CN109666094B - Preparation method of carbon dioxide indicating label material for food packaging - Google Patents
Preparation method of carbon dioxide indicating label material for food packaging Download PDFInfo
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- CN109666094B CN109666094B CN201710960504.1A CN201710960504A CN109666094B CN 109666094 B CN109666094 B CN 109666094B CN 201710960504 A CN201710960504 A CN 201710960504A CN 109666094 B CN109666094 B CN 109666094B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
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Abstract
The invention provides a preparation method of a carbon dioxide indicating label material for food packaging, which is characterized in that UCST or LCST polymer with carbon dioxide responsiveness is prepared in one step by carrying out RAFT (reversible addition-fragmentation chain transfer), ATRP (atom transfer radical polymerization) or NMRP (N-terminal-N. The carbon dioxide indicating label material prepared by the method has high sensitivity to carbon dioxide generated by putrefaction in food, can respond to carbon dioxide with the concentration of 0-3.0mmol/L, has the transparency changed along with the emission of the carbon dioxide, can realize the identification of the freshness of the food by human eyes, and is simple and convenient.
Description
Technical Field
The invention relates to the field of food packaging, in particular to a preparation method of a carbon dioxide indicating label material for food packaging and application of the label material in food packaging and food quality monitoring.
Background
Freshness of food is one of the most important factors affecting quality, safety, price, etc. of food, and it determines the safety factor of food consumption, the purchase intention of consumers, and profits of manufacturers and distributors. In recent years, with the increasing demand of consumers for food quality and freshness information, rapid development of food quality safety monitoring technology is also promoted, and particularly how to rapidly identify the freshness of food has become a research hotspot in the food field.
The traditional food quality determination method mainly adopts physicochemical analysis methods, such as a wet digestion method, a dry ashing method, a gas chromatography, a liquid chromatography, a gas-liquid combined chromatography and the like, but the detection process is relatively complicated, the time consumption is long, the sample amount is small, and the appearance and the structure of a corresponding sample need to be damaged during the determination. The gas detection technology, the computer vision technology, the near infrared spectrum technology, the nuclear magnetic resonance detection technology, the biosensing technology and the like which are gradually developed in recent years belong to nondestructive detection methods, and the quality of food can be detected on the premise of not damaging the structure of the food according to the mechanical, optical, electrical and biological characteristics and the like of the food. Although the food quality detection technology can quickly detect freshness characterization data such as food physical and chemical indexes, the data information cannot follow the change of food quality and present the current food freshness in real time. In 2005, Journal of Food Science, 2005, 70(1):1-10) first proposed the definition of an intelligent tag and its related concept, and by indicating the change of the tag color with the environment experienced in the Food package, the visual monitoring of the Food quality and freshness was achieved, and a scientific management means was provided for the manager. In recent years, many companies and research teams at home and abroad have been dedicated to the work, and the food intelligent label is commercially applied to part of products. The intelligent label is a visual material which can accurately represent food freshness and visually feed back food freshness information to consumers, can visually represent quality change of food in a package according to changes of environmental parameters such as temperature and time of the food, and is known as an effective means for further realizing refined management of a food supply chain, reducing loss of perishable food and improving food safety.
The gas indication intelligent label monitors the freshness of the food by directly collecting special gas generated by the food due to the metabolism of spoilage microorganisms. Respiration of food constantly changes the gas composition within the package and these changes in gas composition are often used as parameters indicative of changes in the quality of the food product inside the package. According to different detection characteristic gases, the gas sensitive intelligent labels are divided into five types of gas sensitive intelligent labels such as carbon dioxide, oxygen, volatile sulfur-containing compounds, volatile nitrogen-containing compounds, ethylene comprehensive gases and the like. In dairy and fermented products, carbon dioxide is a major metabolite in the growth process of microorganisms, and therefore, an increase in the content of carbon dioxide indicates a decrease in freshness of food. Jung et al (LWT-Food Science and Technology, 2013, 54(1): 101-. Based on the principle, the color difference change of carbon dioxide generated by different chitosan dissolution rates can be used for preparing the indicating material for representing the freshness of the pickle.
The UCST (highest critical temperature co-solution) and LCST (lowest critical temperature co-solution) polymers are polymers that change from an original swollen (dissolved) state to a contracted (insoluble) state when the temperature is lowered (raised) to a particular temperature. And a carbon dioxide sensitive unit is introduced into the UCST or LCST polymer, the UCST or LCST of the polymer can be correspondingly changed according to the amount of carbon dioxide participating in reaction, and the material is intuitively observed to be changed from transparent to opaque or vice versa through human eyes, so that the material is applied to food packaging, and the quality conditions of dairy products, fermented products and the like can be effectively monitored in real time. To date, there has been no report of using such materials for food packaging. As a new food packaging technology, smart tags have been commercially used for food sales in developed regions such as europe and america. The application of food intelligent labels in the current stage of China is still in the research stage, and the food circulation with intelligent label packages is basically avoided in the market. However, with the increasing concern of food manufacturers, retailers and consumers on food safety, quality and the like in China and the increasing perfection of modern packaging technology, the development, production and application of intelligent food labels must have huge market potential.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon dioxide indicating label material for food packaging, which is used for preparing a UCST or LCST polymer with carbon dioxide responsiveness in one step by using a RAFT (reversible addition-fragmentation chain transfer) polymerization (or active polymerization such as ATRP, NMRP and the like) method through UCST or LCST polymer monomers, carbon dioxide responsive monomers and an optionally added initiator.
It is another object of the present invention to provide the use of an indicator label material (preferably in the form of a solution, film, etc.) comprising carbon dioxide in the above UCST or LCST polymers for food packaging and for monitoring food quality.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a carbon dioxide indicating label material for food packaging comprises the following preparation steps: dissolving a UCST polymer monomer or LCST polymer monomer, a carbon dioxide responsive monomer and an optionally added initiator in a solvent, uniformly mixing, freezing, vacuumizing, unfreezing, and then carrying out polymerization reaction on a reactor under a closed condition to prepare the carbon dioxide responsive UCST or LCST polymer material, namely the carbon dioxide indicating label material.
According to the invention, the label material is prepared by forming the polymer material or the mixture of the polymer materials into a solution or a film.
According to the invention, the polymerization is selected from living polymerization such as RAFT, ATRP or NMRP.
Further, in the preparation method of the present invention, the UCST polymer monomer or LCST polymer monomer and the carbon dioxide responsive monomer are mixed in a molar ratio of (10-35):1, preferably 15-30: 1, the materials are fed.
Further, as a preferred method of the present invention, the UCST polymer monomers are acrylamide (AAm) and Acrylonitrile (AN), and the molar ratio of acrylamide to acrylonitrile is preferably (1-10: 1, preferably 2-8: 1.
As another preferable embodiment of the present invention, the LCST polymer monomer is one or more selected from vinylamides, acrylamides, methylvinyl ethers, oxazolines, acrylates, ethylene oxide-propylene oxide block copolymers, and the like, preferably N, N-Dimethylacrylamide (DMAA), N-isopropylacrylamide (NIPAM), dimethylaminoethyl methacrylate (DMAEMA), ethyl 2- (2-methoxyethoxy) Methacrylate (MEO)2MA), oligo (ethylene glycol) methyl ether methacrylate (OE)GMA) in the production of a medicament.
Further, the carbon dioxide responsive monomer is selected from the group consisting of: (1) a primary amine system; (2) amidino/guanidino systems; (3) a tertiary amine system; (4) a nitrogen-containing azole heterocyclic system; (5) an amide system; (6) an amine ester system; (7) a carboxylic acid system.
Further, the carbon dioxide responsive monomer according to the present invention may be specifically selected from, but not limited to, the following types: allylamine (AAm) compounds, N-methyl-N-vinylformamide (MVF), di-N-vinylformamide (DVFE), N-amidinododecylacrylamide, 3-Dimethylaminopropylacrylamide (DMAPM), dimethylaminoethyl methacrylate (DMAEMA), diethylaminoethyl methacrylate (DEAEMA), dipropylaminoethyl methacrylate (DPAEMA), N-dimethyl-styrene (DMSt), acrylic acid, methacrylic acid, ethacrylic acid, propylacrylic acid, and the like. More preferably: DMAEMA, DEAEMA, acrylic.
Further, the initiator in the method of the present invention is selected from a peroxy initiator or an azo initiator; the peroxy initiator is preferably benzoyl peroxide, ammonium persulfate, potassium persulfate, or the like, and the azo initiator is preferably azobisisobutyronitrile, 4' -azobis (4-cyanovaleric acid), azobisisobutylamidine hydrochloride, azobisisopropylimidazoline hydrochloride, or the like.
Further, the solvent of the present invention may be selected from: dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetone, diethyl ether, petroleum ether, methanol, ethanol, water, etc.
Further, the polymerization reaction (preferably RAFT polymerization reaction) in the present invention is preferably carried out at a temperature of 60 to 100 ℃ for 5 to 16 hours.
As a preferred embodiment, the preparation method of the present invention comprises washing with a solvent after the RAFT polymerization reaction is completed, dialyzing, and freeze-drying to obtain the carbon dioxide responsive UCST or LCST polymer material.
Further, the above method of the present invention optionally includes repeating the above steps, and by changing the ratio of the UCST polymer monomer or LCST polymer monomer, carbon dioxide responsive monomer, a series of carbon dioxide responsive UCST or LCST polymer materials are prepared and mixed according to a certain ratio.
According to the invention, the reaction is preferably carried out by a RAFT polymerisation process.
In addition, the invention also provides the carbon dioxide indicating label material prepared by the method.
Further, a food packaging material is provided, and the carbon dioxide indicating label material prepared by the method is prepared.
The invention also provides the use of the carbon dioxide indicating label material prepared by the method or the food packaging material for monitoring the quality change of food, wherein the transparency of the label material changes along with the emission of carbon dioxide in the food, and the change of the quality of the food inside the package is characterized by the change of the transparency of the material, such as the change from non (semi) transparent to (semi) transparent or the reverse. In particular, the transition from opaque to translucent or transparent; the semi-transparency is changed into the transparency; alternatively, a transition from transparent to translucent or opaque; transitioning from translucent to opaque.
The invention has the following advantages:
1. according to the invention, the carbon dioxide responsive monomer and the UCST or LCST polymer monomer are copolymerized by adopting a one-pot method to prepare the carbon dioxide indicating label material, so that the preparation method is simple and easy to operate; particularly in RAFT polymerization reaction, the one-pot reaction has outstanding advantages and the performance of the reaction product is excellent;
2. the carbon dioxide indicating label material prepared by the invention adopts a RAFT polymerization method with normal pressure and low reaction temperature, is easy to control and has no explosion danger;
3. the carbon dioxide indicating label material prepared by the invention has high sensitivity to carbon dioxide generated by putrefaction in food, and can respond to carbon dioxide with the concentration of 0-3.0 mmol/L;
4. the freshness of the food can be recognized through the change of the transparency of the label material by human eyes, so that the method is simple and convenient;
5. the carbon dioxide indicating label material prepared by the invention has reversibility and can be repeatedly used;
6. the invention can be applied to the fields of food packaging, environmental monitoring and the like.
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the following detailed description of the technical solutions of the present invention will be made with reference to the following specific examples, which should not be construed as limiting the implementable scope of the present invention.
Example 1
1.83g (25.8mmol) of acrylamide (AAm), 0.25g (4.7mmol) of Acrylonitrile (AN) and 0.18g (1.3mmol) of diethylaminoethyl methacrylate (DEAEMA) were dissolved in 8ml of dimethyl sulfoxide, and the mixture was uniformly mixed in a reactor, subjected to freeze-vacuum-thawing, the reactor was sealed, placed in AN oil bath at 60 ℃ to carry out RAFT polymerization for 10 hours, washed with a solvent after the completion of the treatment, and finally dialyzed and freeze-dried.
In this example, the monomer conversion was 85%, and the label indicator material could undergo a sharp transition from opaque to clear at 25 ℃ when the carbon dioxide concentration reached 1.7 mmol/L.
Example 2
Dissolving 1.83g acrylamide (AAm), 0.25g Acrylonitrile (AN) and 0.30g diethylaminoethyl methacrylate (DEAEMA) in 8ml dimethyl sulfoxide, uniformly mixing in a reactor, sealing the reactor through a freezing-vacuum-thawing process, placing in AN oil bath at 80 ℃, carrying out RAFT polymerization for 10 hours, washing with a solvent after the treatment is finished, finally dialyzing, and freeze-drying.
In this example, the monomer conversion was 82%, and the label indicator material could undergo a sharp transition from opaque to clear at 25 ℃ when the carbon dioxide concentration reached 1.2 mmol/L.
Example 3
Dissolving 1.83g acrylamide (AAm), 0.25g Acrylonitrile (AN) and 0.42g diethylaminoethyl methacrylate (DEAEMA) in 8ml dimethyl sulfoxide, uniformly mixing in a reactor, sealing the reactor through a freezing-vacuum-thawing process, placing in AN oil bath at 60 ℃, carrying out RAFT polymerization for 10 hours, washing with a solvent after the treatment is finished, finally dialyzing, and freeze-drying.
In this example, the monomer conversion was 75%, and the label indicator material could undergo a sharp transition from opaque to clear at 25 ℃ when the carbon dioxide concentration reached 0.5 mmol/L.
Example 4
(a) Dissolving 1.83g acrylamide (AAm), 0.25g Acrylonitrile (AN) and 0.18g diethylaminoethyl methacrylate (DEAEMA) in 8ml dimethyl sulfoxide, uniformly mixing in a reactor, sealing the reactor through a freezing-vacuum-thawing process, placing in AN oil bath at 60 ℃, carrying out RAFT polymerization for 10 hours, washing with a solvent after the treatment is finished, finally dialyzing, and freeze-drying.
In step (a), the monomer conversion was 70%.
(b) 1.61g acrylamide (AAm), 0.40g Acrylonitrile (AN), 0.17g diethylaminoethyl methacrylate (DEAEMA) were dissolved in 7ml dimethyl sulfoxide, mixed uniformly in a reactor, subjected to freeze-vacuum-thawing, the reactor was sealed, placed in AN oil bath at 60 ℃ to carry out RAFT polymerization for 6 hours, washed with a solvent after the completion of the treatment, and finally dialyzed and freeze-dried.
In step (b), the monomer conversion was 86%.
Mixing the materials obtained in the step (a) and the step (b) in a certain ratio. At 25 ℃, when the concentration of the carbon dioxide is gradually changed from 0 to 3.0mmol/L, the label indicating material is correspondingly subjected to a gradual change process from opaque to transparent.
Example 5
(a) 20g of dimethylaminoethyl methacrylate (DMAEMA), 89.4mg of s, s ' -bis (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate (BTC) and 10.3mg of Azobisisobutyronitrile (AIBN) were dissolved in 32ml of dioxane, mixed uniformly in a reactor, subjected to freezing-vacuum-thawing, the reactor was sealed, placed in an oil bath at 70 ℃ to carry out RAFT polymerization for 12 hours, washed with a solvent after the completion of the treatment, and finally dialyzed and freeze-dried.
In step (a), the monomer conversion was 80%.
(b) 0.8g of the above product, 0.8g N-isopropylacrylamide (NIPAM), 0.95mg of Azobisisobutyronitrile (AIBN) were dissolved in 4.8ml of dioxane, mixed uniformly in a reactor, subjected to freeze-vacuum-thawing, sealed, placed in an oil bath at 70 ℃ for RAFT polymerization for 3 hours, washed with a solvent after the completion of the treatment, dialyzed, and freeze-dried.
In step (b), the monomer conversion was 75%.
In this example, the label indicator material may undergo a sharp transition from opaque to transparent when the carbon dioxide concentration reaches 1.5mmol/L at 25 ℃.
Example 6
(a) 20g of dimethylaminoethyl methacrylate (DMAEMA), 89.4mg of s, s ' -bis (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate (BTC) and 10.3mg of Azobisisobutyronitrile (AIBN) were dissolved in 32ml of dioxane, mixed uniformly in a reactor, subjected to freezing-vacuum-thawing, the reactor was sealed, placed in an oil bath at 70 ℃ to carry out RAFT polymerization for 12 hours, washed with a solvent after the completion of the treatment, and finally dialyzed and freeze-dried.
In step (a), the monomer conversion was 80%.
(b) 1.6g of the above product, 0.8g N-isopropylacrylamide (NIPAM), 0.95mg of Azobisisobutyronitrile (AIBN) were dissolved in 4.8ml of dioxane, mixed uniformly in a reactor, subjected to freeze-vacuum-thawing, sealed, placed in an oil bath at 70 ℃ for RAFT polymerization for 3 hours, washed with a solvent after the completion of the treatment, dialyzed, and freeze-dried.
In step (b), the monomer conversion was 72%.
In this example, the label indicator material may undergo a sharp transition from opaque to transparent when the carbon dioxide concentration reaches 0.8mmol/L at 25 ℃.
Claims (17)
1. A preparation method of a carbon dioxide indicating label material is characterized by comprising the following preparation steps: dissolving a UCST polymer monomer, a carbon dioxide responsive monomer and an optionally added initiator in a solvent, uniformly mixing, freezing, vacuumizing, unfreezing, and then carrying out polymerization reaction on a reactor under a closed condition to prepare a carbon dioxide responsive UCST polymer material, namely a carbon dioxide indicating label material; wherein:
the UCST polymer monomer is acrylamide and acrylonitrile, and the molar ratio of the acrylamide to the acrylonitrile is 1-10: 1;
the carbon dioxide responsive monomer is selected from allylamine compounds, N-methyl-N-vinylformamide, di-N-vinylformamide, N-amidinododecylacrylamide, 3-dimethylaminopropylacrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropaminoethyl methacrylate, N-dimethyl-p-styrene, acrylic acid, methacrylic acid, ethacrylic acid, and propylacrylic acid;
the UCST polymer monomer and the carbon dioxide responsive monomer are fed according to the molar ratio of 10-35: 1.
2. The method of claim 1, wherein said label material is prepared by forming said polymeric material or a mixture of said polymeric materials into a solution or film.
3. The method of claim 1, wherein the polymerization is selected from RAFT, ATRP or NMRP living polymerization.
4. The method of claim 3, wherein the reaction is a RAFT polymerization.
5. The method of claim 1, wherein the UCST polymer monomers and the carbon dioxide-responsive monomers are present in a molar ratio of 15-30: 1, the materials are fed.
6. The method according to claim 1, wherein the molar ratio of acrylamide to acrylonitrile is 2-8: 1.
7. The production method according to claim 1, characterized in that the carbon dioxide responsive monomer is selected from the group consisting of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dipropylaminoethyl methacrylate.
8. The process according to any one of claims 1 to 7, wherein the initiator is selected from a peroxy initiator or azo initiator;
the solvent is selected from dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetone, diethyl ether, petroleum ether, methanol, ethanol and water.
9. The process according to claim 8, wherein said peroxy initiator is selected from the group consisting of benzoyl peroxide, ammonium persulfate, and potassium persulfate.
10. The process according to claim 8, wherein the azo initiator is selected from the group consisting of azobisisobutyronitrile, 4' -azobis (4-cyanovaleric acid), azobisisobutylamidine hydrochloride, azobisdiisopropylimidazoline, and azobisisopropylimidazoline hydrochloride.
11. A method according to claim 3 or 4, characterised in that the RAFT polymerisation is carried out at a temperature of 60 to 100 ℃ for 5 to 16 hours.
12. The method of claim 11, wherein the RAFT polymerization is followed by solvent washing, dialysis, and freeze-drying to obtain a carbon dioxide responsive UCST polymer material.
13. The method of any one of claims 1-7, further optionally comprising repeating the method to produce a series of carbon dioxide responsive UCST polymer materials by varying the ratio of UCST polymer monomer to carbon dioxide responsive monomer and mixing.
14. A carbon dioxide indicating label material prepared according to the method of any one of claims 1 to 13.
15. A food packaging material, characterized in that it is produced using a carbon dioxide indicator label material produced according to the method of any one of claims 1-13.
16. Use of a carbon dioxide indicating label material prepared according to the method of any one of claims 1 to 13 or a food packaging material according to claim 15 for monitoring changes in the quality of a food product, wherein the transparency of the label material changes with the amount of carbon dioxide emitted from the food product and changes in the quality of the food product inside the package are characterized by changes in the transparency of the material.
17. Use according to claim 16, characterized in that said change in transparency is selected from: the non-transparent is changed into semi-transparent or transparent; the semi-transparency is changed into the transparency; alternatively, a transition from transparent to translucent or opaque; transitioning from translucent to opaque.
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| CN110452484B (en) * | 2019-09-04 | 2021-10-29 | 仲恺农业工程学院 | Modified starch/PVA (polyvinyl alcohol) fruit and vegetable preservative film with sensitivity to carbon dioxide and preparation method thereof |
| CN110927151A (en) * | 2019-12-04 | 2020-03-27 | 六安屹珹新材料科技有限公司 | Quality guarantee state indicator and preparation method thereof |
| CN112635875B (en) * | 2020-03-27 | 2023-05-26 | 苏州清陶新能源科技有限公司 | Soft shell for battery, preparation method and application thereof |
| CN115124656B (en) * | 2022-08-11 | 2024-01-30 | 北方民族大学 | Cellulose-based grafted carbon dioxide responsive polymer material and preparation method thereof |
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