Biodegradable antioxidant functional ethyl cellulose-based intelligent active packaging film and application thereof
By adding multifunctional active antioxidants to ethyl cellulose materials, the problem of lack of antioxidant and intelligent activity of ethyl cellulose materials was solved, and a biodegradable packaging film with excellent antioxidant, ammonia response and mechanical properties was prepared, which expanded its application in multiple fields.
Patent Information
- Application Number
- CN202411956714.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-29
- Publication Date
- 2025-03-28
AI Technical Summary
The lack of antioxidant activity, intelligent activity and mechanical properties of existing ethyl cellulose materials limits their widespread use in food packaging and other applications.
By using multifunctional active antioxidant as a reinforcing filler, combining complex crystals obtained by reacting ethyl cellulose, glycerol and ferrous sulfate with syringic acid, a biodegradable packaging film with antioxidant, ammonia response discoloration, ultraviolet barrier and other properties were prepared.
It has achieved the efficient antioxidant activity, ammonia response function, mechanical strength and ultraviolet barrier properties of ethyl cellulose-based intelligent active packaging film, and expanded its application in the fields of smart materials, food packaging, etc.
Smart Images
Figure CN119708648A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polymer composite materials, and in particular relates to a biodegradable antioxidant functional ethyl cellulose-based intelligent active packaging film and its application. Background Art
[0002] Ethyl cellulose is an ethylated cellulose ether polymer biomaterial. It is hydrophobic and biodegradable. It is an environmentally friendly organic polymer with good film-forming properties and biocompatibility. It has broad application prospects in food packaging, biomedicine, smart gels and other fields. The use of ethyl cellulose polymers continues to grow. However, ethyl cellulose itself is a brittle material and lacks antioxidant activity and intelligent activity (such as ammonia response color change), which limits its practical application. In recent years, antioxidant active materials have attracted widespread attention as a kind of "active packaging". This is an innovative food preservation technology mainly based on the mass transfer interaction between the "food / packaging" system, in which the positive interaction between food packaging materials and food will promote the release of positive antioxidants and extend the shelf life of food by preventing oxidation reactions. The present invention uses ethyl cellulose as a matrix and a multifunctional active antioxidant as a reinforcing filler to improve the antioxidant activity, ammonia response color change, mechanical strength, toughness, ultraviolet blocking and other properties of the ethyl cellulose composite material, develops a biodegradable ethyl cellulose-based intelligent active packaging film with both high-efficiency antioxidant activity and ammonia response function, and broadens its application in the fields of intelligent materials, ammonia response materials, ammonia detection, food packaging, biomedicine, environmental monitoring and safety. Summary of the invention
[0003] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a biodegradable antioxidant functional ethyl cellulose-based intelligent active packaging film. The film material has high-efficiency ammonia response color change, excellent antioxidant ability, good ultraviolet blocking, mechanical strength, and toughness, and the composite material preparation process is simple, environmentally friendly, low-cost, and suitable for scale-up production.
[0004] Technical solution of the present invention:
[0005] The present invention provides a biodegradable ethyl cellulose-based intelligent active packaging film, characterized in that it is composed of the following components in parts by weight: 150 parts of ethyl cellulose, 7.5 parts of glycerol, and 1.5-7.5 parts of a multifunctional active antioxidant;
[0006] The multifunctional active antioxidant is a complex crystal obtained by reacting ferrous sulfate and syringic acid as raw materials, and the preparation method comprises the following steps:
[0007] (1) Disperse 19.81 parts of syringic acid in 5000 parts of ethanol as a solvent, stir at room temperature for 30 min to obtain a uniform syringic acid dispersion for later use;
[0008] (2) Take 13.9 parts of ferrous sulfate heptahydrate and dissolve it in 1000 parts of deionized water to obtain a uniform ferrous sulfate solution for later use;
[0009] (3) Add the ferrous sulfate solution obtained in step (2) to the syringic acid dispersion obtained in step (1), stir and react at room temperature for 30 min, then centrifuge, wash and dry in sequence to obtain a multifunctional active antioxidant.
[0010] The present invention also provides a method for preparing the above-mentioned biodegradable ethyl cellulose-based intelligent active packaging film, which is characterized by comprising the following steps:
[0011] (1) Add 150 parts of ethyl cellulose and 7.5 parts of glycerol to 3000 parts of ethanol, stir at 55°C for 30 minutes to obtain a uniform blend solution, cool to room temperature and set aside;
[0012] (2) Disperse 1.5-7.5 parts of multifunctional active antioxidant in 500 parts of ethanol, stir at room temperature for 10 minutes to obtain a uniform dispersion, and set aside;
[0013] (3) adding the dispersion obtained in step (2) to the blended solution obtained in step (1), stirring at room temperature for 30 min to obtain a uniform film-forming solution for later use;
[0014] (4) The film-forming liquid obtained in step (3) is poured into a flat-bottomed glass dish and dried in an oven at 55° C. for 24 h to obtain a biodegradable ethyl cellulose-based smart active packaging film.
[0015] The application of the biodegradable ethyl cellulose-based intelligent active packaging film is characterized by being used in the fields of food packaging, intelligent materials, biomedicine, ammonia responsive materials, ammonia detection, environmental monitoring and safety, etc.
[0016] Compared with the prior art, the present invention has the following beneficial effects:
[0017] The biodegradable ethyl cellulose-based intelligent active packaging film prepared by the present invention has excellent mechanical strength, toughness, ultraviolet blocking, high-energy blue light blocking, ammonia response color change, antioxidant activity, biodegradability and other properties, while maintaining a high visible light transparency.
[0018] The biodegradable ethyl cellulose-based intelligent active packaging film prepared by the present invention can be used as an intelligent indicator material to timely and effectively indicate the freshness changes of meat foods (such as shrimp, pork, fish, etc.) during storage. The film material has a simple preparation process, is environmentally friendly, low cost, and is suitable for large-scale production. It has wide application value in the fields of intelligent materials, ammonia response materials, ammonia detection, food packaging, biomedicine, environmental monitoring and safety. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 is a scanning electron microscope image of the multifunctional active antioxidant involved in the present invention;
[0020] Figure 2 The figures are of the ethyl cellulose packaging film sample prepared in the comparative example of the present invention and the ethyl cellulose-based intelligent active packaging film sample prepared in the embodiment. DETAILED DESCRIPTION
[0021] In order to better explain the present invention, the present invention is further explained in detail below in conjunction with specific examples, but the embodiments of the present invention are not limited thereto.
[0022] In the following specific embodiments and comparative example formulas and preparation methods, the ethyl cellulose used is a product provided by McLean Biochemical Technology Co., Ltd. (item number: E915394-500g); the syringic acid used is an analytically pure reagent provided by Shanghai Yien Chemical Technology Co., Ltd.; and the ferrous sulfate heptahydrate and propylene glycol are analytically pure reagents provided by Xilong Scientific Co., Ltd.
[0023] In the following specific examples and comparative examples, the formulations and preparation methods, the multifunctional active antioxidant is a complex crystal obtained by reacting ferrous sulfate and syringic acid as raw materials (the scanning electron microscope image of which is shown in Figure 1 ), the preparation method comprises the following steps:
[0024] (1) Disperse 19.81 parts of syringic acid in 5000 parts of ethanol as a solvent, stir at room temperature for 30 min to obtain a uniform syringic acid dispersion for later use;
[0025] (2) Take 13.9 parts of ferrous sulfate heptahydrate and dissolve it in 1000 parts of deionized water to obtain a uniform ferrous sulfate solution for later use;
[0026] (3) Add the ferrous sulfate solution obtained in step (2) to the syringic acid dispersion obtained in step (1), stir and react at room temperature for 30 min, then centrifuge, wash and dry in sequence to obtain a multifunctional active antioxidant.
[0027] Example 1
[0028] The biodegradable ethyl cellulose-based intelligent active packaging film is characterized in that it is composed of the following components in parts by weight: 150 parts of ethyl cellulose, 7.5 parts of glycerol, and 1.5 parts of a multifunctional active antioxidant.
[0029] The preparation method comprises the following steps:
[0030] (1) Add 150 parts of ethyl cellulose and 7.5 parts of glycerol to 3000 parts of ethanol, stir at 55°C for 30 minutes to obtain a uniform blend solution, cool to room temperature and set aside;
[0031] (2) Disperse 1.5 parts of the multifunctional active antioxidant in 500 parts of ethanol, stir at room temperature for 10 minutes to obtain a uniform dispersion, and set aside;
[0032] (3) adding the dispersion obtained in step (2) to the blended solution obtained in step (1), stirring at room temperature for 30 min to obtain a uniform film-forming solution for later use;
[0033] (4) The film-forming liquid obtained in step (3) is poured into a flat-bottomed glass dish and dried in an oven at 55° C. for 24 h to obtain a biodegradable ethyl cellulose-based smart active packaging film.
[0034] Example 2
[0035] The biodegradable ethyl cellulose-based intelligent active packaging film is characterized in that it is composed of the following components in parts by weight: 150 parts of ethyl cellulose, 7.5 parts of glycerol, and 4.5 parts of a multifunctional active antioxidant.
[0036] The preparation method comprises the following steps:
[0037] (1) Add 150 parts of ethyl cellulose and 7.5 parts of glycerol to 3000 parts of ethanol, stir at 55°C for 30 minutes to obtain a uniform blend solution, cool to room temperature and set aside;
[0038] (2) Disperse 4.5 parts of the multifunctional active antioxidant in 500 parts of ethanol, stir at room temperature for 10 minutes to obtain a uniform dispersion, and set aside;
[0039] (3) adding the dispersion obtained in step (2) to the blended solution obtained in step (1), stirring at room temperature for 30 min to obtain a uniform film-forming solution for later use;
[0040] (4) The film-forming liquid obtained in step (3) is poured into a flat-bottomed glass dish and dried in an oven at 55° C. for 24 h to obtain a biodegradable ethyl cellulose-based smart active packaging film.
[0041] Example 3
[0042] The biodegradable ethyl cellulose-based intelligent active packaging film is characterized in that it is composed of the following components in parts by weight: 150 parts of ethyl cellulose, 7.5 parts of glycerol, and 7.5 parts of a multifunctional active antioxidant.
[0043] The preparation method comprises the following steps:
[0044] (1) Add 150 parts of ethyl cellulose and 7.5 parts of glycerol to 3000 parts of ethanol, stir at 55°C for 30 minutes to obtain a uniform blend solution, cool to room temperature and set aside;
[0045] (2) Disperse 7.5 parts of the multifunctional active antioxidant in 500 parts of ethanol, stir at room temperature for 10 minutes to obtain a uniform dispersion, and set aside;
[0046] (3) adding the dispersion obtained in step (2) to the blended solution obtained in step (1), stirring at room temperature for 30 min to obtain a uniform film-forming solution for later use;
[0047] (4) The film-forming liquid obtained in step (3) is poured into a flat-bottomed glass dish and dried in an oven at 55° C. for 24 h to obtain a biodegradable ethyl cellulose-based smart active packaging film.
[0048] Comparative Example
[0049] As a comparison standard of the above embodiments, the present invention provides an ethyl cellulose packaging film material prepared without a multifunctional active antioxidant, comprising the following steps:
[0050] (1) Add 150 parts of ethyl cellulose and 7.5 parts of glycerol to 3000 parts of ethanol, stir at 50°C for 30 minutes to obtain a uniform blend solution, cool to room temperature, and set aside;
[0051] (2) Add 500 parts of ethanol to the blended solution obtained in step (1), and stir at room temperature for 30 minutes to obtain a uniform film-forming solution for later use;
[0052] (3) The film-forming solution obtained in step (2) is poured into a flat-bottomed glass dish and dried in an oven at 55°C for 24 h to obtain an ethyl cellulose packaging film.
[0053] Structure and performance test:
[0054] The structure and performance tests were carried out on the ethyl cellulose packaging film prepared in the above comparative example and the ethyl cellulose-based intelligent active packaging film prepared in the example, wherein the UV-visible performance was tested using a UV-visible spectrometer, and the average UV transmittance was calculated with reference to GB / T 18830-2009; the tensile performance was tested in accordance with GB / T 1040-2006; the ammonia response test method was as follows: the sample material was placed in an ammonia environment, and the color change of the sample material was observed.
[0055] The DPPH free radical scavenging experimental method is as follows:
[0056] In the experimental group, 0.2 g of the membrane sample was cut into pieces and soaked in 5 mL of ethanol. After soaking for 24 h, 2 mL of the supernatant of the soaking solution was extracted and set aside. Then, 1 mL of 50 mg / L DPPH solution was added to the 2 mL of the supernatant, and the mixture was shaken and placed in the dark at room temperature for 1 h. Then, the absorbance of the mixture at 517 nm (denoted as A) was measured using an ultraviolet spectrophotometer. sample ); For the control group, 1 mL of 50 mg / L DPPH solution was added to 2 mL of ethanol, and the mixture was shaken and placed in the dark at room temperature for 1 h; then, the absorbance of the mixture at 517 nm (denoted as A) was measured by a UV spectrophotometer. control ); DPPH free radical scavenging rate (%) = 100* (A control - A sample ) / A control .
[0057] The above performance test data is shown in Table 1.
[0058] Table 1 Sample performance test data
[0059]
[0060] The results of the ammonia response test show that the ethyl cellulose packaging film prepared in the comparative example is colorless and transparent. After being exposed to an ammonia environment, its color does not change, and it still presents white and transparent optical properties, and its ∆E value is 0.66 (that is, the color difference is negligible and cannot be distinguished by the human eye); the ethyl cellulose-based smart active packaging film prepared in Example 1 is light yellow, and after being exposed to an ammonia environment, its color changes significantly, and its ∆E can reach 6.46 (Note: ∆E>3 indicates a significant color change visible to the human eye); the ethyl cellulose-based smart active packaging film prepared in Example 2 is light yellow, and after being exposed to an ammonia environment, its color changes to light reddish brown, and its ∆E can reach 31.51 (Note: ∆E>3 indicates a significant color change visible to the human eye); the ethyl cellulose-based smart active packaging film prepared in Example 3 is yellow, and after being exposed to an ammonia environment, its color changes to reddish brown, and its ∆E can reach 47.59 (Note: ∆E>3 indicates a significant color change visible to the human eye).
[0061] The results of the DPPH radical scavenging experiment show that the ethyl cellulose-based intelligent active packaging film prepared in Example 3 has a DPPH radical scavenging rate of 78.24%, indicating that it has excellent antioxidant activity, while the ethyl cellulose packaging film prepared in the comparative example has no obvious antioxidant activity.
[0062] In summary, it can be seen from the sample performance test data (see Table 1) that the ethyl cellulose-based intelligent active packaging film prepared by the present invention has excellent mechanical strength, toughness, ultraviolet blocking, high-energy blue light blocking, ammonia response color change, DPPH free radical scavenging activity (i.e., antioxidant activity), biodegradability and other properties, while maintaining a high visible light transparency. The composite material preparation process is simple, environmentally friendly, low-cost, and suitable for scale-up production. It has wide application value in the fields of intelligent materials, ammonia response materials, ammonia detection, food packaging, biomedicine, environmental monitoring and safety.
[0063] The content of the present invention is not limited to the embodiments listed, and any equivalent changes made to the technical solution of the present invention by ordinary technicians in this field after reading the description of the present invention are covered by the claims of the present invention.
Claims
1. A biodegradable ethylcellulose-based intelligent active packaging film, characterized in that: The invention is composed of the following components in parts by weight: 150 parts of ethyl cellulose, 7.5 parts of glycerol, and 1.5-7.5 parts of a multifunctional active antioxidant; The multifunctional active antioxidant, its preparation method comprises the following steps: (1) Disperse 19.81 parts of syringic acid in 5000 parts of ethanol as a solvent, stir at room temperature for 30 min to obtain a uniform syringic acid dispersion for later use; (2) Take 13.9 parts of ferrous sulfate heptahydrate and dissolve it in 1000 parts of deionized water to obtain a uniform ferrous sulfate solution for later use; (3) Add the ferrous sulfate solution obtained in step (2) to the syringic acid dispersion obtained in step (1), stir and react at room temperature for 30 min, then centrifuge, wash and dry in sequence to obtain a multifunctional active antioxidant.
2. The method for preparing the biodegradable ethyl cellulose-based intelligent active packaging film according to claim 1, characterized in that The steps include: (1) Add 150 parts of ethyl cellulose and 7.5 parts of glycerol to 3000 parts of ethanol, stir at 50°C for 30 minutes to obtain a uniform blend solution, cool to room temperature, and set aside; (2) Disperse 1.5-7.5 parts of multifunctional active antioxidant in 500 parts of ethanol, stir at room temperature for 10 minutes to obtain a uniform dispersion, and set aside; (3) adding the dispersion obtained in step (2) to the blended solution obtained in step (1), stirring at room temperature for 30 min to obtain a uniform film-forming solution for later use; (4) The film-forming liquid obtained in step (3) is poured into a flat-bottomed glass dish and dried in an oven at 55° C. for 24 h to obtain a biodegradable ethyl cellulose-based smart active packaging film.
3. The use of the biodegradable ethyl cellulose-based intelligent active packaging film according to claim 1, characterized in that: Used in smart materials, ammonia responsive materials, ammonia detection, food packaging, environmental monitoring and safety fields.