CAB / PEG composite membrane with antibacterial, antioxidant and ammonia-sensitive functions and processing technology of CAB / PEG composite membrane

Abstract

The invention belongs to the technical field of polymer composite materials, and particularly relates to a CAB / PEG (cellulose acetate butyrate / polyethylene glycol) composite membrane with antibacterial, antioxidant and ammonia-sensitive functions and a processing technology thereof, and the CAB / PEG composite membrane is prepared from the following raw materials: cellulose acetate butyrate, polyethylene glycol and multifunctional urchin-like nanoparticles. The CAB / PEG composite membrane material prepared by the invention not only has excellent antibacterial activity, antioxidant activity and ammonia-sensitive discoloration function, but also shows excellent mechanical strength, ductility, ultraviolet barrier property and the like, and can be used as an intelligent indicating material to timely and effectively indicate the freshness change condition of meat foods such as shrimps in the storage process; the method has wide application value in the fields of antibiosis, antioxidation, visual detection of ammonia gas, ultraviolet protection, food packaging, intelligent materials and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer composite materials, and in particular to a CAB / PEG composite membrane having antibacterial, antioxidant and ammonia-sensitive functions and a processing technology thereof. Background Art

[0002] Cellulose acetate butyrate (CAB) is a loose white powder that is tasteless, odorless and non-toxic. Because its molecules contain acetyl and butyryl groups, it has the advantages of good chemical stability, excellent biocompatibility and biodegradability. However, cellulose acetate butyrate film materials show poor mechanical strength and ductility, which is not conducive to their application in packaging and other fields. Polyethylene glycol (PEG) is a non-ionic water-soluble polymer that can be compatible with many substances with high polarity. Polyethylene glycol has good softness, stretchability, lubricity and moisturizing properties, and has been widely used in packaging, cosmetics and other fields. Blending CAB with PEG to prepare CAB / PEG composite film can combine the advantages of both, which is conducive to the preparation of composite film materials with excellent performance. However, CAB / PEG composite film materials lack antibacterial, antioxidant and ammonia-sensitive color change functions, which limits their application in antibacterial, antioxidant, visual detection of ammonia, UV protection, food packaging, smart materials and other fields. Therefore, in order to expand the application field of CAB / PEG composite membrane materials, it is necessary to improve the mechanical strength, ductility, UV shielding, antibacterial, antioxidant and ammonia-sensitive discoloration properties of CAB / PEG composite membrane materials.

[0003] Using multifunctional nanoparticles to modify membrane materials is a common strategy. In particular, multifunctional sea urchin-like nanoparticles have significant advantages in the fields of enhanced modification of polymer materials, gas adsorption, gas sensing detection, catalysis, surface plasmon resonance and biomedicine due to their unique structure, extremely high specific surface area and diverse functionality. Therefore, the present invention constructs a new type of multifunctional sea urchin-like nanoparticles, which are used to carry out composite modification of CAB / PEG membrane materials, and develop a high-performance CAB / PEG composite membrane with antibacterial, antioxidant and ammonia-sensitive functions, broadening its application in the fields of antibacterial, antioxidant, visual detection of ammonia, ultraviolet protection, food packaging, smart materials, etc. Summary of the invention

[0004] The purpose of the present invention is to address the deficiencies of the prior art and construct a novel, multifunctional sea urchin-shaped nanoparticle, which is used to carry out composite modification of CAB / PEG membrane materials, effectively improving the antibacterial, antioxidant and ammonia-sensitive color-changing functions as well as mechanical strength, ductility and other properties of the CAB / PEG-based membrane materials, and broadening their applications in the fields of antibacterial, antioxidant, visual detection of ammonia, ultraviolet protection, food packaging, smart materials, etc.

[0005] The technical solution of the present invention:

[0006] The CAB / PEG composite membrane with antibacterial, antioxidant and ammonia-sensitive functions is composed of the following components in parts by weight: 100 parts of cellulose acetate butyrate, 10 parts of polyethylene glycol, and 1-5 parts of multifunctional sea urchin-shaped nanoparticles.

[0007] The method for preparing the multifunctional sea urchin-shaped nanoparticles comprises the following steps:

[0008] (1) dissolving 19.4 parts by weight of ferulic acid in 5000 parts by weight of ethanol for later use;

[0009] (2) dissolving 27.8 parts by mass of ferrous sulfate heptahydrate in 1000 parts by mass of deionized water for later use;

[0010] (3) The ferrous sulfate heptahydrate solution of step (2) is added dropwise to the solution of step (1), and the mixture is stirred at room temperature for 10 min, and then centrifuged, washed, and dried to obtain multifunctional sea urchin-like nanoparticles.

[0011] The method for preparing the CAB / PEG composite membrane having antibacterial, antioxidant and ammonia-sensitive functions comprises the following steps:

[0012] (1) Add 100 parts of cellulose acetate butyrate to 2500 parts of ethanol, stir at 55°C for 30 minutes, then add 10 parts of polyethylene glycol, continue stirring at 55°C for 30 minutes to obtain a uniform CAB / PEG solution for later use;

[0013] (2) Dispersing 1-5 parts of the multifunctional sea urchin-like nanoparticles in 500 parts of ethanol, stirring at room temperature for 30 minutes to obtain a uniform dispersion for later use;

[0014] (3) adding the dispersion obtained in step (2) to the CAB / PEG solution obtained in step (1), and stirring at 55° C. for 1 h to obtain a uniform film-forming solution for later use;

[0015] (4) The film-forming liquid in step (3) is poured onto a glass mold and dried in an oven at 55° C. for 24 h to obtain a CAB / PEG composite membrane having antibacterial, antioxidant and ammonia-sensitive functions.

[0016] The present invention has the beneficial effects:

[0017] Compared with the prior art, the present invention constructs a novel, multifunctional sea urchin-shaped nanoparticle, which is used to carry out composite modification of CAB / PEG membrane materials, which can not only effectively improve the antibacterial, antioxidant and ammonia-sensitive color-changing functions of the CAB / PEG-based membrane materials, but also effectively improve the mechanical strength, ductility, UV blocking and other properties of the CAB / PEG-based membrane materials, thereby broadening its application in the fields of antibacterial, antioxidant, visual detection of ammonia, UV protection, food packaging, smart materials and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a scanning electron microscope image of the multifunctional sea urchin-shaped nanoparticles involved in the present invention;

[0019] Figure 2 This is a cross-sectional scanning electron micrograph of the CAB / PEG composite membrane sample prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0020] The present invention is further described in detail below with reference to specific embodiments.

[0021] In the specific embodiments and comparative example formulations, the ferulic acid is an analytically pure reagent provided by Shanghai Yien Chemical Technology Co., Ltd., ferrous sulfate heptahydrate is an analytically pure reagent provided by Xilong Chemical Co., Ltd., ethanol is an analytically pure reagent provided by Tianjin Fuyu Fine Chemical Co., Ltd., cellulose acetate butyrate (CAB) is a product provided by Roen Reagent Co., Ltd. (item number: R096800-500g), and polyethylene glycol (PEG) is a product provided by Shanghai Aladdin Biochemical Technology Co., Ltd. (item number: P103730-500g).

[0022] In the specific embodiment and comparative example formulation, the preparation method of the multifunctional sea urchin-shaped nanoparticles comprises the following steps: (1) dissolving 19.4 parts by mass of ferulic acid in 5000 parts by mass of ethanol for later use; (2) dissolving 27.8 parts by mass of ferrous sulfate heptahydrate in 1000 parts by mass of deionized water for later use; (3) dropping the ferrous sulfate heptahydrate solution of the above step (2) into the solution of step (1), stirring the reaction at room temperature for 10 minutes, and then centrifuging, washing, and drying to obtain the multifunctional sea urchin-shaped nanoparticles.

[0023] Example 1

[0024] The CAB / PEG composite membrane having antibacterial, antioxidant and ammonia-sensitive functions is composed of the following components in parts by weight: 100 parts of cellulose acetate butyrate, 10 parts of polyethylene glycol, and 1 part of multifunctional sea urchin-shaped nanoparticles.

[0025] The preparation method comprises the following steps:

[0026] (1) Add 100 parts of cellulose acetate butyrate to 2500 parts of ethanol, stir at 55°C for 30 minutes, then add 10 parts of polyethylene glycol, continue stirring at 55°C for 30 minutes to obtain a uniform CAB / PEG solution for later use;

[0027] (2) Dispersing 1 part of the multifunctional sea urchin-like nanoparticles in 500 parts of ethanol, stirring at room temperature for 30 minutes to obtain a uniform dispersion for later use;

[0028] (3) adding the dispersion obtained in step (2) to the CAB / PEG solution obtained in step (1), and stirring at 55° C. for 1 h to obtain a uniform film-forming solution for later use;

[0029] (4) The film-forming solution in step (3) is poured onto a glass mold and dried in an oven at 55° C. for 24 h to obtain a CAB / PEG composite film having antibacterial, antioxidant and ammonia-sensitive functions.

[0030] Example 2

[0031] The CAB / PEG composite membrane having antibacterial, antioxidant and ammonia-sensitive functions is composed of the following components in parts by weight: 100 parts of cellulose acetate butyrate, 10 parts of polyethylene glycol, and 3 parts of multifunctional sea urchin-shaped nanoparticles.

[0032] The preparation method comprises the following steps:

[0033] (1) Add 100 parts of cellulose acetate butyrate to 2500 parts of ethanol, stir at 55°C for 30 minutes, then add 10 parts of polyethylene glycol, continue stirring at 55°C for 30 minutes to obtain a uniform CAB / PEG solution for later use;

[0034] (2) Dispersing 3 parts of multifunctional sea urchin-like nanoparticles in 500 parts of ethanol, stirring at room temperature for 30 minutes to obtain a uniform dispersion for later use;

[0035] (3) adding the dispersion obtained in step (2) to the CAB / PEG solution obtained in step (1), and stirring at 55° C. for 1 h to obtain a uniform film-forming solution for later use;

[0036] (4) The film-forming solution in step (3) is poured onto a glass mold and dried in an oven at 55° C. for 24 h to obtain a CAB / PEG composite film having antibacterial, antioxidant and ammonia-sensitive functions.

[0037] Example 3

[0038] The CAB / PEG composite membrane having antibacterial, antioxidant and ammonia-sensitive functions is composed of the following components in parts by weight: 100 parts of cellulose acetate butyrate, 10 parts of polyethylene glycol, and 5 parts of multifunctional sea urchin-shaped nanoparticles.

[0039] The preparation method comprises the following steps:

[0040] (1) Add 100 parts of cellulose acetate butyrate to 2500 parts of ethanol, stir at 55°C for 30 minutes, then add 10 parts of polyethylene glycol, continue stirring at 55°C for 30 minutes to obtain a uniform CAB / PEG solution for later use;

[0041] (2) Dispersing 5 parts of multifunctional sea urchin-like nanoparticles in 500 parts of ethanol, stirring at room temperature for 30 minutes to obtain a uniform dispersion for later use;

[0042] (3) Add the dispersion obtained in step (2) to the CAB / PEG solution obtained in step (1), and stir at 55° C. for 1 h to obtain a uniform film-forming solution for later use;

[0043] (4) The film-forming solution in step (3) is poured onto a glass mold and dried in an oven at 55°C for 24 hours to obtain a CAB / PEG composite membrane with antibacterial, antioxidant and ammonia-sensitive functions.

[0044] Comparative Example

[0045] As a comparison standard for each of the above embodiments, the present invention provides a pure CAB / PEG membrane material prepared without multifunctional sea urchin-like nanoparticles, comprising the following steps:

[0046] (1) Add 100 parts of cellulose acetate butyrate to 2500 parts of ethanol, stir at 55°C for 30 minutes, then add 10 parts of polyethylene glycol, continue stirring at 55°C for 30 minutes to obtain a uniform CAB / PEG solution for later use;

[0047] (2) Add 500 parts of ethanol to the CAB / PEG solution obtained in step (1), and stir at 55° C. for 1 hour to obtain a uniform film-forming solution for later use;

[0048] (3) The membrane-forming solution in step (2) was poured onto a glass mold and dried in an oven at 55°C for 24 h to obtain a pure CAB / PEG membrane material.

[0049] Performance Test:

[0050] The performance tests were carried out on the pure CAB / PEG membrane material prepared in the above comparative example and the CAB / PEG composite membrane material prepared in the embodiment, wherein the cross-sectional morphology of the CAB / PEG membrane material was characterized by SEM (SU-5000, Japan High-Tech Corporation), the tensile properties were tested according to GB / T1040-2006, the UV-visible properties were tested by UV spectrophotometer, and the average transmittance of ultraviolet rays (UVA, UVB and UVC) was calculated with reference to GB / T 18830-2009, and the antibacterial property test of the membrane material was carried out according to QBT2591-2003.

[0051] The DPPH free radical scavenging experimental method is as follows: 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 .

[0052] The ammonia response test method is as follows: the film sample material is exposed to an ammonia environment, and the color change of the film sample material is observed.

[0053] Shrimp freshness monitoring experiment: Fresh shrimps were purchased from the market, and the shrimps (mass: 30 g) were placed in a Petri dish and sealed with a Petri dish cover. The pure CAB / PEG membrane material prepared in the comparative example and the CAB / PEG composite membrane material prepared in Example 3 (pre-cut into sample materials with a diameter of 1 cm) were attached under the cover. The shrimp samples were then stored in an oven at 25°C, and the changes in the freshness of the shrimps and the color changes of the sample materials were observed and recorded.

[0054] The above performance test data are shown in Table 1 and Table 2.

[0055] Table 1 Performance test data

[0056]

[0057] Table 2 Shrimp freshness monitoring experiment results (where t is the storage time of fresh shrimp)

[0058]

[0059] SEM results of CAB / PEG composite membrane materials prepared in Example (see Figure 2 ) showed that the cross-sectional morphology was uniform, which meant that the multifunctional sea urchin-like nanoparticles had good compatibility with the CAB / PEG matrix, which was conducive to obtaining composite membrane materials with excellent performance.

[0060] The results of the ammonia response test experiment show that the pure CAB / PEG film prepared in the comparative example is colorless and transparent. After being exposed to an ammonia environment, its color does not change significantly, and it still exhibits colorless and transparent optical properties; the CAB / PEG composite film prepared in Example 3 is yellow, and after being exposed to an ammonia environment, its color changes to brown.

[0061] The results of the antibacterial test experiment show that the pure CAB / PEG membrane material prepared in the comparative example did not show obvious antibacterial activity against Escherichia coli and Staphylococcus aureus, while the CAB / PEG composite membrane material prepared in Example 3 had an inhibition rate of 100% against Escherichia coli and Staphylococcus aureus, that is, the CAB / PEG composite membrane material prepared in the example had excellent antibacterial activity.

[0062] In summary, it can be seen from the above sample performance test data that the CAB / PEG composite membrane material prepared by the present invention, which has antibacterial, antioxidant and ammonia-sensitive functions, not only has excellent antibacterial activity, DPPH free radical scavenging rate (i.e., antioxidant activity) and ammonia-sensitive color-changing function, but also exhibits excellent mechanical strength, tensile elongation at break (i.e., ductility), UV blocking and other properties, and can be used as an intelligent indicator material to timely and effectively indicate the freshness changes of meat foods such as shrimp during storage (see Table 2). The preparation process of the composite membrane material is simple, environmentally friendly, low-cost, and suitable for large-scale production. It has a wide range of application value in the fields of antibacterial, antioxidant, visual detection of ammonia, UV protection, food packaging, and intelligent materials.

[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. CAB / PEG composite membrane with antibacterial, antioxidant and ammonia-sensitive functions, characterized by: The invention is composed of the following components in parts by weight: 100 parts of cellulose acetate butyrate, 10 parts of polyethylene glycol, and 1-5 parts of multifunctional sea urchin-shaped nanoparticles; The preparation method of the multifunctional sea urchin-shaped nanoparticles comprises the following steps: (1) Dissolve 19.4 parts by weight of ferulic acid in 5000 parts by weight of ethanol, stir at room temperature for 10 minutes, and set aside; (2) dissolving 27.8 parts by mass of ferrous sulfate heptahydrate in 1000 parts by mass of deionized water for later use; (3) The ferrous sulfate heptahydrate solution of step (2) is added dropwise to the solution of step (1), and the mixture is stirred at room temperature for 10 min, and then centrifuged, washed, and dried to obtain multifunctional sea urchin-like nanoparticles.

2. The processing technology of the CAB / PEG composite membrane having antibacterial, antioxidant and ammonia-sensitive functions according to claim 1, characterized in that: The following steps are involved: (1) Add 100 parts of cellulose acetate butyrate to 2500 parts of ethanol, stir at 55°C for 30 minutes, then add 10 parts of polyethylene glycol, continue stirring at 55°C for 30 minutes to obtain a uniform CAB / PEG solution for later use; (2) dispersing 1-5 parts of the multifunctional sea urchin-like nanoparticles in 500 parts of ethanol, stirring at room temperature for 30 minutes to obtain a uniform dispersion for later use; (3) adding the dispersion obtained in step (2) to the CAB / PEG solution obtained in step (1), and stirring at 55° C. for 1 h to obtain a uniform film-forming solution for later use; (4) The film-forming liquid in step (3) is poured onto a glass mold and dried in an oven at 55° C. for 24 h to obtain a CAB / PEG composite membrane having antibacterial, antioxidant and ammonia-sensitive functions.

3. The use of the CAB / PEG composite membrane having antibacterial, antioxidant and ammonia-sensitive functions according to claim 1, characterized in that: It can be applied to antibacterial, anti-oxidant, visual detection of ammonia, UV protection, food packaging, and smart materials.

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