Polyfluorene green fluorescent high molecular material, preparation method and application thereof
By synthesizing polyfluorene-based green fluorescent polymer materials through palladium catalysis, the problem of insufficient photostability of organic fluorescent materials has been solved, resulting in anti-counterfeiting materials with high stability and strong green light emission, which are suitable for anti-counterfeiting inks.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-04-24
- Publication Date
- 2026-03-20
AI Technical Summary
The photostability of existing organic fluorescent materials is insufficient, leading to material degradation and failure under prolonged light exposure, which limits their application in the field of anti-counterfeiting.
Anti-counterfeiting inks were prepared by using polyfluorene-based green fluorescent polymer materials and synthesizing terpolymers through palladium-catalyzed Suzuki or Stille polymerization reactions, combined with specific organic solvent solubility and high stability.
It provides fluorescent materials with high stability and strong green light emission, suitable for anti-counterfeiting inks, resistant to high temperatures and ultraviolet light, and extends service life.
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Figure CN116574242B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of fluorescent anti-counterfeiting materials, in particular to a polyfluorene green fluorescent polymer material, a preparation method and application thereof. BACKGROUND
[0002] Photoluminescence refers to the absorption of external light radiation by a substance to obtain energy, produce excitation and emit light of other wavelengths. Photoluminescence is a ubiquitous and important luminescence phenomenon, and materials based on photoluminescence have been widely used in lighting, display, anti-counterfeiting and other fields. Compared with traditional inorganic luminescent materials, organic luminescent materials have higher luminescent brightness and efficiency; active light source, fast response speed, large observation angle, easy to realize full and multi-functional display effect; soluble in specific organic solvents, convenient for application; can be combined with other various organic fluorescent materials, and combined into various color effects. Therefore, organic luminescent materials as core components are concerned in the field of organic electronic and optoelectronic functions. In organic luminescent materials, high polymers have excellent processability, thermal stability, flexibility, amorphous state and other advantages, effectively avoiding the problems of poor crystal stability and processability of small molecules, therefore, photoluminescent materials based on high polymers are increasingly valued by people.
[0003] In the field of anti-counterfeiting technology, photoluminescent materials are usually used as photosensitive anti-counterfeiting materials, however, due to the fact that organic anti-counterfeiting materials usually have insufficient light stability, long-time light irradiation leads to degradation and failure of the materials, therefore, there are relatively few commercially available organic anti-counterfeiting materials. Considering the advantages of high polymer materials in processing and cost, it is urgent to develop high-stability organic high polymer anti-counterfeiting materials through reasonable molecular design, in order to solve the problem of insufficient stability of organic anti-counterfeiting materials in the prior art. SUMMARY
[0004] In order to solve the problem of poor stability of existing organic fluorescent materials, the present application provides a polyfluorene green fluorescent polymer material, a preparation method and application thereof.
[0005] The technical scheme of the present application is as follows:
[0006] A polyfluorene green fluorescent polymer material, the structural formula is as follows:
[0007]
[0008] Among them, Ar is
[0009] R is
[0010] Wherein x is any decimal between 0-0.5, y is any decimal between 0-0.5, m is any integer between 1-20, n is any integer between 0-10, j is any integer between 1-20, k is any integer between 1-20.
[0011] Preferably, the structure of the polyfluorene green fluorescent high molecular material is as follows:
[0012]
[0013]
[0014] A method for preparing the polyfluorene green fluorescent high molecular material as described above, the method is as follows:
[0015] The boron ester or boronic acid or tin salt monomer of fluorene, the brominated monomer of benzene and the brominated monomer of Ar are single-bond connected through palladium catalyzed polymerization reaction;
[0016] Or the boron ester or boronic acid or tin salt monomer of fluorene, the boron ester or boronic acid or tin salt monomer of benzene and the brominated monomer of Ar are single-bond connected through palladium catalyzed polymerization reaction;
[0017] Or the brominated monomer of fluorene, the boron ester or boronic acid or tin salt monomer of benzene and the boron ester or boronic acid or tin salt monomer of Ar are single-bond connected through palladium catalyzed polymerization reaction;
[0018] Or the brominated monomer of fluorene, the brominated monomer of benzene and the boron ester or boronic acid or tin salt monomer of Ar are single-bond connected through palladium catalyzed polymerization reaction;
[0019] Or the boron ester or boronic acid or tin salt monomer of fluorene, the boron ester or boronic acid or tin salt monomer of Ar and the brominated monomer of benzene are single-bond connected through palladium catalyzed polymerization reaction;
[0020] Or the brominated monomer of fluorene, the brominated monomer of Ar and the boron ester or boronic acid or tin salt monomer of benzene are single-bond connected through palladium catalyzed polymerization reaction.
[0021] Preferably, the polymerization reaction is Suzuki polymerization reaction or Stille polymerization reaction.
[0022] An application of the polyfluorene green fluorescent high molecular material as described above, the polyfluorene green fluorescent high molecular material is applied as fluorescent powder in fluorescent anti-fake material.
[0023] An anti-fake ink, the anti-fake ink is mixed uniformly with the linking material, the filling material and the additional material by taking the polyfluorene green fluorescent high molecular material as described above as fluorescent powder, then is grinded through a grinding machine and finally is adjusted to obtain.
[0024] Preferably, the particle size of the ground polyfluorene green fluorescent high polymer material is 10-500 nm.
[0025] Preferably, the mixing proportion of the polyfluorene green fluorescent high polymer material is 0.5-20%.
[0026] Preferably, the filler is one or a mixture of at least two of colloidal calcium carbonate, aluminum hydroxide, gypsum powder, silicon dioxide, talc powder or diatomite.
[0027] Preferably, the additional material includes plasticizers, stabilizers, lubricants, adhesion promoters, drying agents and leveling agents.
[0028] Compared with the prior art, the present application solves the problem of poor stability of organic fluorescent materials, and has the following specific beneficial effects:
[0029] 1. The green fluorescent high polymer material provided by the present application is a terpolymer of fluorenyl, phenyl and bithiophene, dithiophene or benzothiadiazole, which has a light color itself, the starting band of the absorption spectrum is between 290-460 nm, and the strong green light emission of the high polymer has a maximum peak in the fluorescence spectrum between 470-590 nm, so that the green fluorescent high polymer material can be used as a fluorescent anti-counterfeiting material for the preparation of anti-counterfeiting ink or anti-counterfeiting ink, and has great application prospect in the field of fluorescent anti-counterfeiting.
[0030] 2. The high polymer provided by the present application can be dissolved in a specific organic solvent, which is convenient for the preparation of anti-counterfeiting ink or anti-counterfeiting ink, and has high stability, can withstand high temperature and ultraviolet radiation in film state, can be applied to actual production, and has long service life. BRIEF DESCRIPTION OF DRAWINGS
[0031] Figure 1 The thermogravimetric curve of the polyfluorene green fluorescent high polymer material 7 prepared in Example 5 is shown in the figure.
[0032] Figure 2 The absorption spectrum of the polyfluorene green fluorescent high polymer material 7 prepared in Example 5 is shown in the figure.
[0033] Figure 3 The emission spectrum of the polyfluorene green fluorescent high polymer material 7 prepared in Example 5 is shown in the figure. DETAILED DESCRIPTION
[0034] In order to make the technical solutions of the present application clearer, the technical solutions in the examples of the present application will be described clearly and completely below in conjunction with the drawings of the present application specification. It should be noted that the following examples are only used to better understand the technical solutions of the present application, and should not be understood as limiting the present application.
[0035] Example 1.
[0036] The present embodiment prepares a polyfluorene green fluorescent high molecular material 1, whose structural formula is as follows:
[0037]
[0038] The synthesis route of the above polyfluorene green fluorescent high molecular material is as follows:
[0039]
[0040] The specific preparation method is as follows:
[0041] Take 154.6 mg of dibromomonomer 1-1, 11.8 mg of dibromomonomer 1-2, 81.0 mg of dibromomonomer 1-3, 433.5 mg of diboron ester monomer 1-4 and 5.8 mg of tetrakis(triphenylphosphine)palladium into a polymerization tube filled with argon, add 1 drop of Aliquat 336, 2 mL of potassium carbonate and 30 mL of toluene, heat the reaction system to reflux under light shielding conditions, and react for 4 h; then add 0.061 g of phenylboronic acid and react for 2 h, add 0.12 mL of bromobenzene and react for 2 h, precipitate with excess methanol, filter, dissolve the solid product with dichloroethane, and remove the palladium catalyst by column; then precipitate with excess methanol, filter, and collect the product, which is dried at 70°C under vacuum to obtain a light yellow fibrous solid product 363.5 mg with a yield of 83%.
[0042] Elemental analysis is performed on the prepared polymer, and the theoretical calculation value is C, 82.93; H, 9.81; S, 7.26; and the experimental value is C, 82.99; H, 9.82; S, 7.19.
[0043] Gel permeation chromatography (GPC, 1,2,4-trichlorobenzene, polystyrene as standard, 150°C) analysis is performed on the prepared polymer, and the results are as follows: Mn=20300, PDI=1.67.
[0044] Example 2.
[0045] The present embodiment prepares a polyfluorene green fluorescent high molecular material 2, whose structural formula is as follows:
[0046]
[0047] The synthesis route of the above polyfluorene green fluorescent high molecular material is as follows:
[0048]
[0049] Into an argon purged polymerization tube, 185.0 mg of dibromomonomer 2-1, 11.8 mg of dibromomonomer 1-2, 81.0 mg of dibromomonomer 1-3, 509.6 mg of diboronate monomer 2-2 and 5.8 mg of tetrakis(triphenylphosphine)palladium were weighed out, 1 drop of Aliquat 336, 2 mL of 2 M potassium carbonate and 30 mL of toluene were added, the reaction system was heated to reflux under dark condition, reacted for 4 h, then 0.061 g of phenylboronic acid was added and reacted for 2 h, 0.12 mL of bromobenzene was added and reacted for 2 h, precipitated with excess methanol, filtered, the solid product was dissolved in dichloroethane, and the palladium catalyst was removed by column. The product was precipitated with excess methanol, filtered, and dried at 70 °C under vacuum to obtain a light yellow fibrous solid product 377.6 mg with a yield of 80%.
[0050] Elemental analysis was performed on the prepared polymer, and the theoretical calculation value was C, 84.66; H, 9.15; S, 6.19; and the experimental value was C, 84.32; H, 9.28; S, 6.40.
[0051] Gel permeation chromatography (GPC, 1,2,4-trichlorobenzene, polystyrene as standard, 160 °C) analysis was performed on the prepared polymer, and the results were as follows: Mn = 21400, PDI = 1.88.
[0052] Example 3.
[0053] In this example, a polyfluorene green fluorescent high molecular material 3 was prepared, and its structural formula was as follows:
[0054]
[0055] The synthetic route of the above polyfluorene green fluorescent high molecular material was as follows:
[0056]
[0057] Into an argon purged polymerization tube, 185.0 mg of dibromomonomer 2-1, 11.8 mg of dibromomonomer 1-2, 81.0 mg of dibromomonomer 1-3, 509.6 mg of diboronate monomer 2-2 and 5.8 mg of tetrakis(triphenylphosphine)palladium were weighed out, 1 drop of Aliquat 336, 2 mL of 2 M potassium carbonate and 30 mL of toluene were added, the reaction system was heated to reflux under dark condition, reacted for 4 h, then 0.061 g of phenylboronic acid was added and reacted for 2 h, 0.12 mL of bromobenzene was added and reacted for 2 h, precipitated with excess methanol, filtered, the solid product was dissolved in dichloroethane, and the palladium catalyst was removed by column. The product was precipitated with excess methanol, filtered, and dried at 70 °C under vacuum to obtain a light yellow fibrous solid product 377.6 mg with a yield of 80%.
[0058] Elemental analysis of the polymer prepared gave the following results: C, 82.12; H, 8.87; S, 6.01; O, 3.00 (theoretical); C, 82.24; H, 8.77; S, 6.05; O, 2.94 (experimental).
[0059] The polymer prepared was analyzed by gel permeation chromatography (GPC, 1,2,4-trichlorobenzene, polystyrene as standard, 160°C) and the results were as follows: Mn = 32000, PDI = 1.88.
[0060] Example 4.
[0061] In this example, a polyfluorene green fluorescent polymer material 4 was prepared, and its structural formula is as follows:
[0062]
[0063] The synthetic route of the polyfluorene green fluorescent polymer material is as follows:
[0064]
[0065] Into a polymerization tube filled with argon, 154.6 mg of dibromomonomer 1-1, 11.8 mg of dibromomonomer 1-2, 81.0 mg of dibromomonomer 4-1, 433.5 mg of diboron ester monomer 1-4 and 5.8 mg of tetrakis(triphenylphosphine)palladium were weighed, 1 drop of Aliquat 336, 2 mL of 2M potassium carbonate and 30 mL of toluene were added, the reaction system was heated to reflux under light-avoiding condition, and reacted for 4 h; then 0.061 g of phenylboronic acid was added and reacted for 2 h, 0.12 mL of bromobenzene was added and reacted for 2 h, precipitated with excess methanol, filtered, the solid product was dissolved in dichloroethane, and the palladium catalyst was removed by column; then precipitated with excess methanol, filtered, and the product was collected, and dried at 70°C under vacuum to obtain a light yellow fibrous solid product 337.2 mg, with a yield of 77%.
[0066] Elemental analysis of the polymer prepared gave the following results: C, 82.65; H, 9.87; S, 7.48 (theoretical); C, 82.63; H, 9.88; S, 7.49 (experimental).
[0067] The polymer prepared was analyzed by gel permeation chromatography (GPC, 1,2,4-trichlorobenzene, polystyrene as standard, 150°C) and the results were as follows: Mn = 21500, PDI = 1.87.
[0068] Example 5.
[0069] In this example, a polyfluorene green fluorescent polymer material 7 was prepared, and its structural formula is as follows:
[0070]
[0071] The synthetic route for the above-mentioned polyfluorene-based green fluorescent polymer materials is as follows:
[0072]
[0073] 154.6 mg of dibromo monomer 1-1, 11.8 mg of dibromo monomer 1-2, 29.4 mg of dibromo monomer 5-1, 433.5 mg of diboron ester monomer 1-4, and 5.8 mg of tetrakis(triphenylphosphine)palladium were weighed into an argon-filled polymerization tube. One drop of Aliquat 336, 2 mL of 2M potassium carbonate, and 30 mL of toluene were added. The reaction system was heated to reflux under light-protected conditions and reacted for 4 h. Then, 0.061 g of phenylboronic acid was added and reacted for 2 h, followed by the addition of 0.12 mL of bromobenzene and reacted for another 2 h. The product was precipitated with excess methanol, filtered, dissolved in dichloroethane, and column-filtered to remove the palladium catalyst. The product was then precipitated again with excess methanol, filtered, collected, and dried under vacuum at 70 °C to obtain 392.0 mg of a pale yellow fibrous solid product, with a yield of 86%.
[0074] Elemental analysis of the prepared polymer yielded theoretical values of C, 83.04; H, 9.92; N, 3.28; and S, 3.27, while experimental values were C, 83.11; H, 9.91; N, 3.23; and S, 3.75.
[0075] The prepared polymer was analyzed by gel permeation chromatography (GPC, 1,2,4-trichlorobenzene, polystyrene as standard, 150℃), and the results are as follows: Mn = 32500, PDI = 1.75.
[0076] Thermogravimetric analysis was performed on the polyfluorene-based green fluorescent polymer material 7 prepared in this embodiment. The results are shown in the figure. Figure 1 As shown, the material shows almost no change below 300℃, and only begins to decompose rapidly when the temperature rises above 350℃. This proves that the polyfluorene-based green fluorescent polymer material prepared in this embodiment has extremely high stability and high temperature resistance.
[0077] The absorption and emission spectra of the polyfluorene-based green fluorescent polymer material 7 prepared in this embodiment were measured. The absorption spectrum is shown in the figure. Figure 2 As shown, the emission spectrum is shown in the image. Figure 3 As shown, the initial sideband of its absorption spectrum is between 290 and 460 nm, and its color is relatively light. The maximum peak of its fluorescence spectrum is between 490 nm and 570 nm, which is strong green light emission. Therefore, it can be used as a fluorescent anti-counterfeiting material for the formulation of anti-counterfeiting inks or anti-counterfeiting inks, and has great application prospects in the field of fluorescent anti-counterfeiting.
[0078] Obviously, the above embodiments are merely example for clearly illustrating but not limitation to the embodiments. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, all the embodiments need not and can not be enumerated. The obvious changes or variations derived from the above description are still within the protection scope of the present application.
Claims
1. An anti-counterfeiting ink, characterized in that, The anti-counterfeiting ink uses polyfluorene-based green fluorescent polymer as the fluorescent powder. It is mixed evenly with binders, fillers, and additives, then ground using a grinding mill, and finally conditioned to obtain the final product. The structural formula of the polyfluorene-based green fluorescent polymer is as follows: ； Where Ar is , or ; R is , , , , or ; Where x is any decimal between 0 and 0.5, y is any decimal between 0 and 0.5, m is any integer between 1 and 20, n is any integer between 0 and 10, j is any integer between 1 and 20, and k is any integer between 1 and 20.
2. The anti-counterfeiting ink according to claim 1, characterized in that, The structural formula of the polyfluorene-based green fluorescent polymer material is: , , , , , , , or .
3. An anti-counterfeiting ink as described in claim 1 or 2, characterized in that, The preparation of the polyfluorene-based green fluorescent polymer material is as follows: Fluorene boron esters or boric acid or tin salt monomers, benzene brominated monomers and Ar brominated monomers are linked by single bonds through a palladium-catalyzed polymerization reaction. Alternatively, fluorene boron esters or boric acid or tin salt monomers, benzene boron esters or boric acid or tin salt monomers, and Ar brominated monomers can be linked by single bonds via palladium-catalyzed polymerization. Alternatively, fluorene bromide monomers, benzene borate or boric acid or tin salt monomers and Ar borate or boric acid or tin salt monomers can be linked by single bonds through palladium-catalyzed polymerization. Alternatively, fluorene brominated monomers, benzene brominated monomers, and Ar boron esters, boric acids, or tin salt monomers can be linked by single bonds via palladium-catalyzed polymerization. Alternatively, fluorene boron esters, boric acids, or tin salt monomers, Ar boron esters, boric acids, or tin salt monomers, and benzene bromine monomers can be linked by single bonds via palladium-catalyzed polymerization. Alternatively, fluorene brominated monomers, Ar brominated monomers, and benzene borate, boric acid, or tin salt monomers can be linked by single bonds via palladium-catalyzed polymerization.
4. The anti-counterfeiting ink according to claim 3, characterized in that, The polymerization reaction is either a Suzuki polymerization reaction or a Stille polymerization reaction.
5. The anti-counterfeiting ink according to claim 1, characterized in that, The particle size of the ground polyfluorene-based green fluorescent polymer material is 10nm~500nm.
6. The anti-counterfeiting ink according to claim 1, characterized in that, The mixed proportion of the polyfluorene-based green fluorescent polymer material is 0.5% to 20%.
7. The anti-counterfeiting ink according to claim 1, characterized in that, The filler is one or a mixture of at least two of the following: colloidal calcium carbonate, aluminum hydroxide, gypsum powder, silica, talc, or diatomaceous earth.
8. The anti-counterfeiting ink according to claim 1, characterized in that, The additives include plasticizers, stabilizers, lubricants, adhesion promoters, drying agents, and leveling agents.
Citation Information
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