CN115260603A - Starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions as well as preparation method and application thereof - Google Patents
Starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions as well as preparation method and application thereof Download PDFInfo
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 104
- 229920002472 Starch Polymers 0.000 title claims abstract description 104
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 104
- 235000019698 starch Nutrition 0.000 title claims abstract description 104
- 239000008107 starch Substances 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000005316 response function Methods 0.000 title claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 55
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 239000011787 zinc oxide Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 24
- 235000013305 food Nutrition 0.000 claims abstract description 9
- 238000012544 monitoring process Methods 0.000 claims abstract description 8
- 230000007613 environmental effect Effects 0.000 claims abstract description 6
- 238000004806 packaging method and process Methods 0.000 claims abstract description 6
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 abstract description 29
- 230000008859 change Effects 0.000 abstract description 17
- 229910021529 ammonia Inorganic materials 0.000 abstract description 12
- 241000143060 Americamysis bahia Species 0.000 abstract description 9
- 230000004888 barrier function Effects 0.000 abstract description 6
- 230000003115 biocidal effect Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
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- 235000013372 meat Nutrition 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
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- 239000003929 acidic solution Substances 0.000 description 2
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- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000012767 functional filler Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
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- 235000013622 meat product Nutrition 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- 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
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Abstract
A starch/polyvinyl alcohol based high-performance composite material with antibacterial and pH response functions, a preparation method and an application thereof are disclosed, wherein the composite material is prepared from the following raw materials: starch, polyvinyl alcohol, glycerol, rhein and rod-shaped zinc oxide nanoparticles. The invention also provides a preparation method of the starch/polyvinyl alcohol based high-performance composite material. The starch/polyvinyl alcohol-based high-performance composite material prepared by the invention has excellent performances of water vapor barrier, mechanics, pH response, ammonia response, thermal response color change, antibiosis, ultraviolet shielding, blue light shielding and the like, can be used as an intelligent indicating material to timely and effectively indicate the freshness change condition of meat food such as shrimps and the like in the storage process, has simple preparation process, environmental protection and low cost, is suitable for amplification production, and has potential application value in the fields of food packaging, biomedicine, antibacterial materials, ammonia detection, environmental monitoring, safety and the like.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions, and a preparation method and application thereof.
Background
Polyvinyl alcohol is a biodegradable polymer which can be produced in large quantities through non-petroleum ways, has the advantages of low cost, good film forming property, high stability, high transparency and the like, and has unique superiority in the field of food and medicine packaging. However, polyvinyl alcohol has disadvantages of high cost, slow degradation rate in soil, and the like. One way to overcome the disadvantages of pure polyvinyl alcohol materials is to mix it with natural biopolymers. Starch is a degradable, renewable natural biopolymer, one of the most important polysaccharides, and is mainly composed of amylose and amylopectin. Because of low cost and high degradation speed, the method has considerable prospect in the aspect of developing environment-friendly materials. The starch is added into the polyvinyl alcohol material, so that the biodegradation speed of the material can be improved, and the more economical and environment-friendly starch/polyvinyl alcohol base material is produced. But simultaneously, the mechanical property and the water vapor barrier property of the starch are weakened due to the difference of the chemical structures of the starch and the polyvinyl alcohol and the starch and the limited compatibility of the starch and the polyvinyl alcohol. In addition, the starch/polyvinyl alcohol-based composite material lacks functions of pH response, ammonia response, thermal response color change, antibiosis, ultraviolet shielding, blue light shielding and the like, so that the practical application of the starch/polyvinyl alcohol-based composite material is limited to a certain extent. The starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions is prepared by taking starch/polyvinyl alcohol as a matrix and utilizing rod-shaped zinc oxide nanoparticles and rhein as functional fillers, so that the performances of water vapor barrier, mechanics, pH response, ammonia response, thermal response color change, antibiosis, ultraviolet shielding, blue light shielding and the like of the starch/polyvinyl alcohol composite material are enhanced, and the application of the starch/polyvinyl alcohol-based high-performance composite material in the fields of food packaging, intelligent materials, biomedicine, antibacterial materials, ammonia detection, environmental monitoring, safety and the like is widened.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions as well as a preparation method and application thereof. The composite material has excellent performances of water vapor barrier, mechanics, pH response, ammonia response, thermal response color change, antibiosis, ultraviolet shielding, blue light shielding and the like, can be used as an intelligent indicating material to timely and effectively indicate the freshness change condition of meat products such as shrimps and the like in the storage process, and is simple in preparation process, environment-friendly, low in cost and suitable for amplification production.
The technical scheme of the invention is as follows:
the invention provides a starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions, which is characterized by comprising the following components in parts by weight: 125 parts of starch, 125 parts of polyvinyl alcohol, 31.25 parts of glycerol, 1.25 parts of rhein and 2.5-12.5 parts of rod-shaped zinc oxide nanoparticles;
the preparation method of the rod-shaped zinc oxide nano particles comprises the following steps: dissolving 5.48 parts of zinc acetate in 86.3 parts of 1,2-propylene glycol, then adding 3.15 parts of deionized water, stirring and mixing uniformly, adding 6.15 parts of sodium acetate into the solution, stirring uniformly, heating to 150 ℃, refluxing for 1h, then carrying out centrifugal separation and drying to obtain the rod-shaped zinc oxide nanoparticles.
The invention also provides a preparation method of the starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions, which comprises the following steps:
(1) Adding 125 parts of polyvinyl alcohol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform polyvinyl alcohol solution for later use;
(2) Adding 125 parts of starch and 31.25 parts of glycerol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform starch solution for later use;
(3) Dispersing 2.5-12.5 parts of rod-shaped zinc oxide nanoparticles into 1000 parts of deionized water, and stirring at room temperature for 30min to obtain uniform dispersion liquid of the rod-shaped zinc oxide nanoparticles for later use;
(4) Dispersing 1.25 parts of rhein in 1000 parts of deionized water, and stirring at room temperature for 30min to obtain a homogeneous rhein dispersion for later use;
(5) Adding the starch solution obtained in the step (2), the zinc oxide dispersion liquid obtained in the step (3) and the rhein dispersion liquid obtained in the step (4) into the polyvinyl alcohol solution obtained in the step (1), and stirring at 85 ℃ for 30min to obtain a uniform film forming liquid for later use;
(6) And (3) pouring the film forming liquid obtained in the step (5) into a flat-bottomed glass dish, and drying in an oven at the temperature of 60 ℃ for 24 hours to obtain the starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions.
Compared with the prior art, the invention has the following beneficial effects:
the starch/polyvinyl alcohol-based high-performance composite material prepared by the invention has excellent properties of water vapor barrier, mechanics, pH response, ammonia response, thermal response color change, antibiosis, ultraviolet shielding, blue-light shielding and the like, can be used as an intelligent indicating material to timely and effectively indicate the freshness change condition of meat food such as shrimps and the like in the storage process, has simple preparation process, environmental protection and low cost, is suitable for amplified production, and has potential application value in the fields of food packaging, intelligent materials, biomedicine, antibacterial materials, ammonia gas detection, environmental monitoring, safety and the like.
Drawings
FIG. 1 is a scanning electron microscope image of rod-like zinc oxide nanoparticles according to the present invention;
FIG. 2 is a scanning electron microscope cross-sectional view of a starch/polyvinyl alcohol-based high performance composite material prepared in example 1 of the present invention.
Detailed Description
In order to better explain the present invention, the present invention is further explained in detail below with reference to specific examples, but the embodiments of the present invention are not limited thereto.
In the following specific examples and comparative example formulations, the preparation methods, the starches used were corn starch (CAS number: 9005-25-8) supplied by Shanghai Aladdin Biotechnology Ltd; the polyvinyl alcohol is a product provided by Changchun chemical industry Co., ltd and has the model of PVA-1788; rhein is an analytical pure-grade reagent provided by Shanghai xiandin biological technology limited company; sodium acetate and zinc acetate are analytical pure grade reagents provided by Shanghai Aladdin Biotechnology GmbH; 1,2-propanediol is an analytical grade reagent supplied by rayne reagents ltd; glycerol is an analytical grade reagent supplied by Shirong scientific Inc.
In the following specific examples and comparative example formulations, preparation methods, the preparation method of the rod-shaped zinc oxide nanoparticles includes the following steps: dissolving 5.48 parts of zinc acetate in 86.3 parts of 1,2-propylene glycol, then adding 3.15 parts of deionized water, stirring and mixing uniformly, adding 6.15 parts of sodium acetate into the solution, stirring uniformly, heating to 150 ℃, refluxing for 1h, then carrying out centrifugal separation and drying to obtain rod-shaped zinc oxide nanoparticles (the diameter of which is 40-60 nm, the length of which is 100-200 nm, and is shown in a scanning electron microscope picture of figure 1).
Example 1
A starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions is characterized by comprising the following components in parts by weight: 125 parts of starch, 125 parts of polyvinyl alcohol, 31.25 parts of glycerol, 1.25 parts of rhein and 2.5 parts of rod-shaped zinc oxide nanoparticles.
The preparation method comprises the following steps:
(1) Adding 125 parts of polyvinyl alcohol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform polyvinyl alcohol solution for later use;
(2) Adding 125 parts of starch and 31.25 parts of glycerol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform starch solution for later use;
(3) Dispersing 2.5 parts of rod-shaped zinc oxide nanoparticles into 1000 parts of deionized water, and stirring at room temperature for 30min to obtain a uniform dispersion liquid of the rod-shaped zinc oxide nanoparticles for later use;
(4) Dispersing 1.25 parts of rhein in 1000 parts of deionized water, and stirring at room temperature for 30min to obtain a homogeneous rhein dispersion for later use;
(5) Adding the starch solution obtained in the step (2), the zinc oxide dispersion liquid obtained in the step (3) and the rhein dispersion liquid obtained in the step (4) into the polyvinyl alcohol solution obtained in the step (1), and stirring at 85 ℃ for 30min to obtain a uniform film forming liquid for later use;
(6) And (3) pouring the film forming liquid obtained in the step (5) into a flat-bottomed glass dish, and drying in an oven at the temperature of 60 ℃ for 24 hours to obtain the starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions.
Example 2
A starch/polyvinyl alcohol based high-performance composite material with antibacterial and pH response functions is characterized by comprising the following components in parts by weight: 125 parts of starch, 125 parts of polyvinyl alcohol, 31.25 parts of glycerol, 1.25 parts of rhein and 7.5 parts of rod-shaped zinc oxide nanoparticles.
The preparation method comprises the following steps:
(1) Adding 125 parts of polyvinyl alcohol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform polyvinyl alcohol solution for later use;
(2) Adding 125 parts of starch and 31.25 parts of glycerol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform starch solution for later use;
(3) Dispersing 7.5 parts of rod-shaped zinc oxide nanoparticles into 1000 parts of deionized water, and stirring at room temperature for 30min to obtain a uniform dispersion liquid of the rod-shaped zinc oxide nanoparticles for later use;
(4) Dispersing 1.25 parts of rhein in 1000 parts of deionized water, and stirring at room temperature for 30min to obtain a rhein uniform dispersion liquid for later use;
(5) Adding the starch solution obtained in the step (2), the zinc oxide dispersion liquid obtained in the step (3) and the rhein dispersion liquid obtained in the step (4) into the polyvinyl alcohol solution obtained in the step (1), and stirring at 85 ℃ for 30min to obtain a uniform film forming liquid for later use;
(6) And (3) pouring the film forming liquid obtained in the step (5) into a flat-bottomed glass dish, and drying in an oven at the temperature of 60 ℃ for 24 hours to obtain the starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions.
Example 3
A starch/polyvinyl alcohol based high-performance composite material with antibacterial and pH response functions is characterized by comprising the following components in parts by weight: 125 parts of starch, 125 parts of polyvinyl alcohol, 31.25 parts of glycerol, 1.25 parts of rhein and 12.5 parts of rod-shaped zinc oxide nanoparticles.
The preparation method comprises the following steps:
(1) Adding 125 parts of polyvinyl alcohol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform polyvinyl alcohol solution for later use;
(2) Adding 125 parts of starch and 31.25 parts of glycerol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform starch solution for later use;
(3) Dispersing 12.5 parts of rod-shaped zinc oxide nanoparticles into 1000 parts of deionized water, and stirring at room temperature for 30min to obtain a uniform dispersion liquid of the rod-shaped zinc oxide nanoparticles for later use;
(4) Dispersing 1.25 parts of rhein in 1000 parts of deionized water, and stirring at room temperature for 30min to obtain a homogeneous rhein dispersion for later use;
(5) Adding the starch solution obtained in the step (2), the zinc oxide dispersion liquid obtained in the step (3) and the rhein dispersion liquid obtained in the step (4) into the polyvinyl alcohol solution obtained in the step (1), and stirring at 85 ℃ for 30min to obtain a uniform film forming liquid for later use;
(6) And (3) pouring the film forming liquid obtained in the step (5) into a flat-bottomed glass dish, and drying in an oven at the temperature of 60 ℃ for 24 hours to obtain the starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions.
Comparative example 1
The preparation method of the starch/polyvinyl alcohol composite material comprises the following steps:
(1) Adding 125 parts of polyvinyl alcohol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform polyvinyl alcohol solution for later use;
(2) Adding 125 parts of starch and 31.25 parts of glycerol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform starch solution for later use;
(3) Adding the starch solution obtained in the step (2) and 2000 parts of deionized water into the polyvinyl alcohol solution obtained in the step (1), and stirring at 85 ℃ for 30min to obtain uniform film forming liquid for later use;
(4) And (4) pouring the film forming liquid obtained in the step (3) into a flat-bottomed glass dish, and drying in a drying oven at the temperature of 60 ℃ for 24 hours to obtain the starch/polyvinyl alcohol composite material.
Comparative example 2
The preparation method of the starch/polyvinyl alcohol/rhein composite material comprises the following steps:
(1) Adding 125 parts of polyvinyl alcohol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform polyvinyl alcohol solution for later use;
(2) Adding 125 parts of starch and 31.25 parts of glycerol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform starch solution for later use;
(3) Dispersing 1.25 parts of rhein in 1000 parts of deionized water, and stirring at room temperature for 30min to obtain a homogeneous rhein dispersion for later use;
(4) Adding the starch solution obtained in the step (2), the rhein dispersion liquid obtained in the step (3) and 1000 parts of deionized water into the polyvinyl alcohol solution obtained in the step (1), and stirring at 85 ℃ for 30min to obtain a uniform film forming liquid for later use;
(5) And (5) pouring the film forming solution obtained in the step (4) into a flat-bottomed glass dish, and drying in a drying oven at the temperature of 60 ℃ for 24 hours to obtain the starch/polyvinyl alcohol/rhein composite material.
And (3) testing structure and performance:
performing structure and performance tests on the starch/polyvinyl alcohol composite material prepared in the comparative example, the starch/polyvinyl alcohol/rhein composite material and the starch/polyvinyl alcohol-based high-performance composite material prepared in the embodiment, wherein the cross-sectional morphology of the starch/polyvinyl alcohol-based high-performance composite material is characterized by an SEM (SU-5000, japan high and new technology company) instrument; the ultraviolet-visible performance was tested using an ultraviolet-visible spectrometer (Lamdba 365, platinum elmer instruments) and the average Ultraviolet (UV) transmittance was calculated with reference to GB/T18830-2009; the tensile property is tested according to GB/T1040-2006; the water vapor transmission coefficient is tested according to ASTME 96; performing antibacterial property test of the material according to QBT 2591-2003; the thermal response discoloration test method is as follows: placing the sample material in an oven at 105 ℃, and observing the color change of the sample material; the pH-responsive discoloration test method is as follows: dripping acidic or alkaline buffer solution with certain pH value on the surface of the sample material, and observing the color change of the sample material; the ammonia response test method is as follows: exposing the sample material to an ammonia gas environment, and observing the color change of the sample material; shrimp freshness monitoring experiment: fresh shrimps were purchased from the market, and the shrimps (mass: 30 g) were placed in petri dishes and sealed using petri dish lids, to the lower sides of which were attached cut sample materials (previously cut into sample materials having a diameter of 1 cm) prepared in comparative example 1, comparative example 2 and example 1, and then the above shrimp samples were stored in an environment of 25 ℃, and changes in freshness of the shrimps and changes in color of the sample materials were observed and recorded, and the values of volatile nitrogen (TVB-N) released from the shrimp samples during storage were measured according to the method of GB 5009.288-2016.
The above performance test data are shown in tables 1,2 and 3.
Table 1 sample performance test data
TABLE 2 pH-responsive discoloration behavior of the samples
TABLE 3 shrimp freshness monitoring test results (where t is the storage time of fresh shrimp)
SEM results of the starch/polyvinyl alcohol based high-performance composite material show that rhein and the rod-shaped zinc oxide nanoparticles can be uniformly dispersed in the starch/polyvinyl alcohol based material, and the starch/polyvinyl alcohol based composite material with excellent performance can be obtained. The results of the thermal response discoloration test experiments prove that the starch/polyvinyl alcohol composite material prepared in the comparative example 1 is colorless and transparent, and has no color change or colorless and transparent optical properties after being placed in an environment at 105 ℃; the starch/polyvinyl alcohol/rhein composite material prepared in the comparative example 2 is yellow, and the color of the composite material is changed into reddish brown after the composite material is placed in an environment at 105 ℃; the starch/polyvinyl alcohol-based high-performance composite material prepared in example 1 is light brown, and the color of the composite material changes into light red after the composite material is placed in an environment at 105 ℃; the starch/polyvinyl alcohol-based high-performance composite material prepared in the example 2 is brown, and the color of the composite material is changed into red after the composite material is placed in an environment at 105 ℃; the starch/polyvinyl alcohol-based high-performance composite material prepared in example 3 is brown, and the color of the composite material rapidly changes into reddish brown after the composite material is placed in an environment at 105 ℃; the starch/polyvinyl alcohol-based high-performance composite material prepared by the invention has excellent thermal response color change performance.
The pH response test experiment result proves that the starch/polyvinyl alcohol composite material prepared in comparative example 1 is colorless and transparent, and the color of the starch/polyvinyl alcohol composite material sample is not changed or the starch/polyvinyl alcohol composite material sample shows colorless and transparent optical properties after an acidic (or alkaline) buffer solution with the pH =5 (or pH = 9) is dripped on the surface of the starch/polyvinyl alcohol composite material sample; the starch/polyvinyl alcohol/rhein composite material prepared in the comparative example 2 is yellow, the color of the starch/polyvinyl alcohol/rhein composite material is not changed or is yellow after an acidic buffer solution with the pH =5 is dripped on the surface of a starch/polyvinyl alcohol/rhein composite material sample, and the color of the starch/polyvinyl alcohol/rhein composite material sample is reddish brown after an alkaline buffer solution with the pH =9 is dripped on the surface of the starch/polyvinyl alcohol/rhein composite material sample, which shows that the starch/polyvinyl alcohol/rhein composite material has a response discoloration property to an alkaline solution, but has no response discoloration property to the acidic solution; the starch/polyvinyl alcohol-based high-performance composite material prepared in the embodiment has excellent pH response discoloration performance, and has obvious response discoloration performance on acidic solutions and alkaline solutions (see table 2).
The ammonia response test experiment result proves that the starch/polyvinyl alcohol composite material prepared in the comparative example 1 is colorless and transparent, and the color of the starch/polyvinyl alcohol composite material is not changed after the starch/polyvinyl alcohol composite material is exposed in an ammonia environment, or the starch/polyvinyl alcohol composite material shows colorless and transparent optical properties; the starch/polyvinyl alcohol/rhein composite material prepared in the comparative example 2 is yellow, and the color of the starch/polyvinyl alcohol/rhein composite material is changed into reddish brown within 15min after the starch/polyvinyl alcohol/rhein composite material is exposed in an ammonia gas environment; the starch/polyvinyl alcohol-based high-performance composite material prepared in example 1 is light brown, and the color of the composite material rapidly changes into light red (within 3 min) after the composite material is exposed to an ammonia gas environment; the starch/polyvinyl alcohol-based high-performance composite material prepared in example 2 is brown, and the color of the composite material rapidly changes into red (within 5 min) after the composite material is exposed to an ammonia gas environment; the starch/polyvinyl alcohol-based high-performance composite material prepared in example 3 is brown, and the color of the composite material rapidly changes into reddish brown (within 5 min) after the composite material is exposed to an ammonia gas environment; the starch/polyvinyl alcohol-based high-performance composite material prepared by the invention has excellent ammonia response color change performance.
The shrimp freshness monitoring experiment result shows that when t =12h, the shrimps are not deteriorated, have no peculiar smell and are still edible, and at the moment, the color of the sample material of the example 1 is not obviously changed; when t =24h, the shrimp had deteriorated and were no longer suitable for consumption (TVB-N greater than 20mg/100g, indicating that the shrimp had deteriorated), at which time the sample material of example 1 had undergone a significant color change (see table 3); these results show that the starch/polyvinyl alcohol-based high-performance composite material prepared in example 1 can be used as an intelligent indicating material to timely and effectively indicate the deterioration of shrimps.
In a word, the sample performance test data (see tables 1,2 and 3) show that the starch/polyvinyl alcohol-based high-performance composite material prepared by the invention has excellent performances such as water vapor barrier, mechanics, pH response, ammonia response, thermal response color change, antibiosis, ultraviolet shielding, blue light shielding and the like, can be used as an intelligent indicating material to timely and effectively indicate the freshness change condition of meat food such as shrimps and the like in the storage process, is simple in preparation process, environment-friendly, low in cost, suitable for amplification production, and has potential application value in the fields of food packaging, intelligent materials, biomedicine, antibacterial materials, ammonia gas detection, environment monitoring, safety and the like.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (3)
1. A starch/polyvinyl alcohol based high-performance composite material with antibacterial and pH response functions is characterized by comprising the following components in parts by weight: 125 parts of starch, 125 parts of polyvinyl alcohol, 31.25 parts of glycerol, 1.25 parts of rhein and 2.5-12.5 parts of rod-shaped zinc oxide nanoparticles;
the preparation method of the rod-shaped zinc oxide nano particles comprises the following steps: dissolving 5.48 parts of zinc acetate in 86.3 parts of 1,2-propylene glycol, then adding 3.15 parts of deionized water, stirring and mixing uniformly, adding 6.15 parts of sodium acetate into the solution, stirring uniformly, heating to 150 ℃, refluxing for 1h, then carrying out centrifugal separation and drying to obtain the rod-shaped zinc oxide nanoparticles.
2. The preparation method of the starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions as claimed in claim 1, is characterized by comprising the following steps:
(1) Adding 125 parts of polyvinyl alcohol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform polyvinyl alcohol solution for later use;
(2) Adding 125 parts of starch and 31.25 parts of glycerol into 3000 parts of deionized water, and stirring at 85 ℃ for 30min to obtain a uniform starch solution for later use;
(3) Dispersing 2.5-12.5 parts of rod-shaped zinc oxide nano particles into 1000 parts of deionized water, and stirring at room temperature for 30min to obtain uniform dispersion liquid of the rod-shaped zinc oxide nano particles for later use;
(4) Dispersing 1.25 parts of rhein in 1000 parts of deionized water, and stirring at room temperature for 30min to obtain a homogeneous rhein dispersion for later use;
(5) Adding the starch solution obtained in the step (2), the zinc oxide dispersion liquid obtained in the step (3) and the rhein dispersion liquid obtained in the step (4) into the polyvinyl alcohol solution obtained in the step (1), and stirring at 85 ℃ for 30min to obtain a uniform film forming liquid for later use;
(6) And (3) pouring the film forming liquid obtained in the step (5) into a flat-bottomed glass dish, and drying in an oven at the temperature of 60 ℃ for 24 hours to obtain the starch/polyvinyl alcohol-based high-performance composite material with antibacterial and pH response functions.
3. The application of the starch/polyvinyl alcohol-based high-performance composite material with the antibacterial and pH response functions as claimed in any one of claims 1 to 2 is characterized by being used in the fields of food packaging, intelligent materials, biomedicine, antibacterial materials, ammonia gas detection, environmental monitoring, safety and the like.
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