CN-117402284-B - High-viscosity fluorine-containing polymer solution and application thereof

Abstract

The invention belongs to the technical field of production of response materials, and particularly relates to a high-viscosity fluorine-containing polymer solution and application thereof, wherein the preparation method of the high-viscosity fluorine-containing polymer solution comprises the following steps: dissolving naphthalene (methyl) acrylate, fluorine-containing methacrylate and vinyl carbazole in a solvent, stirring and dissolving to obtain a clear and transparent solution, adding an initiator, heating to 60-90 ℃ under magnetic stirring for polymerization for 16-24h to obtain a transparent high-viscosity polymer solution after the reaction is finished, wherein the viscosity range is 800-8000 Pa.s, the high-viscosity fluorine-containing polymer solution forms an anti-counterfeiting coating after a substrate is formed into a film, can be stimulated by ultraviolet light, trifluoroacetic acid and the like, and shows excellent multiple stimulation responsiveness.

Inventors

• LIU XIA
• GONG WEI
• FENG DIANYING
• ZHAI CONGCONG
• ZHAO HUA
• LIN SHUAI
• ZHANG KUN
• HAN JIQING
• GENG YUXUAN
• WANG WEI

Assignees

• 山东非金属材料研究所

Dates

Publication Date

20260505

Application Date

20231110

Claims (9)

1. 1. Dissolving naphthalene methacrylate, fluorine-containing methacrylate and vinyl carbazole in a solvent A, stirring to obtain a clear and transparent solution, adding an initiator, heating to 60-90 ℃ under magnetic stirring, and polymerizing for 16-24h to obtain a transparent high-viscosity polymer solution with the viscosity ranging from 800 Pa-8000 Pa.s after the reaction is finished; wherein the weight percentage of the naphthalene methacrylate is 2-20%, the weight percentage of the fluorine-containing methacrylate is 30-60%, the weight percentage of the vinyl carbazole is 2-30%, the weight percentage of the solvent A is 10-50%, and the initiator accounts for 0.01-10% of the total mass of the monomer.
2. 2. A high viscosity fluoropolymer solution according to claim 1, wherein, the fluorine-containing methacrylate is trifluoroethyl methacrylate tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate tetrafluoropropyl methacrylate hexafluorobutyl methacrylate.
3. 3. The high-viscosity fluorine-containing polymer solution according to claim 1, wherein the preparation of the naphthalene methacrylate is characterized in that naphthol, triethylamine and anhydrous tetrahydrofuran are firstly added, methacryloyl chloride is dropwise added under the condition of ice water bath while stirring, the ice water bath is removed after the dropwise addition, the reaction is carried out at room temperature for 19-30 hours, transparent liquid is obtained after the reaction is finished, white solid is obtained after solvent is distilled off, and the naphthalene methacrylate is obtained after post treatment.
4. 4. The high-viscosity fluoropolymer solution according to claim 3, wherein the molar ratio of naphthol to triethylamine is 1:1-3, the molar ratio of naphthol to methacryloyl chloride is 1:1-1.5, and the addition amount of tetrahydrofuran is 50-70wt% of the system.
5. 5. A high-viscosity fluoropolymer solution according to claim 3, wherein said post-treatment comprises dissolving the white solid in solvent B, washing with deionized water, saturated sodium bicarbonate and saturated saline solution, drying with anhydrous magnesium sulfate, and removing solvent to obtain the desired product naphthalene methacrylate.
6. 6. The high-viscosity fluoropolymer solution according to claim 1, wherein said initiator is one of azobisisobutyronitrile, benzoyl peroxide, tert-butyl peroxypivalate, and said solvent A is one of N, N-dimethylformamide, butyl acetate, ethyl acetate, and dimethyl sulfoxide.
7. 7. Use of the high viscosity fluoropolymer solution according to any one of claims 1-6 in the field of dual anti-counterfeiting.
8. 8. The use of a high viscosity fluoropolymer solution according to claim 7 in dual anti-counterfeit applications, wherein the high viscosity polymer solution is applied to a substrate by spin coating or dip-dyeing or casting to form a film, thereby obtaining an anti-counterfeit coating.
9. 9. The application of the high-viscosity fluorine-containing polymer solution in the dual anti-counterfeiting field according to claim 8, wherein the preparation method of the anti-counterfeiting coating is characterized in that the high-viscosity polymer solution is dissolved in a solvent C to prepare a polymer solution with the concentration of 0.5-10wt%, the polymer solution is stirred to form a uniform transparent solution, the transparent solution is arranged on a substrate in a spin coating or dip dyeing or casting mode at room temperature, and the anti-counterfeiting coating is obtained by vacuum drying.

Description

High-viscosity fluorine-containing polymer solution and application thereof Technical Field The invention belongs to the technical field of production of response materials, and particularly relates to a high-viscosity fluorine-containing polymer solution and application thereof. Background The common watermark anti-counterfeiting technology not only needs complex technology and complicated anti-counterfeiting process, but also can be easily copied, and is difficult to achieve the effective anti-counterfeiting purpose. The optical anti-counterfeiting technology has attracted wide attention in the anti-counterfeiting field because of the advantages of convenient design, good visibility, low cost, strong mass production capacity and the like. At present, the optical anti-counterfeiting material mainly comprises a structural color anti-counterfeiting material, a liquid crystal anti-counterfeiting material, a fluorescent anti-counterfeiting material and the like. However, the anti-counterfeiting and information encryption modes based on a single optical phenomenon have limitations in the reliability and information density of the anti-counterfeiting. Therefore, the combination of different stimulus-responsive anti-counterfeiting materials has become a research hotspot in recent years. Although some composite materials combining multiple stimulus responses have appeared in recent years, the information density and the dimension of anti-counterfeiting can be effectively increased, but the problems of high preparation cost, complex preparation process, short service life and the like still exist. Patent CN108424482B discloses a multiple-response dendritic polymer containing spiropyran and a preparation method thereof, firstly, polyester and caprolactone are subjected to ring opening to obtain dendritic polycaprolactone, then the dendritic polycaprolactone reacts with dibromoisobutyryl bromide and triethylamine to obtain dendritic macromolecular initiator, then the dendritic macromolecular initiator reacts with tert-butyl methacrylate to obtain HPs-Star-PCL-B-PtbMA, the product is hydrolyzed and then reacted with hydroxyl spiropyran through esterification to obtain HPs-Star-PCL-B-PMAA-SP, and the micelle with light response and pH response is obtained after self-assembly. However, the expensive cost and the complex synthesis process of the spiropyran are unfavorable for industrialized application, the spiropyran structure is closely packed in a solid state, and a certain free volume is needed for isomerization ring opening, so that the spiropyran is difficult to open in the solid state under the stimulation of external conditions such as ultraviolet light, acid and the like due to the contradiction between the spiropyran structure and the spiropyran, and the spiropyran is slow in color change and even does not change. CN113788972B discloses a color-changing anti-counterfeiting film with multiple responses, the color-changing anti-counterfeiting film is composed of three layers, an upper layer and a lower layer are obtained by solidifying a pre-solid solution composed of a polymer monomer and a solidifying agent into a film, and a middle layer is a photonic crystal layer formed by self-assembly of fluorescent colloid particles. Wherein the fluorescent colloid particles are obtained by coating a shell layer on the outer layer after the quantum dots are loaded on the colloid microspheres. The color-changing anti-counterfeiting film can show fluorescent color under the irradiation of an ultraviolet lamp, can generate visual structural color change after being stretched to a certain extent, and can recover the initial shape and color after the pulling force is removed. Compared with single structural color anti-counterfeiting and single fluorescent anti-counterfeiting, the film has multiple response color-changing characteristics, realizes the synergistic anti-counterfeiting of the photonic crystal structural color and the quantum dot fluorescence, improves the anti-counterfeiting level, and has wide application prospect in the anti-counterfeiting field. However, the complex multilayer film forming technology of the photonic crystal is not beneficial to the industrial application, and in addition, the film structure can be damaged by long-time ultraviolet irradiation, so that the service life is influenced. Disclosure of Invention Aiming at the existing problems, the invention provides the high-viscosity fluorine-containing polymer solution and the application thereof, the high-viscosity fluorine-containing polymer solution forms the anti-counterfeiting coating after a substrate is formed into a film, the anti-counterfeiting coating can be stimulated by ultraviolet light, trifluoroacetic acid and the like, and excellent multiple stimulation responsiveness is shown. The novel fluorine-containing polymer prepared by the invention has the advantages that naphthol can generate light Fries rearrangement reaction in the struc