PMMA (polymethyl methacrylate) grafted polyaniline battery film and preparation method thereof
By preparing PMMA-grafted polyaniline battery films, the problems of high brittleness of inorganic oxide films and poor solubility of polyaniline were solved, and polyaniline battery films with high mechanical stability and good ductility were achieved, improving conductivity and antibacterial properties.
Patent Information
- Application Number
- CN202511562076.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-29
- Publication Date
- 2025-12-26
AI Technical Summary
Existing inorganic oxide films are brittle and have poor toughness, which limits their application in optoelectronic materials. The rigidity of polyaniline chains and strong inter-chain interactions result in extremely poor solubility, low mechanical strength and mechanical properties, which limit their widespread application.
A PMMA-grafted polyaniline battery film was prepared by hydrolyzing tetraethyl orthosilicate with triethanolamine, adding stearic acid and camphor sulfonic acid as a catalyst, and combining it with methylcellulose dispersion to form a sol ester amine, which was then mixed with PMMA polyaniline to carry out a quaternization reaction, thereby improving the dispersion compatibility of the sol and the mechanical stability of the film.
It improves the mechanical stability and strength of PMMA-grafted polyaniline battery films, enhances ductility, improves ionic conductivity, and improves the film's elongation at break and haze index.
Abstract
Description
Technical Field
[0001] This invention belongs to the field of battery materials, specifically relating to a PMMA-grafted polyaniline battery film and its preparation method. Background Technology
[0002] Conductive thin films are a very important optoelectronic material. They are characterized by low resistance and are widely used in various optoelectronic materials such as solar cells, electrode materials, and displays. Currently, inorganic oxide thin films are the most widely used because they have good light transmittance, low resistivity, and good chemical temperature characteristics. However, as inorganic fillers, their films are relatively brittle, have poor toughness, and require high synthesis temperatures, which limits their further development. Therefore, polymer conductive materials, including polyaniline and polypyridine, have gradually appeared on the market.
[0003] Polyaniline is widely used due to its good stability in air, readily available raw materials, inexpensive monomers, simple synthesis methods, and easily adjustable conductivity. It is used in various applications, such as electrode materials, electrochromic materials, metal corrosion protection materials, electromagnetic shielding materials, antistatic materials, and molecular devices. However, the rigidity of the polyaniline chain and the strong interactions between the chains make it extremely insoluble in solvents, which limits its widespread application in technology. In addition, polyaniline has the disadvantages of low mechanical strength and poor mechanical properties.
[0004] Therefore, it is of great significance to find a PMMA-grafted polyaniline battery film with strong mechanical stability and good ductility. Summary of the Invention
[0005] To address the problems in the prior art, this invention provides a PMMA-grafted polyaniline battery film and its preparation method.
[0006] To achieve the above objectives, the present invention adopts the following technical solution: A PMMA-grafted polyaniline battery film comprises PMMA polyaniline, dimethyl carbonate, triethanolamine, stearic acid, catalyst, methylcellulose, and tetraethyl orthosilicate; by mass parts, the PMMA polyaniline is 100-120 parts; dimethyl carbonate is 270-300 parts; triethanolamine is 20-30 parts; stearic acid is 14-18 parts; catalyst is 0.2-0.25 parts; methylcellulose is 6-8 parts; and tetraethyl orthosilicate is 30-40 parts.
[0007] Preferably, the degree of substitution (DS) of the methylcellulose is 2 to 2.5.
[0008] Preferably, the catalyst is camphor sulfonic acid.
[0009] Preferably, the mass grafting rate of the PMMA polyaniline is 10% to 15%.
[0010] A method for preparing a PMMA-grafted polyaniline battery film, comprising the following steps: (1) Add 20-30 parts of triethanolamine to 20-30 times its weight of deionized water, stir evenly, add 30-40 parts of tetraethyl orthosilicate, stir for 3-5 hours, add 14-18 parts of stearic acid and 0.2-0.25 parts of catalyst, introduce nitrogen gas, adjust the temperature of the reactor to 150℃-180℃, stir and react for 5-6 hours, cool to room temperature, discharge and cool, send to an oven, dry at 75-80℃ for 1-2 hours, discharge and cool to obtain sol ester amine; (2) Take 6-8 parts of methylcellulose and add it to 270-300 parts of dimethyl carbonate. Raise the temperature to 60-70℃ and stir for 1-2 hours to obtain a fiber dispersion. (3) Take 100-120 parts of PMMA polyaniline, mix it with the sol ester amine obtained in step (1), and then add it to the fiber dispersion obtained in step (2). Stir evenly, send it into the reactor, introduce nitrogen gas, adjust the reactor temperature to 55℃-60℃, react for 30-40 hours, discharge and cool, coat it evenly on a glass plate, send it into an oven, dry it at 70-75℃ for 10-13 hours, discharge and cool, peel off the film, and obtain the PMMA grafted polyaniline battery film.
[0011] As can be seen from the above description, the present invention has the following advantages: This invention first uses tetraethyl orthosilicate as a precursor, hydrolyzes it in an aqueous solution containing triethanolamine, blends it with stearic acid, and reacts it under the catalysis of camphor sulfonic acid to obtain sol-ester amine. Then, methylcellulose is dispersed in dimethyl carbonate, the sol-ester amine is added, and a quaternization reaction is carried out under nitrogen. During the reaction, a PMMA-grafted polyaniline host is introduced, thereby improving the dispersion compatibility of the sol among various organic raw materials, and improving the mechanical stability and strength of the finished film. Camphor sulfonic acid acts as a catalyst to improve the ionic conductivity of the film, and PMMA grafting improves the elongation at break and haze index, thus improving the film's ductility. Detailed Implementation
[0012] The features of the present invention will be further illustrated below through examples, but the claims of the present invention are not limited in any way.
[0013] Example 1: (1) Add 25 parts of triethanolamine to 25 times its weight of deionized water, stir evenly, add 35 parts of tetraethyl orthosilicate, stir for 4 hours, add 16 parts of stearic acid and 0.25 parts of camphor sulfonic acid catalyst, introduce nitrogen gas, adjust the temperature of the reactor to 160℃, stir and react for 5.5 hours, cool to room temperature, discharge and cool, send to an oven, dry at 75℃ for 1.5 hours, discharge and cool to obtain sol ester amine; (2) Take 7 parts of methylcellulose with a degree of substitution DS of 2 and add it to 280 parts of dimethyl carbonate. Raise the temperature to 60°C and stir for 1.5 hours to obtain a fiber dispersion. (3) Take 100 parts of PMMA polyaniline, mix it with the sol ester amine obtained in step (1), and then add it to the fiber dispersion obtained in step (2). Stir evenly, send it into the reactor, introduce nitrogen gas, adjust the reactor temperature to 55℃, react for 35 hours, discharge and cool, coat it evenly on a glass plate, send it into an oven, dry it at 70℃ for 10 hours, discharge and cool, peel off the film, and obtain the PMMA grafted polyaniline battery film.
[0014] The performance test results of the grafted polyaniline battery film obtained in Example 1 are as follows: Tensile strength: 16.3 MPa; Elongation at break: 15.8%; The conductivity was tested using the four-probe method, and the result was 4.5 S / cm; The inhibition rate against Escherichia coli was 99.8%; Haze (3mm film thickness): 6.20%.
[0015] Example 2: (1) Add 30 parts of triethanolamine to 30 times its weight of deionized water, stir evenly, add 40 parts of tetraethyl orthosilicate, stir for 5 hours, add 18 parts of stearic acid and 0.2 parts of camphor sulfonic acid catalyst, introduce nitrogen gas, adjust the temperature of the reactor to 180°C, stir for 6 hours, cool to room temperature, discharge and cool, send to an oven, dry at 80°C for 2 hours, discharge and cool to obtain sol ester amine; (2) Take 8 parts of methylcellulose with a degree of substitution (DS) of 2.5 and add it to 300 parts of dimethyl carbonate. Raise the temperature to 70°C and stir for 2 hours to obtain a fiber dispersion. (3) Take 120 parts of PMMA polyaniline, mix it with the sol ester amine obtained in step (1), and then add it to the fiber dispersion obtained in step (2). Stir evenly, send it into the reactor, introduce nitrogen gas, adjust the reactor temperature to 60℃, react for 40 hours, discharge and cool, coat it evenly on a glass plate, send it into an oven, dry it at 75℃ for 13 hours, discharge and cool, peel off the film, and obtain the PMMA grafted polyaniline battery film.
[0016] The performance test results of the grafted polyaniline battery film obtained in Example 2 are as follows: Tensile strength: 18.2 MPa; Elongation at break: 20.5%; The conductivity was tested using the four-probe method, and the result was 5.2 S / cm; The inhibition rate against Escherichia coli was 99.8%; Haze (3mm film thickness): 5.10%.
[0017] Example 3: (1) Add 20 parts of triethanolamine to 20 times its weight of deionized water, stir evenly, add 30 parts of tetraethyl orthosilicate, stir for 3 hours, add 14 parts of stearic acid and 0.25 parts of camphor sulfonic acid catalyst, introduce nitrogen gas, adjust the temperature of the reactor to 150°C, stir for 5 hours, cool to room temperature, discharge and cool, send to an oven, dry at 75°C for 1 hour, discharge and cool to obtain sol ester amine; (2) Take 6 parts of methylcellulose with a degree of substitution DS of 2 and add it to 270 parts of dimethyl carbonate. Raise the temperature to 60°C and stir for 1 hour to obtain a fiber dispersion. (3) Take 100 parts of PMMA polyaniline, mix it with the sol ester amine obtained in step (1), and then add it to the fiber dispersion obtained in step (2). Stir evenly, send it into the reactor, introduce nitrogen gas, adjust the reactor temperature to 55℃, react for 30 hours, discharge and cool, coat it evenly on a glass plate, send it into an oven, dry it at 70℃ for 10 hours, discharge and cool, peel off the film, and obtain the PMMA grafted polyaniline battery film.
[0018] The performance test results of the grafted polyaniline battery film obtained in Example 3 are as follows: Tensile strength: 17.5 MPa; Elongation at break: 15.6%; The conductivity was tested using the four-probe method, and the result was 8.6 S / cm; The inhibition rate against Escherichia coli was 99.8%; Haze (3mm film thickness): 9.2%.
[0019] It is understood that the above detailed description of the present invention is for illustrative purposes only and is not intended to limit the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention to achieve the same technical effects; as long as the usage requirements are met, they are all within the protection scope of the present invention.
Claims
1. A PMMA-grafted polyaniline battery film, characterized in that, It includes PMMA (polyaniline), dimethyl carbonate, triethanolamine, stearic acid, catalyst, methylcellulose, and tetraethyl orthosilicate; by mass parts, the PMMA (polyaniline) is 100-120 parts; dimethyl carbonate is 270-300 parts; triethanolamine is 20-30 parts; stearic acid is 14-18 parts; catalyst is 0.2-0.25 parts; methylcellulose is 6-8 parts; and tetraethyl orthosilicate is 30-40 parts.
2. The PMMA-grafted polyaniline battery film according to claim 1, characterized in that, The degree of substitution (DS) of the methylcellulose is 2 to 2.
5.
3. The PMMA-grafted polyaniline battery film according to claim 1, characterized in that, The catalyst is camphor sulfonic acid.
4. The PMMA-grafted polyaniline battery film according to claim 1, characterized in that, The mass grafting rate of the PMMA polyaniline is 10% to 15%.
5. A method for preparing a PMMA-grafted polyaniline battery film, characterized in that, The steps are as follows: (1) Add 20-30 parts of triethanolamine to 20-30 times its weight of deionized water, stir evenly, add 30-40 parts of tetraethyl orthosilicate, stir for 3-5 hours, add 14-18 parts of stearic acid and 0.2-0.25 parts of catalyst, introduce nitrogen gas, adjust the temperature of the reactor to 150℃-180℃, stir and react for 5-6 hours, cool to room temperature, discharge and cool, send to an oven, dry at 75-80℃ for 1-2 hours, discharge and cool to obtain sol ester amine; (2) Take 6-8 parts of methylcellulose and add it to 270-300 parts of dimethyl carbonate. Raise the temperature to 60-70℃ and stir for 1-2 hours to obtain a fiber dispersion. (3) Take 100-120 parts of PMMA polyaniline, mix it with the sol ester amine obtained in step (1), and then add it to the fiber dispersion obtained in step (2). Stir evenly, send it into the reactor, introduce nitrogen gas, adjust the reactor temperature to 55℃-60℃, react for 30-40 hours, discharge and cool, coat it evenly on a glass plate, send it into an oven, dry it at 70-75℃ for 10-13 hours, discharge and cool, peel off the film, and obtain the PMMA grafted polyaniline battery film.