High-performance ca-based nanocomposite membrane, preparation method and application thereof

Abstract

The application belongs to the technical field of high polymer composite materials, and particularly relates to a high-performance CA-based nanocomposite film and a preparation method and application thereof, which is prepared from the following raw materials: cellulose acetate, glycerol and multifunctional nanoparticles. The application further provides a preparation method of the high-performance CA-based nanocomposite film. The multifunctional nanoparticles are used as fillers based on the CA matrix, so that the performance of the CA-based composite material can be effectively improved. The high-performance CA-based nanocomposite film prepared by the application has excellent ultraviolet shielding performance, high-energy short-wave blue light blocking performance, mechanical performance and ammonia gas response color-changing performance. The composite material preparation process is simple, environmentally friendly, low in cost and suitable for large-scale production, and has wide application value in the fields of food packaging, intelligent materials, ammonia gas detection, environmental monitoring and safety.

Description

Technical Field

[0001] This invention belongs to the field of polymer composite materials technology, specifically relating to a high-performance CA-based nanocomposite film, its preparation method, and its application. Background Technology

[0002] Cellulose acetate (CA) is a thermoplastic resin obtained by esterification using acetic acid as a solvent and acetic anhydride as an acetylation agent under the action of a catalyst. It is the earliest commercially produced and continuously developing cellulose organic ester among cellulose derivatives. Due to its non-toxicity, good processing performance, biodegradability, biocompatibility, and cost-effectiveness, CA can be used to manufacture films, fibers, plastic products, and tactile actuators, attracting widespread attention from researchers. As a porous membrane material, CA has advantages such as high selectivity, high water permeability, and simple processing. However, CA also has its own weaknesses, such as poor toughness, poor UV shielding performance, and lack of ammonia-responsive color change, which limits its application in food packaging and UV protection. Therefore, there is an urgent need to develop high-performance CA films to broaden its application areas. This invention uses CA as a matrix and multifunctional nanoparticles as functional fillers to improve the mechanical, ultraviolet blocking, high-energy blue light blocking, and ammonia-responsive color-changing properties of CA films. It develops high-performance CA-based nanocomposite films and expands their applications in food packaging, smart materials, ammonia-responsive materials, ammonia detection, environmental monitoring and safety. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a high-performance CA-based nanocomposite film, its preparation method, and its applications. This composite film possesses excellent mechanical strength, toughness, UV blocking, high-energy blue light blocking, and ammonia-responsive color change properties. Furthermore, the preparation process of this composite material is simple, environmentally friendly, low-cost, and suitable for large-scale production.

[0004] Technical solution of the present invention:

[0005] This invention provides a high-performance CA-based nanocomposite membrane, characterized in that it is composed of the following components in parts by weight: 100 parts cellulose acetate, 10 parts glycerol, and 1-5 parts multifunctional nanoparticles.

[0006] The preparation method of the multifunctional nanoparticles includes the following steps:

[0007] (1) Dissolve 13.3 parts of D-aspartic acid in a mixed solvent of 1500 parts of deionized water and 2500 parts of anhydrous ethanol, adjust the pH to 9 with 1 mol / L sodium hydroxide solution to obtain a homogeneous solution for later use;

[0008] (2) Dissolve 10 parts of ferric sulfate in a mixed solvent of 1000 parts of deionized water and 1000 parts of anhydrous ethanol to obtain a homogeneous ferric sulfate solution for later use.

[0009] (3) Add the ferric sulfate solution obtained in step (2) to the solution obtained in step (1), control the pH to 7 with 1 mol / L sodium hydroxide solution, stir the reaction at room temperature for 15 min, then centrifuge, wash and dry to obtain multifunctional nanoparticles.

[0010] This invention also provides a method for preparing the above-mentioned high-performance CA-based nanocomposite film, characterized by comprising the following steps:

[0011] (1) Add 100 parts of cellulose acetate and 10 parts of glycerol to 1300 parts of acetone and stir at room temperature for 60 minutes to obtain a homogeneous blend solution for later use.

[0012] (2) Disperse 1-5 parts of multifunctional nanoparticles in 200 parts of acetone and stir at room temperature for 30 minutes to obtain a uniform dispersion for later use.

[0013] (3) Add the dispersion obtained in step (2) to the blend solution obtained in step (1), stir at room temperature for 30 min to obtain a uniform film-forming solution for later use;

[0014] (4) Pour the film-forming liquid obtained in step (3) into a flat-bottomed glass dish and dry it in an oven at 30°C for 15 hours to obtain a high-performance CA-based nanocomposite film.

[0015] The application of the high-performance CA-based nanocomposite membrane is characterized by its use in fields such as food packaging, smart materials, ammonia detection, environmental monitoring and safety.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] The high-performance CA-based nanocomposite film prepared by this invention has excellent mechanical strength, toughness, ultraviolet blocking, high-energy blue light blocking, and ammonia-responsive color change properties. Moreover, the preparation process of this composite material is simple, environmentally friendly, low-cost, and suitable for large-scale production. It has wide application value in food packaging, smart materials, ammonia-responsive materials, ammonia detection, environmental monitoring and safety and other fields. Attached Figure Description

[0018] Figure 1 This is a scanning electron microscope image of the multifunctional nanoparticles involved in this invention.

[0019] Figure 2 Fourier transform infrared spectra of the multifunctional nanoparticles involved in this invention.

[0020] Figure 3 The images show actual photographs of the CA membrane samples prepared for the comparative example of this invention and the high-performance CA-based nanocomposite membrane samples prepared for the examples. Detailed Implementation

[0021] The present invention will be specifically described below through embodiments. It should be noted that these embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the above description of the present invention. Unless otherwise specified, the parts of raw materials mentioned are all parts by weight.

[0022] In the following specific embodiments and comparative formulations and preparation methods, the D-aspartic acid used is an analytical grade reagent provided by Ron Reagent Co., Ltd.; the ferric sulfate used is an analytical grade reagent provided by Xilong Scientific Co., Ltd.; the cellulose acetate used is a product provided by Aladdin Reagent Co., Ltd.; the acetone used is an analytical grade reagent provided by Xilong Scientific Co., Ltd.; the glycerol used is an analytical grade reagent provided by Xilong Scientific Co., Ltd.; and the anhydrous ethanol used is a product provided by Tianjin Fuyu Fine Chemical Co., Ltd.

[0023] In the following specific embodiments and comparative formulations and preparation methods, the preparation method of the multifunctional nanoparticles includes the following steps:

[0024] (1) Dissolve 13.3 parts of D-aspartic acid in a mixed solvent of 1500 parts of deionized water and 2500 parts of anhydrous ethanol, adjust the pH to 9 with 1 mol / L sodium hydroxide solution to obtain a homogeneous solution for later use;

[0025] (2) Dissolve 10 parts of ferric sulfate in a mixed solvent of 1000 parts of deionized water and 1000 parts of anhydrous ethanol to obtain a homogeneous ferric sulfate solution for later use.

[0026] (3) Add the ferric sulfate solution obtained in step (2) to the solution obtained in step (1), control the pH to 7 with 1 mol / L sodium hydroxide solution, stir the reaction at room temperature for 15 min, then centrifuge, wash and dry to obtain multifunctional nanoparticles.

[0027] Example 1

[0028] A high-performance CA-based nanocomposite membrane is characterized by being composed of the following components in parts by weight: 100 parts cellulose acetate, 10 parts glycerol, and 1 part multifunctional nanoparticles.

[0029] The preparation method includes the following steps:

[0030] (1) Add 100 parts of cellulose acetate and 10 parts of glycerol to 1300 parts of acetone and stir at room temperature for 60 minutes to obtain a homogeneous blend solution for later use.

[0031] (2) Disperse 1 part of multifunctional nanoparticles in 200 parts of acetone and stir at room temperature for 30 min to obtain a uniform dispersion for later use;

[0032] (3) Add the dispersion obtained in step (2) to the blend solution obtained in step (1), stir at room temperature for 30 min to obtain a uniform film-forming solution for later use;

[0033] (4) Pour the film-forming liquid obtained in step (3) into a flat-bottomed glass dish and dry it in an oven at 30°C for 15 hours to obtain a high-performance CA-based nanocomposite film.

[0034] Example 2

[0035] A high-performance CA-based nanocomposite membrane is characterized by being composed of the following components in parts by weight: 100 parts cellulose acetate, 10 parts glycerol, and 3 parts multifunctional nanoparticles.

[0036] The preparation method includes the following steps:

[0037] (1) Add 100 parts of cellulose acetate and 10 parts of glycerol to 1300 parts of acetone and stir at room temperature for 60 minutes to obtain a homogeneous blend solution for later use.

[0038] (2) Disperse 3 parts of multifunctional nanoparticles in 200 parts of acetone and stir at room temperature for 30 min to obtain a uniform dispersion for later use;

[0039] (3) Add the dispersion obtained in step (2) to the blend solution obtained in step (1), stir at room temperature for 30 min to obtain a uniform film-forming solution for later use;

[0040] (4) Pour the film-forming liquid obtained in step (3) into a flat-bottomed glass dish and dry it in an oven at 30°C for 15 hours to obtain a high-performance CA-based nanocomposite film.

[0041] Example 3

[0042] A high-performance CA-based nanocomposite membrane is characterized by being composed of the following components in parts by weight: 100 parts cellulose acetate, 10 parts glycerol, and 5 parts multifunctional nanoparticles.

[0043] The preparation method includes the following steps:

[0044] (1) Take 100 parts of cellulose acetate and 10 parts of glycerol and add them to 1300 parts of acetone. Stir at room temperature for 60 minutes to obtain a uniform blend solution for later use.

[0045] (2) Disperse 5 parts of multifunctional nanoparticles in 200 parts of acetone and stir at room temperature for 30 min to obtain a uniform dispersion for later use;

[0046] (3) Add the dispersion obtained in step (2) to the blend solution obtained in step (1), stir at room temperature for 30 min to obtain a uniform film-forming solution for later use;

[0047] (4) Pour the film-forming liquid obtained in step (3) into a flat-bottomed glass dish and dry it in an oven at 30°C for 15 hours to obtain a high-performance CA-based nanocomposite film.

[0048] Comparative Example

[0049] As a comparative standard with the above embodiments, the present invention provides a CA film prepared without containing multifunctional nanoparticles, comprising the following steps:

[0050] (1) Add 100 parts of cellulose acetate and 10 parts of glycerol to 1300 parts of acetone and stir at room temperature for 60 minutes to obtain a homogeneous blend solution for later use.

[0051] (2) Add 200 parts of acetone to the blend solution obtained in step (1) and stir for 30 minutes at room temperature to obtain a uniform film-forming solution for later use;

[0052] (3) Pour the film-forming solution obtained in step (2) into a flat-bottomed glass dish and dry it in an oven at 30°C for 15 hours to obtain the CA film.

[0053] Structural and performance testing:

[0054] The CA films prepared in the comparative examples and the high-performance CA-based nanocomposite films prepared in the examples were subjected to structural and performance tests. The ultraviolet-visible properties were tested using an ultraviolet-visible spectrometer (Lamdba365, Platinum Elmer Instruments), and the average ultraviolet transmittance was calculated according to GB / T 18830-2009. The tensile properties were tested according to GB / T 1040-2006. The ammonia response test method was as follows: the sample material was exposed to an ammonia environment for 2 h, the color change of the sample material was observed and recorded, and the color difference value ∆E of the sample material before and after the ammonia response was calculated (Note: ∆E > 3 indicates a significant color change visible to the human eye).

[0055] The above performance test data are shown in Table 1.

[0056] Table 1 Sample performance test data

[0057] Group Example 1 Example 2 Example 3 Comparative Example Average UVA transmittance (%) 1.4 0.4 0 34.6 Average UVB transmittance (%) 0.2 0.1 0 27.6 Average transmittance of UVC (%) 0 0 0 7.8 Average transmittance of high-energy short-wave blue light (%) 9.8 1.3 0 39.5 Tensile strength (MPa) 36.3 34.5 32.0 29.2 Elongation at break (%) 6.4 5.5 5.3 5.1 <![CDATA[Toughness (MJ / m 3 )]]> 1.7 1.2 0.98 0.78

[0058] The ammonia response test results showed that the CA film prepared in the comparative example was white and transparent. After exposure to ammonia, its color did not change, maintaining its white and transparent optical properties, with a ∆E value of 0.93 (meaning the color difference was negligible and imperceptible to the human eye). The CA-based nanocomposite film prepared in Example 1 was pale yellow. After exposure to ammonia, its color changed significantly, with a ∆E as high as 14.61 (Note: ∆E > 3 indicates a noticeable color change visible to the human eye). The CA-based nanocomposite film prepared in Example 2 was pale yellow. After exposure to ammonia, its color changed significantly, with a ∆E as high as 18.767 (Note: ∆E > 3 indicates a noticeable color change visible to the human eye). The CA-based nanocomposite film prepared in Example 3 was yellow. After exposure to ammonia, its color changed significantly, with a ∆E as high as 22.24 (Note: ∆E > 3 indicates a noticeable color change visible to the human eye).

[0059] In summary, the sample performance test data (see Table 1) show that the high-performance CA-based nanocomposite film prepared by this invention has excellent mechanical strength, toughness, ultraviolet blocking, high-energy blue light blocking, and ammonia-responsive color change properties. Moreover, the preparation process of this composite material is simple, environmentally friendly, low-cost, and suitable for large-scale production. It has wide application value in food packaging, smart materials, ammonia-responsive materials, ammonia detection, environmental monitoring and safety, and other fields.

[0060] The content of this invention is not limited to the embodiments listed. Any equivalent modifications made by those skilled in the art to the technical solutions of this invention by reading this specification are covered by the claims of this invention.

Claims

1. A high performance CA-based nanocomposite film, characterized in that, It is made of the following components by weight: 100 parts of cellulose acetate, 10 parts of glycerol, 3-5 parts of multifunctional nanoparticles; The preparation method of the multifunctional nanoparticles comprises the following steps: (1) 13.3 parts of D-aspartic acid are dissolved in a mixed solvent of 1500 parts of deionized water and 2500 parts of anhydrous ethanol, and the pH is adjusted to 9 with 1 mol / L sodium hydroxide solution to obtain a uniform solution, which is ready for use; (2) 10 parts of iron sulfate are dissolved in a mixed solvent of 1000 parts of deionized water and 1000 parts of anhydrous ethanol to obtain a uniform iron sulfate solution, which is ready for use; (3) The iron sulfate solution obtained in step (2) is added to the solution obtained in step (1), and the pH is controlled to 7 with 1 mol / L sodium hydroxide solution, and stirred at room temperature for 15 min, then centrifuged, washed and dried to obtain multifunctional nanoparticles.

2. The method for preparing a high-performance CA-based nanocomposite film according to claim 1, characterized in that... It comprises the following steps: (1) 100 parts of cellulose acetate, 10 parts of glycerol are added to 1300 parts of acetone, stirred at room temperature for 60 min to obtain a uniform blending solution, which is ready for use; (2) 1-5 parts of multifunctional nanoparticles are dispersed in 200 parts of acetone, stirred at room temperature for 30 min to obtain a uniform dispersion, which is ready for use; (3) The dispersion obtained in step (2) is added to the blending solution obtained in step (1), stirred at room temperature for 30 min to obtain a uniform film-forming solution, which is ready for use; (4) The film-forming solution obtained in step (3) is poured into a flat-bottomed glass dish, dried in an oven at 30°C for 15 h to obtain a high-performance CA-based nanocomposite film.

3. Use of a high performance CA-based nanocomposite film according to claim 1, characterized in that, It is used in food packaging, smart materials, ammonia detection, environmental monitoring and safety fields.

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