CN119798639A - White fluorescent hyperbranched polyether and preparation method thereof - Google Patents
White fluorescent hyperbranched polyether and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of polymer luminescent materials, and particularly relates to white fluorescent hyperbranched polyether and a preparation method thereof. Hyperbranched polyethers are prepared by autocatalysis of ring-opening and oxygen-Michael addition reactions of epoxy monomers and vinyl monomers under tertiary amine conditions in a solvent from monomers containing alcoholic hydroxyl groups and epoxy structures and from a variety of amide-containing vinyl monomers. The white fluorescent emission in room temperature environment can be realized by changing various terminal amide structures of hyperbranched polyether, and the material can be applied to the fields of living illumination, optical devices, anti-counterfeiting and the like. The preparation method has the advantages of simplicity, low price, environmental friendliness and the like, is suitable for large-scale production, and has good application prospect.
Description
Technical Field
The invention belongs to the field of polymer luminescent materials, and particularly relates to white fluorescent hyperbranched polyether and a preparation method thereof.
Background
With the recent trend of white fluorescent polymers in solid light sources, full-information display screen backlights and other fields, the white fluorescent polymers are increasingly colored. Compared with the traditional small molecular system, the polymer white light material has the advantages of simple process, low cost, easy large-area manufacture and the like. However, since white fluorescence needs to cover the entire visible light region emission, it is difficult to achieve by a single molecule, which results in difficulty in achieving such span of visible light emission in the same polymer.
Hyperbranched polymers stand out during research in the scientific community to find dendrimer substitutes. The unique topological structure and convenient synthesis advantages of the novel compound lead to wide interests of researchers. Among these hyperbranched polyethers are one of the most common and interesting hyperbranched polymers. The hyperbranched polyether structure generally contains 50-60% of branched structures. Because of the simple synthesis, special structure and unique property, a large number of terminal groups are very easy to introduce terminal functional groups according to the needs by a chemical or physical modification method so as to enhance or add special properties. Hyperbranched polyethers are generally modified by a single polyether backbone structure, and therefore, the modification is concentrated in a terminal group, and the terminal is modified into a functional group by a chemical bond reaction, thereby imparting a special function to the hyperbranched polyether. The functionalized hyperbranched polyether has been widely applied to biomedical science, nanotechnology, marine antifouling, surface modification, polyelectrolyte and other applications indispensible from people's production and living. However, hyperbranched polyethers with various terminal amide structures have not been reported as white fluorescent emission materials.
Disclosure of Invention
The invention aims to provide a hyperbranched polyether polymer material with white fluorescent emission and a preparation method thereof. The polymer material with the advantages of white fluorescence emission, good stability, wide monomer adaptability, low cost and the like is prepared.
In order to achieve the aim, the hyperbranched polyether is prepared by a one-step method under the self-catalysis condition by using a monomer containing alcoholic hydroxyl groups and epoxy structures and a plurality of vinyl monomers containing amide. The preparation method comprises the steps of preparing hyperbranched polyether by a one-step method under the self-catalysis condition in a solvent by using a monomer containing an alcoholic hydroxyl group and an epoxy structure and a plurality of vinyl monomers containing amide;
Wherein the monomer containing the alcoholic hydroxyl and the epoxy structure is one or more of glycidol, glycidyl methacrylate or allyl glycidyl ether.
The vinyl monomer is one or more of dimethylaminopropyl acrylamide, N-dimethylacrylamide or N-phenylmaleimide.
The molar ratio of the monomer containing the alcoholic hydroxyl group and the epoxy structure to the vinyl monomer is 1000:10-200.
The solvent is one or a mixture of a plurality of tetrahydrofuran, dimethyl sulfoxide, N' -dimethylformamide and dioxane organic solvents, and the mass of the solvent is 0.1-5 times of the mass of the monomer.
The reaction temperature adopted in the polymerization reaction stage is more than or equal to 25 ℃, and the reaction time range is 8-48 h.
The hyperbranched polyether polymer is dissolved in any one or two mixtures of tetrahydrofuran, dimethyl sulfoxide, N' -dimethylformamide and dioxane to prepare a 5mg/ml solution, and can emit macroscopic white fluorescence under excitation and irradiation of a point light source at 365 nm. Therefore, the white fluorescent hyperbranched polyether prepared by the invention can be used in the fields of living illumination, optical devices or anti-counterfeiting.
The beneficial effects are that:
(1) The invention has the advantages of cheap and industrially available raw materials, good material performance and wide application range, and is suitable for mass preparation.
(2) The polymerization reaction condition is mild, the reaction temperature is 25-100 ℃, and the hyperbranched polyether product does not need to remove the catalyst and does not influence the polymer properties due to the existence of the catalyst by adopting an autocatalysis mode.
(3) The polymer can be prepared by a simple compound through a one-step method under the autocatalysis condition, and white fluorescence emission can be realized by preparing solution after simple sedimentation.
Drawings
FIG. 1 is a photograph of examples 2, 3 and 6 under 365nm ultraviolet lamp excitation.
FIG. 2 is a HNHR test of the white fluorescent hyperbranched polyether polymer of example 3.
FIG. 3 is an FT-IR spectrum of a white fluorescent hyperbranched polyether polymer of example 3.
FIG. 4 is a fluorescence spectrum of the white fluorescent hyperbranched polyether polymer of example 4.
FIG. 5 is an ultraviolet absorbance graph of the white fluorescent hyperbranched polyether polymer of example 5.
FIG. 6 is a graph of quantum yields of the white fluorescent hyperbranched polyether polymer of example 7.
FIG. 7 is a plot of lifetime decay for the white fluorescent hyperbranched polyether polymer of example 8.
FIG. 8 is a normalized fluorescence spectrum of the white fluorescent hyperbranched polyether polymers of comparative example 1 and comparative example 3.
Detailed Description
The invention is further illustrated, but not limited to, the following examples, with reference to conventional techniques for process parameters not specifically identified.
Example 1
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, 2g (26.9 mmol) glycidol, 1.15g (6.7 mmol) dimethylaminopropyl acrylamide, 0.24g (3.4 mmol) acrylamide and 3.55g tetrahydrofuran were added thereto to cover the rubber stopper, and the mixture was placed in a 40℃oil bath for reaction for 6 hours. After the reaction, a pale yellow viscous liquid was obtained, which was precipitated in 100ml of n-hexane and dried, and then a polymer solution of 5mg/ml was prepared using dimethyl sulfoxide, and white fluorescence was emitted under excitation at 365 nm.
Example 2
The dried 100mL oil round bottom flask with rotor was placed in a glove box filled with argon atmosphere, 2g (26.9 mmol) glycidol, 1.15g (6.7 mmol) dimethylaminopropyl acrylamide, 0.34g (3.4 mmol) N, N-dimethylacrylamide and 3.55g tetrahydrofuran were added to the flask covered with rubber stopper, and the flask was placed in a 40℃oil bath to react for 6h. After the reaction, a white viscous liquid was obtained, which was precipitated in 100ml of n-hexane and dried, and then a polymer solution of 5mg/ml was prepared using dimethyl sulfoxide, which was excited at 365nm, and emitted blue fluorescence.
Example 3
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, 3.83g (51.7 mmol) glycidol, 0.91g (12.9 mmol) acrylamide, 0.64g (6.5 mmol) N, N-dimethylacrylamide and 196g tetrahydrofuran were added thereto to cover the rubber stopper, and the mixture was placed in a 40℃oil bath to react for 12 hours. After the reaction, a colorless viscous liquid was obtained, which was precipitated in 150ml of n-hexane and dried, and then a 5mg/ml polymer solution was prepared with tetrahydrofuran, and white fluorescence was emitted under excitation at 365 nm.
Example 4
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, 3.80 (51.3 mmol) glycidol, 1.27g (12.8 mmol) N, N-dimethylacrylamide, 1.11g (6.4 mmol) N-phenylmaleimide and 10g N, N-dimethylformamide were added thereto to cover the rubber stopper, and the mixture was placed in an 80℃oil bath to react for 48 hours. After the reaction, a white viscous liquid was obtained, which was precipitated in 50ml of n-hexane and dried, and then a polymer solution of 5mg/ml was prepared using dimethyl sulfoxide, and white fluorescence was emitted under excitation at 365 nm.
Example 5
A dried 100mL round bottom flask with a rotor was placed in a glove box filled with argon, 4.53g (31.9 mmol) of glycidyl methacrylate, 10.2g (8 mmol) of dimethylaminopropyl acrylamide, 1.04g (4 mmol) of acrylamide and 20g of N, N-dimethylformamide were added thereto to cover the rubber stopper, and the mixture was placed in a 100℃oil bath and reacted for 24 hours. After the reaction, a yellow viscous liquid was obtained, which was precipitated in 100ml of n-hexane and dried, and then a polymer solution of 5mg/ml was prepared using dimethyl sulfoxide, and white fluorescence was emitted under excitation at 365 nm.
Example 6
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, 2g (26.9 mmol) of glycidol, 0.48g (6.7 mmol) of acrylamide, 0.59g (3.4 mmol) of N-phenylmaleimide and 3.55g of tetrahydrofuran were added thereto to cover the rubber stopper, and the mixture was placed in a 40 ℃ oil bath for reaction for 6 hours. After the reaction, a pale yellow viscous liquid was obtained, which was precipitated in 100ml of n-hexane and dried, and then a polymer solution of 5mg/ml was prepared using dimethyl sulfoxide, and red fluorescence was emitted under excitation at 365 nm.
Example 7
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, 3.55g (25 mmol) of glycidyl methacrylate, 0.44g (6.25 mmol) of acrylamide, 0.31g (3.13 mmol) of N, N-dimethylacrylamide and 20g of N, N-dimethylformamide were added thereto to cover the rubber stopper, and the mixture was placed in a 60℃oil bath to react for 2 hours. After the reaction, a pale yellow viscous liquid was obtained, which was precipitated in 150ml of n-hexane and dried, and then a 5mg/ml polymer solution was prepared with tetrahydrofuran, and white fluorescence was emitted under excitation at 365 nm.
Example 8
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, to which 3.27g (20.4 mmol) of glycidyl methacrylate, 6.63g (10.2 mmol) of N, N-dimethylacrylamide, 1.56g (10.2 mmol) of N-phenylmaleimide and 50g of dimethyl sulfoxide were added to cover the rubber stopper, and placed in a 50℃oil bath to react for 6 hours. After the reaction, a pale yellow viscous liquid was obtained, which was precipitated in 150ml of n-hexane and dried, and then a 5mg/ml polymer solution was prepared with tetrahydrofuran, and white fluorescence was emitted under excitation at 365 nm.
Example 9
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, 3.39g (29.7 mmol) allyl glycidyl ether, 0.63 (7.4 mmol) dimethylaminopropyl acrylamide, 1.49g (3.7 mmol) acrylamide and 30g dioxane were added to it covered a rubber stopper, placed in a 40℃oil bath and reacted for 6h. After the reaction, a pale yellow viscous liquid was obtained, which was precipitated in 100ml of n-hexane and dried, and then a 5mg/ml polymer solution was prepared with tetrahydrofuran, and white fluorescence was emitted under excitation at 365 nm.
Example 10
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, 3.07g (26.9 mmol) allyl glycidyl ether, 0.48g (6.7 mmol) acrylamide, 0.59g (3.4 mmol) N-phenyl maleimide and 3.55g tetrahydrofuran were added thereto to cover the rubber stopper, and the mixture was placed in a 40℃oil bath to react for 6 hours. After the reaction, a pale yellow viscous liquid was obtained, which was precipitated in 100ml of n-hexane and dried, and then a polymer solution of 5mg/ml was prepared using dimethyl sulfoxide, and red fluorescence was emitted under excitation at 365 nm.
Example 11
A dried 100mL round bottom flask with a rotor was placed in a glove box filled with argon, 5.00g (43.8 mmol) allyl glycidyl ether, 0.78g (10.9 mmol) acrylamide, 0.44g (5.5 mmol) N, N-dimethylacrylamide and 30g N, N-dimethylformamide were added thereto to cover the rubber stopper, and the mixture was placed in a 50℃oil bath to react for 6 hours. After the reaction, a pale yellow viscous liquid was obtained, which was precipitated in 100ml of n-hexane and dried, and a 5mg/ml polymer solution was prepared using dioxane, and white fluorescence was emitted under excitation at 365 nm.
Example 12
A dried 100mL round bottom flask with a rotor was placed in a glove box filled with argon atmosphere, 3.84g (27.2 mmol) of allyl glycidyl ether, 0.67g (6.8 mmol) of N, N-dimethylacrylamide, 0.72g (3.4 mmol) of N-phenylmaleimide and 20g of tetrahydrofuran were added thereto to cover the rubber stopper, and the mixture was placed in a 25℃oil bath to react for 2 hours. After the reaction was completed, a pale yellow viscous liquid was obtained, which was precipitated in 150ml of n-hexane and dried, and then a 5mg/ml polymer solution was prepared using dioxane, and white fluorescence was emitted under excitation at 365 nm.
Comparative example 1
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, 0.2g (2.7 mmol) of glycidol, 0.28g (0.14 mmol) of dimethylaminopropyl acrylamide and 3g of N, N-dimethylformamide were added thereto to cover the rubber stopper, and the mixture was placed in a 40 ℃ oil bath for reaction for 6 hours. After the reaction, a white viscous liquid was obtained, which was precipitated in 150ml of n-hexane and dried, and a 5mg/ml polymer solution was prepared using dioxane, and blue fluorescence was emitted under excitation at 365 nm.
Comparative example 2
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, 1g (13.5 mmol) of glycidol, 0.24g (3.37 mmol) of acrylamide and 3g of N, N-dimethylformamide were added thereto to cover the rubber stopper, and the mixture was placed in an 80℃oil bath for reaction for 6 hours. After the reaction, a pale yellow viscous liquid was obtained, which was precipitated in 150ml of N-hexane and dried, and then a polymer solution of 5mg/ml was prepared with N, N-dimethylformamide, and red fluorescence was emitted under excitation at 365 nm.
Comparative example 3
The dried 100mL round-bottomed flask with the rotor was placed in a glove box filled with argon atmosphere, to which 1g (13.5 mmol) of glycidol, 0.58g (3.37 mmol) of N-phenylmaleimide and 3g of dimethyl sulfoxide were added to cover the rubber stopper, and reacted in a 50℃oil bath for 12 hours. After the reaction, a pale yellow viscous liquid was obtained, which was precipitated in 100ml of N-hexane and dried, and then a polymer solution of 5mg/ml was prepared with N, N-dimethylformamide, and red fluorescence was emitted under excitation at 365 nm.
Comparative example 4
The dried 100mL round bottom flask with the rotor was placed in a glove box filled with argon atmosphere, 1g (13.5 mmol) of glycidol, 0.28g (0.14 mmol) of N, N-dimethylacrylamide and 3g of tetrahydrofuran were added thereto to cover the rubber stopper, and the mixture was placed in a 40 ℃ oil bath to react for 8 hours. After the reaction, a colorless viscous liquid was obtained, which was precipitated in 100ml of N-hexane and dried, and then a polymer solution of 5mg/ml was prepared with N, N-dimethylformamide, and blue fluorescence was emitted under excitation at 365 nm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20120238641A1 (en) * | 2009-11-27 | 2012-09-20 | Basf Se | Dendritic polyurea for solubilizing active substances of low solubility |
| CN107652443A (en) * | 2017-10-31 | 2018-02-02 | 江南大学 | A kind of surface and the internal hyperbranched poly (ester amine) containing functional group and preparation method thereof |
| CN114292408A (en) * | 2021-12-07 | 2022-04-08 | 恩泰环保科技（常州）有限公司 | Hyperbranched phosphorus-free water treatment agent containing tertiary amine and preparation method and application thereof |
| CN115678243A (en) * | 2022-10-19 | 2023-02-03 | 常州大学 | A polymer phosphorescent material with high quantum yield and long phosphorescent lifetime and its preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120238641A1 (en) * | 2009-11-27 | 2012-09-20 | Basf Se | Dendritic polyurea for solubilizing active substances of low solubility |
| CN107652443A (en) * | 2017-10-31 | 2018-02-02 | 江南大学 | A kind of surface and the internal hyperbranched poly (ester amine) containing functional group and preparation method thereof |
| CN114292408A (en) * | 2021-12-07 | 2022-04-08 | 恩泰环保科技（常州）有限公司 | Hyperbranched phosphorus-free water treatment agent containing tertiary amine and preparation method and application thereof |
| CN115678243A (en) * | 2022-10-19 | 2023-02-03 | 常州大学 | A polymer phosphorescent material with high quantum yield and long phosphorescent lifetime and its preparation method |
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