CN112759785A - Antifogging self-cleaning polyimide film and preparation method thereof - Google Patents
Antifogging self-cleaning polyimide film and preparation method thereof Download PDFInfo
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Abstract
The invention provides an anti-fog self-cleaning film, aiming at solving the problem that a transparent polyimide film is easy to stain in the use process. The surface of the transparent polyimide film provided by the invention is subjected to etching treatment, and then a polymer brush is formed on the surface of the treated transparent polyimide film and comprises an initiator, a monomer 1 and a monomer 2; in the initiator, R1 represents propyl or butyl; in monomer 1, R2 and R3 each independently represent ethyl, propyl, butyl, or pentyl; in monomer 2: r4 and R5 each independently represent a hydrogen atom, a methyl group, a carboxyl group, a pyrrolidone group, a benzenesulfonyl group, a carboxymethyl oligoethylene glycol ester, a carboxymethyl hydroxyethyl ester, a carboxymethyl hydroxypropyl ester, or a carboxymethyl hydroxybutyl ester. The polyimide film provided by the invention has the characteristics of high transmittance, good surface hydrophilicity and the like.
Description
Technical Field
The invention belongs to the field of materials, particularly relates to a film material with an anti-fog self-cleaning function, and particularly relates to a polymer brush with good anti-fog and self-cleaning performances and a preparation method thereof.
Background
The transparent Polyimide (PI) film is widely applied to the field of flexible display due to excellent heat resistance, high strength and high modulus and good light transmittance. However, in the using process, the surface of the film is easily polluted by air, especially dust and suspended particles are easily attached to the outer wall of a building to become dirt, and the display effect is greatly influenced. Traditional manual cleaning mode not only wastes time and energy, brings extra risk moreover.
For this reason, it is important to develop antifouling and self-cleaning film materials. It is known that this way achieves the self-cleaning effect mainly by the action of water, and the super-hydrophilic coating is to put water close to the glass surface and isolate the dirt from the glass. People have great breakthrough on the research of bionics. The research shows that the surface of the outer cell membrane has a layer of phosphorylcholine group at the head of phospholipid, and the group has strong hydrophilicity. Based on the understanding of the structure and the characteristics of phosphorylcholine, betaine type zwitterionic compounds with similar structures can be modified on the surface of the material to construct a bionic surface similar to an extracellular membrane, so that the modified surface of the material has strong hydrophilicity.
The self-cleaning function of the material can be endowed by constructing the surface structure and the surface chemical composition multi-element synergistic action, and a plurality of hydrophilic polymers are proved to have good antifouling property.
Disclosure of Invention
In order to solve the problems that the transparent polyimide film is easy to be polluted in the using process and the like, and further influence the display effect, the invention provides an anti-fog self-cleaning film. The anti-fog self-cleaning method provided by the invention is realized by the following technical scheme:
a preparation method of polyimide film containing copolymer brush is characterized in that Atom Transfer Radical Polymerization (ATRP) initiated on the surface of the polyimide film comprises the following steps;
(1) and etching the surface of the transparent polyimide film by adopting plasma.
(2) And adopting an initiator to couple to the surface of the polyimide film by a vapor deposition method.
(3) Weighing a proper amount of monomer 1, monomer 2, cuprous bromide, 2' -bipyridyl and the treated film, placing the mixture into a solvent, and stirring and reacting for 6-18h under the protection of argon atmosphere and at the temperature of 50-90 ℃.
(4) And repeatedly washing the film by using deionized water and acetone to remove the catalyst on the surface and unreacted monomers, thus obtaining the polyimide film of the copolymer brush.
Wherein the initiator is one of 2-bromo-2-methylpropanoic acid-3- (trichlorosilyl) propyl ester or 2-bromo-2-methylpropanoic acid-4- (trichlorosilyl) butyl ester, and has the following structure:
wherein the monomer 1 is one or more of N, N-dimethyl-N- (methacryloyloxyethyl) -N- (2-sulfoalkyl) ammonium inner salt, N-dimethyl-N- (methacryloyloxypropyl) -N- (2-sulfoalkyl) ammonium inner salt or N, N-dimethyl-N- (methacryloyloxybutyl) -N- (2-sulfoalkyl) ammonium inner salt (N ═ 2-5), and has the following structure:
wherein the monomer 2 is methacrylic acid, N-methyl pyrrolidone, sodium styrene sulfonate,Oligo (ethylene glycol methyl ether) Methacrylic acid estersOne or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl methacrylate, having the structure shown below:
the step (1) of etching the surface of the transparent polyimide film by the plasma comprises the steps of putting the transparent polyimide film into a plasma vacuum reaction cavity, continuously vacuumizing the plasma cavity to be below 0.1Pa, introducing argon gas at the flow rate of 15-25mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and the etching treatment time is 1-5 minutes.
Wherein, the mass fraction of the initiator is 0.02-0.08% relative to the mass of the film in the step (2).
Wherein, relative to the mass of the film in the step (3), the mass fraction of the monomer 1 is 5-10%, the mass fraction of the monomer 2 is 2-6%, and the mass fraction of the cuprous bromide is 0.05-0.25%.
Wherein, the solvent used in the step (3) is one of benzene, xylene, cyclohexanone and anisole.
Wherein, the monomer 1 and the monomer 2 in the step (3) can be added into the reaction system at the same time to form a random copolymer; or added to the reaction system in steps to form the block copolymer.
An antifogging self-cleaning polyimide film is characterized in that the light transmittance of the polyimide film is more than 83%, and the contact angle of the polyimide film is less than or equal to 42.6 degrees.
Wherein, the polyimide film preferably has light transmittance of more than 86% and a contact angle of less than or equal to 36.6 °.
The invention has the advantages that the prepared film surface material has good antifogging self-cleaning effect, thereby having very wide application prospect; simultaneously still possess following technological effect:
(1) the film prepared by the invention has high transmittance;
(2) compared with the traditional solution soaking mode, the method for modifying the surface of the thin film by adopting the vapor deposition method avoids the side reaction of the silane coupling agent and water, reduces the using amount of the coupling agent, has stronger gas permeability than liquid, and is more suitable for modifying the surface of the thin film with high density.
(3) The film prepared by the invention is nontoxic and pollution-free, and cannot influence production and living environments.
Drawings
Fig. 1 is a schematic structural diagram of a polyimide film surface modified by a polymer brush according to the present invention.
A is a copolymer brush, and B is a polyimide film.
Detailed Description
Fig. 1 is a schematic structural diagram of a polyimide film surface modified by a polymer brush according to the present invention, and the present invention is further described with reference to the following embodiments.
The light transmittance test method comprises the following steps: the transmittance of the film was measured using a spectrophotometer.
Contact angle test method: the contact angle of the film was measured using a contact angle tester.
And (3) hydrophilicity judgment standard: a smaller contact angle indicates a more hydrophilic film.
Example 1
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 20mL/min, starting microwave plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 1 minute.
(2) The vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid 3- (trichlorosilyl) propyl ester on the surface of 100g of the film.
(3) 6g N, N-dimethyl-N- (methacryloyloxyethyl) -N- (2-sulfoethyl) ammonium inner salt, 5g of methacrylic acid and 0.06g of cuprous bromide were weighed and reacted with the film in a toluene solution under stirring at 60 ℃ under an argon atmosphere for 6 hours.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 2
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 25mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 1 minute.
(2) The vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid 3- (trichlorosilyl) propyl ester on the surface of 100g of the film.
(3) 6g N, N-dimethyl-N- (methacryloyloxyethyl) -N- (2-sulfopropyl) ammonium inner salt, 3g of methacrylic acid and 0.06g of cuprous bromide are weighed and stirred with the film in a toluene solution for reaction for 6 hours under an inert gas atmosphere and at a temperature of 80 ℃.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 3
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 23mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 1 minute.
(2) The vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid 3- (trichlorosilyl) propyl ester on the surface of 100g of the film.
(3) 6g N, N-dimethyl-N- (methacryloyloxyethyl) -N- (2-sulfobutyl) ammonium inner salt, 5g of methacrylic acid and 0.06g of cuprous bromide are weighed and stirred with the film in a toluene solution under an inert gas atmosphere and at a temperature of 80 ℃ for reaction for 12 hours.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 4
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 21mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 1 minute.
(2) The vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid 3- (trichlorosilyl) propyl ester on the surface of 100g of the film.
(3) 8g N, N-dimethyl-N- (methacryloyloxyethyl) -N- (2-sulfobutyl) ammonium inner salt, 5g of methacrylic acid and 0.06g of cuprous bromide are weighed and stirred with the film in a toluene solution under an inert gas atmosphere and at a temperature of 80 ℃ for reaction for 18 h.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 5
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 19mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 1 minute.
(2) The vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid 3- (trichlorosilyl) propyl ester on the surface of 100g of the film.
(3) 6g N, N-dimethyl-N- (methacryloxypropyl) -N- (2-sulfopropyl) ammonium inner salt, 3g N-vinyl pyrrolidone and 0.06g of cuprous bromide are weighed and stirred with the film in a toluene solution for reaction for 6 hours under the conditions of inert gas atmosphere and 80 ℃.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 6
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 17mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 1 minute.
(2) The vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid 3- (trichlorosilyl) propyl ester on the surface of 100g of the film.
(3) 8g N, N-dimethyl-N- (methacryloxypropyl) -N- (2-sulfobutyl) ammonium inner salt, 5g N-vinyl pyrrolidone and 0.06g of cuprous bromide are weighed and stirred with the film in a toluene solution for reaction for 6 hours under the conditions of inert gas atmosphere and 80 ℃.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 7
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 15mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 1 minute.
(2) The vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid-3- (trichlorosilyl) propyl ester on the surface of 100g of the film.
(3) 8g N, N-dimethyl-N- (methacryloxypropyl) -N- (2-sulfobutyl) ammonium inner salt, 5g N-vinyl pyrrolidone and 0.06g of cuprous bromide are weighed and stirred with the film in a toluene solution for 18 hours under the conditions of inert gas atmosphere and 80 ℃.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 8
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 25mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 1 minute.
(2) A vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid-4- (trichlorosilyl) butyl ester on the surface of 100g of the film.
(3) 6g N, N-dimethyl-N- (methacryloyloxyethyl) -N- (2-sulfopropyl) ammonium inner salt, 3g N-vinyl pyrrolidone and 0.06g of cuprous bromide are weighed and stirred with the film in a toluene solution for reaction for 6 hours under the conditions of inert gas atmosphere and 60 ℃.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 9
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 19mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 3 minutes.
(2) A vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid-4- (trichlorosilyl) butyl ester on the surface of 100g of the film.
(3) 6g N, N-dimethyl-N- (methacryloxypropyl) -N- (2-sulfopropyl) ammonium inner salt and 4g were weighedOligo (A) Polyethylene glycol methyl ether methacrylateAnd 0.06g of cuprous bromide, which reacts with the film in a toluene solution under an inert gas atmosphere at a temperature of 60 ℃ for 12 hours with stirring.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 10
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 23mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 3 minutes.
(2) A vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid-4- (trichlorosilyl) butyl ester on the surface of 100g of the film.
(3) 6g N, N-dimethyl-N- (methacryloxypropyl) -N- (2-sulfobutyl) ammonium inner salt and 5g were weighedOligo (A) Polyethylene glycol methyl ether methacrylateAnd 0.06g of cuprous bromide, which reacts with the film in a toluene solution under an inert gas atmosphere at a temperature of 60 ℃ for 12 hours with stirring.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 11
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 25mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 3 minutes.
(2) A vapor deposition method is adopted to couple 0.03g of initiator 2-bromo-2-methylpropanoic acid-4- (trichlorosilyl) butyl ester on the surface of 100g of the film.
(3) 6g N, N-dimethyl-N- (methacryloyloxybutyl) -N- (2-sulfoethyl) ammonium inner salt and 5g were weighedOligo (A) Polyethylene glycol methyl ether methacrylateAnd 0.06g of cuprous bromide, which reacts with the film in a toluene solution under an inert gas atmosphere and at a temperature of 80 ℃ with stirring for 6 hours.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 12
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 15mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 3 minutes.
(2) A vapor deposition method is adopted to couple 0.05g of initiator 2-bromo-2-methylpropanoic acid-4- (trichlorosilyl) butyl ester on the surface of 100g of the film.
(3) 6g N, N-dimethyl-N- (methacryloyloxybutyl) -N- (2-sulfoethyl) ammonium inner salt, 7g of hydroxyethyl methacrylate and 0.20g of cuprous bromide were weighed and reacted with the film in a toluene solution under stirring for 6 hours under an inert gas atmosphere at a temperature of 80 ℃.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 13
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 17mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 3 minutes.
(2) A vapor deposition method is adopted to couple 0.05g of initiator 2-bromo-2-methylpropanoic acid-4- (trichlorosilyl) butyl ester on the surface of 100g of the film.
(3) 8g N, N-dimethyl-N- (methacryloyloxyethyl) -N- (2-sulfobutyl) ammonium inner salt, 3g of hydroxypropyl methacrylate and 0.20g of cuprous bromide were weighed and reacted with the film in a toluene solution under stirring for 12 hours under an inert gas atmosphere at a temperature of 80 ℃.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 14
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 20mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 5 minutes.
(2) A vapor deposition method is adopted to couple 0.08g of initiator 2-bromo-2-methylpropanoic acid-4- (trichlorosilyl) butyl ester on the surface of 100g of the film.
(3) 8g N, N-dimethyl-N- (methacryloyloxybutyl) -N- (2-sulfopropyl) ammonium inner salt, 5g hydroxypropyl methacrylate and 0.20g cuprous bromide were weighed and reacted with the film in toluene solution under stirring for 12 hours under an inert gas atmosphere at a temperature of 60 ℃. A
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
Example 15
A preparation method of an antifogging self-cleaning polyimide film comprises the following steps:
(1) placing the transparent polyimide film in a plasma vacuum reaction cavity, continuously vacuumizing the cavity to be below 0.1Pa, introducing argon at the flow rate of 25mL/min, starting microwave type plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and continuously discharging for 5 minutes.
(2) A vapor deposition method is adopted to couple 0.08g of initiator 2-bromo-2-methylpropanoic acid-4- (trichlorosilyl) butyl ester on the surface of 100g of the film.
(3) 8g N, N-dimethyl-N- (methacryloyloxybutyl) -N- (2-sulfobutyl) ammonium inner salt, 5g of hydroxybutyl methacrylate and 0.020g of cuprous bromide were weighed and reacted with the film in a toluene solution under stirring at 60 ℃ under an inert gas atmosphere for 18 hours.
(4) After the reaction is finished, the film is respectively cleaned for 3 times by methanol and acetone, and nitrogen is used until the film is dried to obtain a finished product.
The optical properties and contact angle test results for the films prepared in examples 1-15 above are shown in Table 1.
TABLE 1 optical Properties and contact Angle test results for films prepared in examples 1-15
Serial number | Light transmittance (%) | Contact angle (°) |
Example 1 | 89.7 | 42.6 |
Example 2 | 88.6 | 39.1 |
Example 3 | 86.0 | 41.3 |
Example 4 | 87.5 | 36.4 |
Example 5 | 88.2 | 40.8 |
Example 6 | 85.3 | 36.6 |
Example 7 | 86.4 | 38.2 |
Example 8 | 87.7 | 36.6 |
Example 9 | 86.2 | 33.3 |
Example 10 | 87.1 | 32.0 |
Example 11 | 85.5 | 31.1 |
Example 12 | 84.6 | 30.7 |
Example 13 | 83.3 | 28.5 |
Example 14 | 83.7 | 28.1 |
Example 15 | 83.5 | 27.3 |
As can be seen from the detection results shown in table 1, the polyimide film provided by the present invention has good integrity, and the surface-modified hydrophilic polymer brush can maintain a high optical transmittance of 83% or more, effectively reduce the contact angle, and improve the hydrophilicity of the film surface.
Meanwhile, the examples 4, 8, 9 and 10 are better, the comprehensive performance is better, the light transmittance is higher than 86 percent,
the technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of polyimide film containing copolymer brush is characterized in that the method comprises the following steps of initiating Atom Transfer Radical Polymerization (ATRP) on the surface of the polyimide film;
(1) etching the surface of the transparent polyimide film by adopting plasma;
(2) adopting an initiator to couple to the surface of the polyimide film by a vapor deposition method;
(3) weighing a proper amount of monomer 1, monomer 2, cuprous bromide, 2' -bipyridyl and the treated film, placing the mixture into a solvent, and stirring and reacting for 6-18h under the protection of argon atmosphere and at the temperature of 50-90 ℃;
(4) and repeatedly washing the film by using deionized water and acetone to remove the catalyst on the surface and unreacted monomers, thus obtaining the polyimide film of the copolymer brush.
3. the method for preparing a polyimide film containing a copolymer brush according to claim 1, wherein the monomer 1 is one or more of N, N-dimethyl-N- (methacryloyloxyethyl) -N- (2-sulfoalkyl) ammonium inner salt, N-dimethyl-N- (methacryloyloxypropyl) -N- (2-sulfoalkyl) ammonium inner salt, or N, N-dimethyl-N- (methacryloyloxybutyl) -N- (2-sulfoalkyl) ammonium inner salt (N ═ 2-5), and has a structure shown as follows:
4. the method of preparing a polyimide film containing a copolymer brush according to claim 1, wherein the monomer 2 is one or more of methacrylic acid, N-methylpyrrolidone, sodium styrene sulfonate, oligo (ethylene glycol methyl ether) methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, or hydroxybutyl methacrylate, and has a structure as shown below:
5. the method for preparing the polyimide film containing the copolymer brush according to claim 1, wherein the step (1) of etching the surface of the transparent polyimide film by the plasma comprises the steps of placing the transparent polyimide film into a plasma vacuum reaction cavity, continuously vacuumizing the plasma cavity to be below 0.1Pa, introducing argon gas at a flow rate of 15-25mL/min, starting microwave plasma discharge to treat the surface of the film, wherein the discharge power is 200W, the frequency is 100MHz, and the etching treatment time is 1-5 minutes.
6. The method for producing a polyimide film containing a copolymer brush according to claim 1, wherein the mass fraction of the initiator with respect to the film mass in the step (2) is 0.02 to 0.08%.
7. The method for preparing a polyimide film containing a brush copolymer according to claim 1, wherein the mass fraction of the monomer 1 is 5 to 10%, the mass fraction of the monomer 2 is 2 to 6%, and the mass fraction of the cuprous bromide is 0.05 to 0.25% with respect to the film mass in the step (3).
8. The method for preparing a polyimide film containing a copolymer brush according to claim 1, wherein the solvent used in the step (3) is one of benzene, xylene, cyclohexanone, and anisole.
9. The method for preparing a polyimide film containing a copolymer brush according to claim 1, wherein the monomer 1 and the monomer 2 in the step (3) may be simultaneously added to the reaction system to form a random copolymer; or added to the reaction system in steps to form the block copolymer.
10. The polyimide film containing the copolymer brush is characterized in that the light transmittance of the antifogging self-cleaning polyimide film is more than 83%, and the contact angle is less than or equal to 42.6 degrees.
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