200-400 mesh.
In one embodiment, the modifying solution in step (3) is sodium alginate, dopamine or tannic acid solution.
In one embodiment, the concentration of the modifying solution in the step (3) is 1-100mg/mL, and the mass-volume ratio of the eggshell powder to the modifying solution is 1:1 to 10:1.
in one embodiment, the pH of the modifying solution of step (3) is from 5 to 10.
In one embodiment, the eggshell powder of step (3) is stirred in the modified solution for a period of time ranging from 0.5 to 2 hours.
In one embodiment, the drying method of step (3) is vacuum freeze drying or air drying.
In one embodiment, the dispersing of step (4) uses ultrasonic dispersion; the power of ultrasonic dispersion is 200-400W, and the dispersion time is 5-30min.
In one embodiment, the plant active substance of step (4) is one or both of catechin and/or curcumin, preferably catechin.
In one embodiment, the concentration of the plant active in step (4) is from 5 to 20mg/mL.
In one embodiment, the plant active solution of step (4) has a pH of 3 to 5.
In one embodiment, the rotary adsorption in step (4) is performed in the absence of light at a rotational speed of 200-800rpm for a period of 1-9 hours.
In one embodiment, the centrifugation speed in step (4) is 4000-10000rpm and the centrifugation time is 5-30min.
In one embodiment, the centrifugation in step (4) is performed at a rotational speed of 8000-10000rpm for a centrifugation time of 5-30min; .
In one embodiment, the method for preparing the starch gelatinization solution of step (5) comprises:
uniformly mixing starch and water, and gelatinizing to obtain a starch gelatinization solution; wherein, the dosage ratio of the starch to the water is 3g:80mL; gelatinization is gelatinization for 10min at 95deg.C.
In one embodiment, the starch in step (5) is one or more of corn starch, potato starch, wheat starch, or sisal starch.
In one embodiment, the mass ratio of the starch in step (5) to the eggshell powder adsorbing the plant active substance is 3:1-30:1.
in one embodiment, the step (5) of uniformly mixing is stirring and uniformly mixing, and the stirring speed is 400-800rpm.
In one embodiment, step (6) is a cast film process; pouring the film forming liquid into a mould, drying the film to form a film, and then taking the film off for balancing; wherein the drying mode is hot air drying or vacuum drying, the drying temperature is 25-60 ℃ and the drying time is 4-48 h; the balance condition is that the temperature is 22-37 ℃, the relative humidity is 50-80% RH, and the balance time is 12-72 h.
In one embodiment, in particular, the method comprises the steps of:
(1) Eggshell washing:
placing the waste eggshell fragments into an alkaline aqueous solution for rotary soaking, repeating for three times after replacing the alkaline aqueous solution, cleaning again by deionized water, and drying at high temperature to obtain eggshell fragments; the alkaline water washing can effectively remove protein and impurities;
(2) Obtaining eggshell powder:
placing the dried eggshell fragments into a pulverizer, pulverizing at high speed to obtain eggshell powder with different sizes, and sieving with a sieve with specific mesh to obtain eggshell powder with specific mesh;
the size and the quality of the eggshell powder are determined by the number of the eggshell powder, the particle size is too large, the aesthetic degree (white spots visible to naked eyes) of the membrane is affected, and the surface of the membrane is also rougher; secondly, the volume is large, the mass is large, so that the precipitation is easy, and the film formation is not easy; while at the same mass, the number of particles is different, the larger the number is, the larger the specific surface area is, and the more the action sites of starch molecules are, the less the contrary is. However, since the number of micropores on the surface of the eggshell is fixed, if the particle size is too small, the pores are more easily damaged, the adsorption degree is affected, and meanwhile, too small particles cause too many particles, and the transparency of the membrane is affected;
(3) Eggshell powder modification
Placing the eggshell powder with the specific mesh into a modified solution with a certain pH value, continuously stirring for a certain time, filtering and drying to obtain modified eggshell powder; the modification can improve the interface hydrophilicity, so that the dispersibility of the modified polymer is improved;
(4) Dispersing eggshell powder to adsorb plant active substances:
placing eggshell powder into an aqueous solution for ultrasonic dispersion to obtain eggshell powder dispersion, adding a plant active substance solution, rotating away from light for self-adsorption, and centrifuging to obtain eggshell powder for adsorbing plant active substances; the plant active substance can effectively improve the antibacterial property of the membrane;
(5) Preparing a film forming liquid:
dispersing eggshell powder adsorbing plant active substances in water to obtain dispersion liquid; then uniformly mixing the dispersion liquid and the starch gelatinization solution to obtain film forming liquid;
(6) And (3) film preparation:
and (3) preparing the film forming liquid into the green active starch-based film with high barrier property by adopting a tape casting method.
The second object of the invention is to provide a green active starch-based film with high barrier property prepared by the method.
The third object of the invention is the application of the green active starch-based film with high barrier property in food, medicine, medical apparatus or agricultural products, mainly for packaging.
In one embodiment, the application is applied to fruit fresh-keeping packaging, and the water vapor barrier property, the oxygen barrier property, the antibacterial property, the environmental protection property and the like of the film are fully utilized.
A fourth object of the present invention is to provide a degradable material or packaging material comprising the green active starch-based film with high barrier properties according to the present invention. Alternatively, the degradable material may be used in agricultural mulch.
[ advantageous effects ]
The invention is based on the porous structure of crushed waste eggshells, promotes the hydrophilic modification of the eggshell powder interface by adjusting the pH value and by means of the interaction of ionic crosslinking and hydrogen bonds, improves the dispersibility of eggshell powder in the water-based starch matrix, simultaneously improves the effective adsorption of eggshell powder to photosensitive plant active substances, reduces the photodegradation degree of the active substances, increases the utilization rate of the active substances, and reduces the degradation of the photosensitive active substances under illumination and simultaneously endows the starch base film with effective antibacterial activity and improved barrier property.
The invention uses the waste eggshells as the main raw materials, effectively controls the size of eggshell powder and the mass ratio of starch to eggshell powder adsorbing plant active substances, prepares the high-barrier green active starch base film, and has the following advantages:
(1) The components are simple, and the process is simple: according to the invention, by adding the waste eggshell powder, the performance can be improved by using extremely simple raw materials and simply modifying the raw materials;
(2) Low cost, full utilization of waste materials, green and environment protection: the invention directly uses the waste eggshells to be ground into powder for use, has simple process, low cost, no other waste materials, green and environment-friendly use and safety;
(3) Film is complete and continuous and has excellent performance: the prepared barrier green active starch-based film is complete and continuous, and compared with a pure starch film, the water vapor barrier performance is improved by 4 to 7 percent, and the oxygen barrier performance is improved by 16 to 28 percent; has certain antibacterial performance, and the antibacterial performance is improved by 18 to 37 percent.
(4) The application range is wide: the barrier green active starch-based film has excellent water vapor and oxygen barrier property and antibacterial property, and can be used in the fields of food, medicine, agricultural product packaging and the like.
Drawings
FIG. 1 is a scanning electron microscope image of eggshell powder in an active starch-based film prepared according to the invention; wherein the left graph is to a 50 μm scale and the right graph is to a 5 μm scale;
FIG. 2 is a diagram of an active starch-based film prepared in accordance with the present invention;
FIG. 3 is a graph showing the water vapor transmission rate of the composite starch-based films prepared in examples 1 to 3 and comparative examples 1 to 5 according to the present invention;
FIG. 4 is a graph showing the oxygen transmission rate of the composite starch-based films prepared in examples 1 to 3 and comparative examples 1 to 5 according to the present invention;
FIG. 5 is a graph showing the antibacterial properties of the composite starch-based films prepared in examples 1 to 3 and comparative examples 1 to 5 according to the present invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
The testing method comprises the following steps:
1. water vapor transmission test: the moisture-permeable cup weighing method is adopted to test the variation of the moisture-permeable cup quality of the composite starch base film with time at a certain temperature and humidity so as to evaluate the water vapor barrier property.
The specific operation steps are as follows: firstly, cutting a film sample into a wafer sample with the diameter of 25mm, clamping the original wafer sample at a grinding port of a moisture permeable cup filled with calcium chloride, placing the clamped moisture permeable cup in an experimental environment with the room temperature and the humidity of 95%, and weighing the mass change every 24 hours.
The water vapor transmission rate is calculated as follows:
WVTR＝△W/(t*A)
wherein: delta W is poor in quality, g; time t, d; film transmission area, m 2 The method comprises the steps of carrying out a first treatment on the surface of the WVTR water vapor transmission rate, g/m 2 /d。
2. Oxygen permeation test: based on the oxidation mechanism of iron, the oxygen transmission rate of the composite starch-based film was tested by a weighing method.
The specific operation steps are as follows: firstly, a film sample is cut into a wafer sample with the diameter of 25mm, the original wafer sample is clamped at an opening of a sample bottle made of organic glass containing 1.5g of sodium chloride, 1g of activated carbon and 0.5g of reduced iron powder, and the sample bottle is placed at room temperature and under the experimental condition of 90% humidity, and the weight change of the sample bottle with time is tested.
The oxygen transmission rate is calculated as follows:
OTR＝△M/(t*A)
wherein: delta M is of poor quality, g; time t, d; film transmission area, m 2 The method comprises the steps of carrying out a first treatment on the surface of the OTR water vapor transmission rate, g/m 2 /d。
3. Antibacterial performance test: and an ultraviolet-visible light spectrophotometer is adopted, and the antibacterial performance of the composite starch-based film is evaluated based on the absorbance value of the bacterial liquid at 600 nm.
The specific test method is as follows: preparation of the composition containing 10 6 CFU of escherichia coli liquid medium, 0.25g of composite starch base film was added to 10mL of escherichia coli liquid medium, the medium was incubated at 37 ℃ for 24 hours, and then the optical density of the medium corresponding to bacterial growth at 600nm spectrum was recorded by means of an ultraviolet-visible light spectrometer.
Example 1
A method of preparing a green active starch-based film having high barrier properties comprising the steps of:
(1) Eggshell washing:
placing the waste eggshell fragments into an alkaline aqueous solution for rotary soaking, repeating for three times after replacing the alkaline aqueous solution, cleaning again by deionized water, and drying at high temperature to obtain eggshell fragments;
(2) Obtaining eggshell powder:
placing the dried eggshell fragments into a pulverizer, pulverizing at high speed to obtain eggshell powder with different sizes, and sieving with 300 mesh sieve to obtain 300 mesh eggshell powder;
(3) Eggshell powder modification
Placing the obtained 300-mesh eggshell powder into a sodium alginate solution with the pH value of 5, continuously stirring for 1h, filtering and drying to obtain sodium alginate modified eggshell powder;
(4) Dispersing eggshell powder to adsorb plant active substances:
weighing 300mg of modified eggshell powder, placing the modified eggshell powder into an aqueous solution for ultrasonic dispersion to obtain a modified eggshell powder dispersion liquid, adding the modified eggshell powder dispersion liquid into 20ml of EGCG solution with the pH of 4.5 and the concentration of 10mg/ml, rotating at 600rpm in the dark to absorb the water for 3h, and centrifuging at 4000rpm to obtain eggshell powder for adsorbing plant active substances;
(5) Gelatinization: weighing 3g of starch, placing the starch into 80mL of water solution, adding 1g of glycerol, gelatinizing for 15min at 95 ℃, and stirring and cooling to 40 ℃ to obtain starch gelatinized solution;
(6) Preparing a film forming liquid:
dispersing 300mg of modified eggshell powder adsorbing plant active substances in water to obtain a dispersion; then uniformly mixing the dispersion liquid and the starch gelatinization solution to obtain film forming liquid;
(7) And (3) film preparation:
pouring the film forming liquid obtained in the step (6) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and drying the flat plate in a baking oven at 40 ℃ to form a film for 6 hours; the film was then peeled off and equilibrated at 53% humidity for 24h to give a film (thickness 0.098 mm) with active starch.
Example 2
A method of preparing a green active starch-based film having high barrier properties comprising the steps of:
(1) Eggshell washing:
placing the waste eggshell fragments into an alkaline aqueous solution for rotary soaking, repeating for three times after replacing the alkaline aqueous solution, cleaning again by deionized water, and drying at high temperature to obtain eggshell fragments;
(2) Obtaining eggshell powder:
placing the dried eggshell fragments into a pulverizer, pulverizing at high speed to obtain eggshell powder with different sizes, and sieving with 300 mesh sieve to obtain 300 mesh eggshell powder;
(3) Eggshell powder modification
Placing the obtained 300-mesh eggshell powder into a sodium alginate solution with the pH value of 5, continuously stirring for 1h, filtering and drying to obtain sodium alginate modified eggshell powder;
(4) Dispersing eggshell powder to adsorb plant active substances:
200mg of modified eggshell powder is weighed and placed in aqueous solution for ultrasonic dispersion to obtain modified eggshell powder dispersion liquid, the modified eggshell powder dispersion liquid is added into 20ml of EGCG solution with the pH of 4.5 and the concentration of 10mg/ml, the EGCG solution is rotated at 600rpm in the dark to absorb water for 3h, and the eggshell powder for adsorbing plant active substances is obtained through centrifugation at 4000 rpm;
(5) Gelatinization: weighing 3g of starch, placing the starch into 80mL of water solution, adding 1g of glycerol, gelatinizing for 15min at 95 ℃, and stirring and cooling to 40 ℃ to obtain starch gelatinized solution;
(6) Preparing a film forming liquid:
dispersing 200mg of modified eggshell powder adsorbing plant active substances in water to obtain a dispersion; then uniformly mixing the dispersion liquid and the starch gelatinization solution to obtain film forming liquid;
(7) And (3) film preparation:
pouring the film forming liquid obtained in the step (6) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and drying the flat plate in a baking oven at 40 ℃ to form a film for 6 hours; the film was then peeled off and equilibrated at 53% humidity for 24 hours to give an active starch-based film (thickness 0.091 mm).
Example 3
A method of preparing a green active starch-based film having high barrier properties comprising the steps of:
(1) Eggshell washing:
placing the waste eggshell fragments into an alkaline aqueous solution for rotary soaking, repeating for three times after replacing the alkaline aqueous solution, cleaning again by deionized water, and drying at high temperature to obtain eggshell fragments;
(2) Obtaining eggshell powder:
placing the dried eggshell fragments into a pulverizer, pulverizing at high speed to obtain eggshell powder with different sizes, and sieving with 300 mesh sieve to obtain 300 mesh eggshell powder;
(3) Eggshell powder modification
Placing the obtained 300-mesh eggshell powder into a sodium alginate solution with the pH value of 5, continuously stirring for 1h, filtering and drying to obtain sodium alginate modified eggshell powder;
(4) Dispersing eggshell powder to adsorb plant active substances:
weighing 400mg of modified eggshell powder, placing the modified eggshell powder into an aqueous solution for ultrasonic dispersion to obtain a modified eggshell powder dispersion liquid, adding the modified eggshell powder dispersion liquid into 20ml of EGCG solution with the pH of 4.5 and the concentration of 10mg/ml, rotating at 600rpm in the dark to absorb the water for 3h, and centrifuging at 4000rpm to obtain eggshell powder for adsorbing plant active substances;
(5) Gelatinization: weighing 3g of starch, placing the starch into 80mL of water solution, adding 1g of glycerol, gelatinizing for 15min at 95 ℃, and stirring and cooling to 40 ℃ to obtain starch gelatinized solution;
(6) Preparing a film forming liquid:
dispersing 400mg of modified eggshell powder adsorbing plant active substances in water to obtain a dispersion; then uniformly mixing the dispersion liquid and the starch gelatinization solution to obtain film forming liquid;
(7) And (3) film preparation:
pouring the film forming liquid obtained in the step (6) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and drying the flat plate in a baking oven at 40 ℃ to form a film for 6 hours; the film was then peeled off and equilibrated at 53% humidity for 24h to give an active starch-based film (thickness 0.110 mm).
Comparative example 1
(1) Preparation of gelatinized starch:
3g of corn starch and 1g of glycerol are weighed and added into 100mL of water solution, and gelatinization is carried out for 15min at 95 ℃ to obtain starch gelatinization solution;
(2) And (3) film preparation:
pouring the film forming liquid into a polytetrafluoroethylene flat plate by adopting a tape casting method, placing the flat plate in a baking oven at 40 ℃ to dry and form a film for 12 hours, then removing the film and balancing the film for 24 hours under 53% humidity to obtain the pure starch film starch base film (the thickness is 0.081 mm).
Comparative example 2
(1) Eggshell washing:
placing the waste eggshell fragments into an alkaline aqueous solution for rotary soaking, repeating for three times after replacing the alkaline aqueous solution, cleaning again by deionized water, and drying at high temperature to obtain eggshell fragments;
(2) Obtaining eggshell powder:
placing the dried eggshell fragments into a pulverizer, pulverizing at high speed to obtain eggshell powder with different sizes, and placing into a 200-mesh screen for sieving to obtain 200-mesh eggshell powder;
(3) Gelatinization: weighing 3g of starch, placing the starch into 80mL of water solution, adding 1g of glycerol, gelatinizing for 15min at 95 ℃, and stirring and cooling to 40 ℃ to obtain starch gelatinized solution;
(4) Preparing a film forming liquid:
dispersing 300mg of 200 mesh eggshell powder in water to obtain a dispersion; then uniformly mixing the dispersion liquid and the starch gelatinization solution to obtain film forming liquid;
(5) And (3) film preparation:
pouring the film forming liquid obtained in the step (4) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and drying the flat plate in a baking oven at 40 ℃ to form a film for 6 hours; the film was then peeled off and equilibrated at 53% humidity for 24 hours to obtain a composite starch-based film (thickness 0.108 mm).
Comparative example 3
(1) Eggshell washing:
placing the waste eggshell fragments into an alkaline aqueous solution for rotary soaking, repeating for three times after replacing the alkaline aqueous solution, cleaning again by deionized water, and drying at high temperature to obtain eggshell fragments;
(2) Obtaining eggshell powder:
placing the dried eggshell fragments into a pulverizer, pulverizing at high speed to obtain eggshell powder with different sizes, and sieving with 300 mesh sieve to obtain 300 mesh eggshell powder;
(3) Gelatinization: weighing 3g of starch, placing the starch into 80mL of water solution, adding 1g of glycerol, gelatinizing for 15min at 95 ℃, and stirring and cooling to 40 ℃ to obtain starch gelatinized solution;
(4) Preparing a film forming liquid:
dispersing 300mg 300 mesh eggshell powder in water to obtain a dispersion; then uniformly mixing the dispersion liquid and the starch gelatinization solution to obtain film forming liquid;
(5) And (3) film preparation:
pouring the film forming liquid obtained in the step (4) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and drying the flat plate in a baking oven at 40 ℃ to form a film for 6 hours; the film was then peeled off and equilibrated at 53% humidity for 24 hours to obtain a composite starch-based film (thickness 0.102 mm).
Comparative example 4
(1) Eggshell washing:
placing the waste eggshell fragments into an alkaline aqueous solution for rotary soaking, repeating for three times after replacing the alkaline aqueous solution, cleaning again by deionized water, and drying at high temperature to obtain eggshell fragments;
(2) Obtaining eggshell powder:
placing the dried eggshell fragments into a pulverizer, pulverizing at high speed to obtain eggshell powder with different sizes, and sieving with a 400-mesh sieve to obtain 400-mesh eggshell powder;
(3) Gelatinization: weighing 3g of starch, placing the starch into 80mL of water solution, adding 1g of glycerol, gelatinizing for 15min at 95 ℃, and stirring and cooling to 40 ℃ to obtain starch gelatinized solution;
(4) Preparing a film forming liquid:
dispersing 300mg of 400 mesh eggshell powder in water to obtain a dispersion; then uniformly mixing the dispersion liquid and the starch gelatinization solution to obtain film forming liquid;
(5) And (3) film preparation:
pouring the film forming liquid obtained in the step (4) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and drying the flat plate in a baking oven at 40 ℃ to form a film for 6 hours; the film was then peeled off and equilibrated at 53% humidity for 24 hours to obtain a composite starch-based film (thickness 0.099 mm).
Comparative example 5
(1) Eggshell washing:
placing the waste eggshell fragments into an alkaline aqueous solution for rotary soaking, repeating for three times after replacing the alkaline aqueous solution, cleaning again by deionized water, and drying at high temperature to obtain eggshell fragments;
(2) Obtaining eggshell powder:
placing the dried eggshell fragments into a pulverizer, pulverizing at high speed to obtain eggshell powder with different sizes, and sieving with 300 mesh sieve to obtain 300 mesh eggshell powder;
(3) Eggshell powder modification
Placing the obtained 300-mesh eggshell powder into a sodium alginate solution with the pH value of 5, continuously stirring for 1h, filtering and drying to obtain sodium alginate modified eggshell powder;
(4) Dispersing eggshell powder to adsorb plant active substances:
weighing 100mg of modified eggshell powder, placing the modified eggshell powder into an aqueous solution for ultrasonic dispersion to obtain a modified eggshell powder dispersion liquid, adding the modified eggshell powder dispersion liquid into 20ml of EGCG solution with the concentration of 10mg/ml, rotating at 600rpm for self absorption for 3h under dark conditions, and centrifuging at 4000rpm to obtain eggshell powder for adsorbing plant active substances;
(5) Gelatinization: weighing 3g of starch, placing the starch into 80mL of water solution, adding 1g of glycerol, gelatinizing for 15min at 95 ℃, and stirring and cooling to 40 ℃ to obtain starch gelatinized solution;
(6) Preparing a film forming liquid:
dispersing 100mg of modified eggshell powder for adsorbing plant active substances in water to obtain a dispersion; then uniformly mixing the dispersion liquid and the starch gelatinization solution to obtain film forming liquid;
(6) And (3) film preparation:
pouring the film forming liquid obtained in the step (5) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and drying the flat plate in a baking oven at 40 ℃ to form a film for 6 hours; the film was then peeled off and equilibrated at 53% humidity for 24 hours to give an active starch-based film (thickness 0.089 mm).
Comparative example 6
(1) Gelatinization: weighing 3g of starch, placing the starch into 80mL of water solution, adding 1g of glycerol, gelatinizing for 15min at 95 ℃, and stirring and cooling to 40 ℃ to obtain starch gelatinized solution;
(2) Preparing a film forming liquid:
uniformly mixing 20ml of EGCG solution with the pH of 4.5 and the concentration of 10mg/ml with the starch gelatinization solution to obtain film forming liquid;
(3) And (3) film preparation:
pouring the film forming liquid obtained in the step (2) into a polytetrafluoroethylene flat plate by adopting a tape casting method, and drying the flat plate in a baking oven at 40 ℃ to form a film for 6 hours; the film was then peeled off and equilibrated at 53% humidity for 24 hours to give an active starch-based film (thickness 0.089 mm).
The performance test is carried out on the obtained green active starch-based film with oxygen resistance and water resistance, and the test results are as follows:
as shown in fig. 1, a 300 mesh eggshell powder scanning electron microscope image of the active starch-based film prepared in example 1; wherein the left graph is to a 50 μm scale and the right graph is to a 5 μm scale; from the figure, the micropore and particle morphology can be visually seen, and the porous structure is the basis of the eggshell for adsorbing active substances.
FIG. 2 is a schematic representation of the active starch-based film prepared in example 1; the patterned paper was placed behind the active starch-based film, which was seen to be uniform, flat, very light in color, and more visually perceived as transparent, as compared to the paper without the film.
Fig. 3 and table 1 show the water vapor barrier properties of the composite starch-based film, as can be seen from fig. 3: the water vapor permeability of comparative example 1 was 382g/m 2 And/d, the water vapor barrier property of the pure starch-based film is poor. The water vapor transmission rates of examples 1 to 3 were 363g/m, respectively 2 /d、367g/m 2 /d、359g/m 2 And/d, the water vapor transmission rate of the pure starch-based film is significantly reduced compared with that of comparative example 1, which shows that the water vapor barrier property can be effectively improved by using eggshell powder. The water vapor transmission rates of comparative examples 2 to 5 were 370g/m, respectively 2 /d、371g/m 2 /d、372g/m 2 /d、374g/m 2 The water vapor transmission rate of the pure starch-based film was still reduced as compared with that of comparative example 1, which suggests that the addition of eggshell powder was advantageous for blocking water vapor although the size of eggshell powder or the treatment of eggshell powder was different, whereas the water vapor blocking property of comparative example 6 was 402g/m 2 And/d, it is stated that the direct addition of the plant active alone is disadvantageous for the barrier to water vapor.
Fig. 4 and table 2 show the oxygen barrier properties of the composite starch-based film, as can be seen from fig. 4: the oxygen transmission rate of the starch-based film of comparative example 1 was 119g/m 2 /d, all examples and pairs except comparative example 6The highest oxygen transmission rate among the ratios confirmed its poor oxygen transmission. The oxygen transmission rates of the composite starch-based films of examples 1 to 3 were 87g/m, respectively 2 /d、100g/m 2 /d、89g/m 2 And/d, compared with the pure starch-based film of comparative example 1, the oxygen barrier property of the composite starch-based film of the invention is improved by 27%, 16% and 25%, respectively, which proves that the composite starch-based film has effective oxygen barrier property.
The starch-based films of comparative examples 2 to 4 are mainly distinguished by the different sizes of the added eggshell powder, and the oxygen transmission rates thereof are respectively 100g/m 2 /d、90g/m 2 /d、105g/m 2 /d; from the results, the oxygen transmission rate was reduced compared to comparative example 1, and it was confirmed that the addition of eggshell powder was also advantageous for blocking oxygen, but the addition of eggshell powder of 300 mesh in comparative example 3 was more advantageous for blocking oxygen, and the addition of eggshell powder of 400 mesh in comparative example 4 was relatively small in effect on blocking oxygen. The oxygen transmission rate of the starch-based film of comparative example 5 was 102g/m 2 Comparative example 5 has a lower oxygen transmission rate than comparative example 1, which proves that the addition of 100mg of modified eggshell powder is also advantageous for blocking oxygen, but the addition of 30mg of modified eggshell powder of example 1 is more effective. The starch-based film of comparative example 6, which is mainly distinguished by the addition of only plant active substances, has an oxygen transmission rate of 125g/m 2 And/d, even higher than the pure starch film of comparative example 1, indicating that the addition of only plant active substances is detrimental to oxygen barrier.
Fig. 5 and table 3 show the antimicrobial properties of starch-based films, as can be seen from fig. 5: the absorbance of the escherichia coli culture solution of the composite starch film of the embodiment 1-3 is 0.891, 0.989 and 0.756 respectively, and compared with 1.212 of the pure starch film, the film has obvious antibacterial activity; comparative examples 1 to 4 do not have bacteriostatic activity. The absorbance of the escherichia coli culture solution of comparative example 5 is 1.121, and the membrane has weak antibacterial activity, which indicates that the modified eggshell powder can have better antibacterial effect only when the addition amount of the membrane is controlled within a proper range. While the absorbance of the E.coli culture solution of comparative example 6 was 0.762, the film had remarkable antibacterial activity, but since the active substance was extremely easily degraded under light, the film did not have long-acting antibacterial activity.
Table 1 water vapor barrier properties of composite starch-based films
| Scheme for the production of a semiconductor device | Water vapor transmission rate (g/m) 2 /d) |
| Example 1 | 363 |
| Example 2 | 367 |
| Example 3 | 359 |
| Comparative example 1 | 382 |
| Comparative example 2 | 370 |
| Comparative example 3 | 371 |
| Comparative example 4 | 372 |
| Comparative example 5 | 374 |
| Comparative example 6 | 395 |
TABLE 2 oxygen Barrier Properties of composite starch-based films
| Scheme for the production of a semiconductor device | Oxygen transmission rate (g/m) 2 /d) |
| Example 1 | 87 |
| Example 2 | 100 |
| Example 3 | 89 |
| Comparative example 1 | 119 |
| Comparative example 2 | 100 |
| Comparative example 3 | 90 |
| Comparative example 4 | 105 |
| Comparative example 5 | 102 |
| Comparative example 6 | 125 |
TABLE 3 antibacterial Properties of starch-based films
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Claims (11)
1. A method for preparing a green active starch-based membrane with barrier property is characterized by comprising the steps of washing eggshells, crushing to obtain eggshell powder with the number of 200-400 meshes, carrying out hydrophilic modification on the eggshell powder, and dispersing the eggshell powder to adsorb plant active substances after drying to obtain eggshell powder adsorbing the plant active substances; then evenly mixing the starch paste solution to obtain film forming solution, and preparing a film to obtain a green active starch base film with barrier property;
wherein the modified solution is sodium alginate, dopamine or tannic acid solution, and the pH value of the modified solution is 5-10;
the plant active substance is one or two of catechin and/or curcumin, and the pH of the plant active substance solution is 3-5;
the mass ratio of the starch to the eggshell powder for adsorbing the plant active substances is 3:1-15:1.
2. The method according to claim 1, wherein the concentration of the modifying solution is 1-100mg/mL, and the mass-volume ratio of eggshell powder to modifying solution is 1:1 to 10:1.
3. the method of claim 1, wherein the plant active is present at a concentration of 5-20mg/mL.
4. A method according to any one of claims 1-3, characterized in that the method comprises the steps of:
(1) Eggshell washing:
washing the waste eggshell fragments with an alkaline aqueous solution to remove proteins and impurities, and drying to obtain eggshell fragments;
(2) Obtaining eggshell powder:
pulverizing eggshell fragments, and sieving to obtain 200-400 mesh eggshell powder;
(3) Modifying eggshell powder:
placing eggshell powder into a modifying solution with a certain pH value for hydrophilic modification, filtering and drying to obtain modified eggshell powder;
(4) The dispersion modified eggshell powder adsorbs plant active substances:
dispersing the modified eggshell powder to obtain eggshell powder dispersion liquid, adding a plant active substance solution, rotating in a dark place to perform self-adsorption, and centrifuging to obtain eggshell powder for adsorbing plant active substances;
(5) Preparing a film forming liquid:
dispersing eggshell powder adsorbing plant active substances in water to obtain dispersion liquid; then uniformly mixing the dispersion liquid and the starch gelatinization solution to obtain film forming liquid;
(6) And (3) film preparation:
and (3) preparing a film from the film forming liquid to obtain the green active starch base film with barrier property.
5. A green active starch-based film prepared according to any one of claims 1-3.
6. Use of the green active starch-based film of claim 5 in the preparation of a food product.
7. The use of the green active starch-based film of claim 5 in the preparation of a medicament.
8. Use of the green activated starch-based film of claim 5 in the manufacture of a medical device.
9. Use of the green activated starch-based film of claim 5 in the manufacture of agricultural products.
10. A degradable material comprising the green activated starch-based film of claim 5.
11. A packaging material comprising the green active starch-based film of claim 5.
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| JPH04363239A (en) * | 1991-04-04 | 1992-12-16 | Goyo Paper Working Co Ltd | Gas barrier material and base material for vessel using the same material |
| CN104448399A (en) * | 2014-12-09 | 2015-03-25 | 北京印刷学院 | Potato starch-based degradable antibacterial packaging film and preparation method thereof |
| CN110862582A (en) * | 2019-11-29 | 2020-03-06 | 河南农业大学 | Hydrophobic organic/inorganic composite preservative film for meat products |
| CN113045786A (en) * | 2021-04-02 | 2021-06-29 | 广西大学 | Multifunctional self-fit film and method and application for quickly positioning and forming film |
| CN113354853A (en) * | 2021-06-30 | 2021-09-07 | 青岛科技大学 | Biodegradable high-barrier antibacterial composite membrane and preparation method thereof |
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2023
- 2023-02-22 CN CN202310149794.7A patent/CN116410496B/en active Active
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| JPH04363239A (en) * | 1991-04-04 | 1992-12-16 | Goyo Paper Working Co Ltd | Gas barrier material and base material for vessel using the same material |
| CN104448399A (en) * | 2014-12-09 | 2015-03-25 | 北京印刷学院 | Potato starch-based degradable antibacterial packaging film and preparation method thereof |
| CN110862582A (en) * | 2019-11-29 | 2020-03-06 | 河南农业大学 | Hydrophobic organic/inorganic composite preservative film for meat products |
| CN113045786A (en) * | 2021-04-02 | 2021-06-29 | 广西大学 | Multifunctional self-fit film and method and application for quickly positioning and forming film |
| CN113354853A (en) * | 2021-06-30 | 2021-09-07 | 青岛科技大学 | Biodegradable high-barrier antibacterial composite membrane and preparation method thereof |
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