CN117209862A - Ammonia-sensitive tough starch-based composite film and preparation method and application thereof - Google Patents
Ammonia-sensitive tough starch-based composite film and preparation method and application thereof Download PDFInfo
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- CN117209862A CN117209862A CN202311215341.6A CN202311215341A CN117209862A CN 117209862 A CN117209862 A CN 117209862A CN 202311215341 A CN202311215341 A CN 202311215341A CN 117209862 A CN117209862 A CN 117209862A
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- starch
- parts
- ammonia
- tough
- based composite
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229920002472 Starch Polymers 0.000 title claims abstract description 73
- 235000019698 starch Nutrition 0.000 title claims abstract description 73
- 239000008107 starch Substances 0.000 title claims abstract description 73
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000000903 blocking effect Effects 0.000 claims abstract description 12
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 238000004806 packaging method and process Methods 0.000 claims abstract description 5
- 230000007613 environmental effect Effects 0.000 claims abstract description 4
- 235000013305 food Nutrition 0.000 claims abstract description 4
- 238000012544 monitoring process Methods 0.000 claims abstract description 4
- 230000000007 visual effect Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 10
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- HNDVDQJCIGZPNO-RXMQYKEDSA-N D-histidine Chemical compound OC(=O)[C@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-RXMQYKEDSA-N 0.000 claims description 4
- 229930195721 D-histidine Natural products 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 230000004044 response Effects 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000012767 functional filler Substances 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 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
Abstract
The invention relates to the technical field of starch-based composite materials, in particular to a tough starch-based composite film with ammonia sensitivity, and a preparation method and application thereof. The invention uses the iron metal organic frame as the functional filler, and can effectively improve the performance and the function of the starch-based material. The ammonia-sensitive tough starch-based composite film material prepared by the invention has excellent ultraviolet shielding performance, high-energy short-wave blue light blocking performance, mechanical strength, toughness, oxygen blocking performance, thermochromic performance and ammonia response color changing performance, is simple in preparation process, environment-friendly, low in cost and suitable for large-scale production, and has wide application value in the fields of visual detection of ammonia, thermochromic materials, ultraviolet blocking materials, food packaging, intelligent materials, ammonia detection, environmental monitoring, safety and the like.
Description
Technical Field
The invention relates to the technical field of starch-based composite materials, in particular to a tough starch-based composite film with ammonia sensitivity, and a preparation method and application thereof.
Background
Starch belongs to a high molecular carbohydrate, is formed by connecting a plurality of glucosides through glycosidic bonds, is a renewable plant resource and widely exists in grains, tubers and beans. The starch has rich sources and low price, has the characteristic of complete degradability, high biocompatibility and good film forming property, and is one of the most potential natural biodegradable materials. However, starch-based materials exhibit some limitations, such as poor mechanical properties, water vapor barrier properties, oxygen barrier properties, uv shielding properties, high energy short wave blue light barrier properties, and lack of ammonia response, thermochromic, antimicrobial, etc., which make them somewhat limited in practical use. The application of the starch-based composite material in the fields of packaging, ultraviolet protection, ammonia response, antibiosis and the like is severely restricted. Therefore, the development of the tough starch-based composite film with ammonia sensitivity has wide application prospect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the tough starch-based composite film with ammonia sensitivity and the preparation method thereof, wherein starch is taken as a base material, an iron metal organic frame is taken as a filler, after the iron metal organic frame nano particles are added into a starch matrix, the ultraviolet shielding performance, the high-energy short-wave blue light blocking performance, the mechanical performance, the oxygen blocking performance, the thermochromic performance and the ammonia response color changing performance of the starch-based film material can be effectively improved, and the preparation process is simple and environment-friendly, has low cost and is suitable for amplified production.
The technical scheme of the invention is as follows:
an ammonia-sensitive tough starch-based composite film comprises the following components in parts by weight: 200 parts of starch and 2-6 parts of an iron metal organic framework.
The preparation method of the iron metal organic frame comprises the following steps:
(1) Dissolving 15.5 parts by mass of D-histidine in 5000 parts by mass of deionized water for later use;
(2) Dissolving 50 parts by mass of ferric sulfate in 1000 parts by mass of deionized water for later use;
(3) And (3) dropwise adding the ferric sulfate solution in the step (2) into the solution in the step (1), stirring at room temperature for reaction 1h, and then centrifuging, washing and freeze-drying to obtain the ferric metal organic frame.
The preparation method of the ammonia-sensitive tough starch-based composite film comprises the following steps:
(1) Adding 200 parts of starch into 3000 parts of deionized water, stirring for 30min at room temperature, and stirring for 30min at 95 ℃ to obtain uniform starch solution for later use;
(2) Dispersing 2-6 parts of an iron metal organic frame in 1000 parts of deionized water, and stirring for 1h to obtain uniform dispersion liquid for later use;
(3) Adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 95 ℃ to obtain uniform film forming liquid for later use;
(4) Pouring the film forming liquid in the step (3) onto a plastic mold, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the ammonia-sensitive tough starch-based composite film.
The invention has the beneficial effects that:
the invention uses self-made iron metal organic frame as modifier, which can effectively improve the performance of starch-based composite film material. The ammonia-sensitive tough starch composite film prepared by the invention has excellent ultraviolet shielding performance, high-energy short-wave blue light blocking performance, mechanical strength, toughness, oxygen blocking performance, thermochromic performance and ammonia response color changing performance, is simple and environment-friendly in preparation process, low in cost and suitable for amplified production, and has good application prospects in the fields of ammonia visual detection, thermochromic materials, ultraviolet blocking materials, food packaging, intelligent materials, environmental monitoring, safety fields and the like.
Drawings
FIG. 1 is a scanning electron microscope picture of an iron metal organic framework according to the present invention;
FIG. 2 is a photograph of a pure starch film sample prepared according to the comparative example of the present invention;
FIG. 3 is a photograph of a sample of the starch-based composite film prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In the specific examples and comparative examples formulations, D-histidine was an analytically pure grade reagent supplied by Shanghai Yi En chemical technology Co., ltd, ferric sulfate, methanol was an analytically pure grade reagent supplied by Shanghai Yi En chemical technology Co., ltd, and starch was a product supplied by Shanghai Yi En chemical technology Co.
In the specific examples and comparative examples formulations, the method of making the iron metal organic framework comprises the steps of: (1) Dissolving 15.5 parts by mass of D-histidine in 5000 parts by mass of deionized water for later use; (2) Dissolving 50 parts by mass of ferric sulfate in 1000 parts by mass of deionized water for later use; (3) And (3) dropwise adding the ferric sulfate solution in the step (2) into the solution in the step (1), stirring at room temperature for reaction 1h, and then centrifuging, washing and freeze-drying to obtain the ferric metal organic frame (the average particle size of which is 200 nm).
Example 1
An ammonia-sensitive tough starch-based composite film comprises the following components in parts by weight: 200 parts of starch and 2 parts of an iron metal organic frame.
The preparation method comprises the following steps:
(1) Adding 200 parts of starch into 3000 parts of deionized water, stirring for 30min at room temperature, and stirring for 30min at 95 ℃ to obtain uniform starch solution for later use;
(2) Dispersing 2 parts of an iron metal organic frame in 1000 parts of deionized water, and stirring for 1h to obtain uniform dispersion liquid for later use;
(3) Adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 95 ℃ to obtain uniform film forming liquid for later use;
(4) Pouring the film forming liquid in the step (3) onto a plastic mold, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the ammonia-sensitive tough starch composite film.
Example 2
An ammonia-sensitive tough starch-based composite film comprises the following components in parts by weight: 200 parts of starch and 4 parts of an iron metal organic frame.
The preparation method comprises the following steps:
(1) Adding 200 parts of starch into 3000 parts of deionized water, stirring for 30min at room temperature, and stirring for 30min at 95 ℃ to obtain uniform starch solution for later use;
(2) Dispersing 4 parts of an iron metal organic frame in 1000 parts of deionized water, and stirring for 1h to obtain uniform dispersion liquid for later use;
(3) Adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 95 ℃ to obtain uniform film forming liquid for later use;
(4) Pouring the film forming liquid in the step (3) onto a plastic mold, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the ammonia-sensitive tough starch composite film.
Example 3
An ammonia-sensitive tough starch-based composite film comprises the following components in parts by weight: 200 parts of starch and 6 parts of an iron metal organic frame.
The preparation method comprises the following steps:
(1) Adding 200 parts of starch into 3000 parts of deionized water, stirring for 30min at room temperature, and stirring for 30min at 95 ℃ to obtain uniform starch solution for later use;
(2) Dispersing 6 parts of an iron metal organic frame in 1000 parts of deionized water, and stirring for 1h to obtain uniform dispersion liquid for later use;
(3) Adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 95 ℃ to obtain uniform film forming liquid for later use;
(4) Pouring the film forming liquid in the step (3) onto a plastic mold, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the ammonia-sensitive tough starch composite film.
Comparative example
As a comparison standard for each of the above examples, the present invention provides a pure starch film material prepared without an iron metal organic framework, comprising the steps of:
(1) Adding 200 parts of starch into 3000 parts of deionized water, stirring for 30min at room temperature, and stirring for 30min at 95 ℃ to obtain uniform starch solution for later use;
(2) Adding 1000 parts of deionized water into the starch solution obtained in the step (1), and stirring for 1h at 95 ℃ to obtain uniform film forming liquid for later use;
(3) Pouring the film forming liquid in the step (2) onto a plastic mold, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the starch film material.
Performance test:
the starch film material prepared in the above comparative example and the starch-based composite film material prepared in the example were subjected to a performance test, wherein tensile properties were tested by an electronic tensile tester (LDW-2G), ultraviolet-visible properties were tested by an ultraviolet spectrophotometer (Lambda 750, perkin elmer instruments) and the average transmittance of ultraviolet rays (UVA, UVB and UVC) was calculated with reference to GB/T18830-2009.
The method for testing the oxygen permeability coefficient comprises the following steps:
the film sample (diameter: 1.8 cm) was sealed into a glass vial containing 3g of deoxidizer (including 1.0g of activated carbon, 1.5g of sodium chloride and 0.5g of reduced iron powder), the vial was weighed (denoted as W1), then placed in a closed container having a relative humidity of 90% and a temperature of 25 ℃ for 48 hours, and after placing, the vial was reweighed (denoted as W2), and the oxygen transmission coefficient OP= (W2-W1)/(S×t), where S and t represent the area and the placing time of the film sample.
The ammonia response test method is as follows: the sample material was exposed to an ammonia atmosphere and the color change of the sample material was observed.
Table 1 performance test data
| Group of | Example 1 | Example 2 | Example 3 | Comparative example |
| Ultraviolet UVA average transmittance (%) | 1.1 | 0 | 0 | 45.0 |
| Ultraviolet UVB average transmittance (%) | 0.3 | 0 | 0 | 37.0 |
| Ultraviolet UVC average transmittance (%) | 0.2 | 0 | 0 | 20.1 |
| High-energy shortwave blue light average transmittance (%) | 7.7 | 1.2 | 0.3 | 48.6 |
| Average transmittance (%) | 26.5 | 12.7 | 9.7 | 53.0 |
| Tensile Strength (MPa) | 28.5 | 29.9 | 35.4 | 23.2 |
| Elongation at break (%) | 4.8 | 6.2 | 5.2 | 2.6 |
| Toughness (MJ/m) 3 ） | 1.02 | 1.52 | 1.46 | 0.45 |
| Oxygen permeability coefficient (10) -3 g/m 2 ⋅s） | 3.37 | 3.32 | 3.14 | 3.40 |
The ammonia response test experiment results prove that the starch film prepared by the comparative example is colorless and transparent, and the color of the starch film is not obviously changed or the starch film shows colorless and transparent optical properties after the starch film is exposed to an ammonia environment; the starch-based composite film material prepared in example 1 was pale yellow, and changed to light tan after being exposed to ammonia gas; the starch-based composite film prepared in example 2 was yellow in color and turned brown after exposure to ammonia; the starch-based composite film prepared in example 3 was yellow in color and turned tan after exposure to ammonia.
The starch film prepared by the comparative example is colorless and transparent, and has no obvious change in color or colorless and transparent optical property when placed in a high-temperature environment of 120 ℃; the starch-based composite film prepared in example 3 is yellow, and changes to black brown in color when placed in a high-temperature environment at 120 ℃, which indicates that the starch-based composite film has obvious thermochromic property.
In a word, the sample performance test data show that the ammonia-sensitive tough starch composite film prepared by the invention has excellent ultraviolet shielding performance, high-energy short-wave blue light blocking performance, mechanical strength, toughness, oxygen blocking performance, thermochromic performance and ammonia response color changing performance, and the preparation process is simple and environment-friendly, low in cost and suitable for amplified production, and has wide application value in the fields of ammonia visual detection, thermochromic materials, ultraviolet blocking materials, food packaging, intelligent materials, environmental monitoring, safety fields and the like.
The content of the invention is not limited to the examples listed, and any equivalent transformation to the technical solution of the invention that a person skilled in the art can take on by reading the description of the invention is covered by the claims of the invention.
Claims (3)
1. The ammonia-sensitive tough starch-based composite film is characterized by comprising the following components in parts by weight: 200 parts of starch and 2-6 parts of an iron metal organic frame;
the iron metal organic framework is nano particles, and the preparation method comprises the following steps:
(1) Dissolving 15.5 parts by mass of D-histidine in 5000 parts by mass of deionized water for later use;
(2) Dissolving 50 parts by mass of ferric sulfate in 1000 parts by mass of deionized water for later use;
(3) And (3) dropwise adding the ferric sulfate solution in the step (2) into the solution in the step (1), stirring at room temperature for reaction 1h, and then centrifuging, washing and freeze-drying to obtain the ferric metal organic frame.
2. The method for preparing the ammonia-sensitive tough starch-based composite film according to claim 1, comprising the steps of:
(1) Adding 200 parts of starch into 3000 parts of deionized water, stirring for 30min at room temperature, and stirring for 30min at 95 ℃ to obtain uniform starch solution for later use;
(2) Dispersing 2-6 parts of an iron metal organic frame in 1000 parts of deionized water, and stirring for 1h to obtain uniform dispersion liquid for later use;
(3) Adding the dispersion liquid obtained in the step (2) into the starch solution obtained in the step (1), and stirring for 1h at 95 ℃ to obtain uniform film forming liquid for later use;
(4) Pouring the film forming liquid in the step (3) onto a plastic mold, and drying in a vacuum oven at 55 ℃ for 24 hours to obtain the ammonia-sensitive tough starch composite film.
3. The application of the ammonia-sensitive tough starch-based composite film according to claim 1, which is applicable to the fields of visual detection of ammonia gas, thermochromic materials, ultraviolet blocking materials, food packaging, intelligent materials, environmental monitoring and safety.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311215341.6A CN117209862A (en) | 2023-09-20 | 2023-09-20 | Ammonia-sensitive tough starch-based composite film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311215341.6A CN117209862A (en) | 2023-09-20 | 2023-09-20 | Ammonia-sensitive tough starch-based composite film and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117209862A true CN117209862A (en) | 2023-12-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311215341.6A Pending CN117209862A (en) | 2023-09-20 | 2023-09-20 | Ammonia-sensitive tough starch-based composite film and preparation method and application thereof |
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| Country | Link |
|---|---|
| CN (1) | CN117209862A (en) |
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2023
- 2023-09-20 CN CN202311215341.6A patent/CN117209862A/en active Pending
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