CN110669170B - Preparation method of polymer with aggregation-induced rare earth luminescence characteristics - Google Patents
Preparation method of polymer with aggregation-induced rare earth luminescence characteristics Download PDFInfo
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Abstract
The invention discloses a preparation method of a polymer with aggregation-induced rare earth luminescence characteristics, which specifically comprises the following steps: step 1, preparing 4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine; step 2, synthesizing a complex polymer according to the product obtained in the step 1; and 3, preparing terbium metal polymer according to the product obtained in the step 2. The metal polymer prepared by the method has stable structure, amphipathy and low toxicity.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a preparation method of a high polymer with aggregation-induced rare earth luminescence characteristics.
Background
In the scientific development process of polymer materials, people have not only satisfied the inherent characteristics of polymer materials, but have paid more attention to the research and development of special materials with special properties such as high and low temperature resistance, aging resistance, excellent electrical properties and some special functions such as light, electricity, magnetism and sound. Rare earth has optical, electrical, magnetic and other characteristics due to the particularity of its electronic structure, and these characteristics are powerful driving force for preparing rare earth metal polymer materials. The rare earth metal polymer exhibits the following advantages: (1) high brightness and good chemical stability; (2) different rare earth ions are doped to prepare luminophors with different characteristics; (3) the luminescent lifetime is much longer than the lifetime of the ordinary atomic excited state. However, since the absorption coefficient of trivalent rare earth ions in the ultraviolet region is very small, and the luminous efficiency is low, a strongly absorbing organic polymer ligand is required to be used as an "antenna" in the ultraviolet region, and the excited state energy is transferred to the emission state of rare earth ions by a nonradiative transition mode, so that the luminescence of rare earth ions is sensitized, which is the antenna effect. Therefore, the defect of small absorption coefficient of the rare earth ions in an ultraviolet-visible light region can be compensated by coordinating the rare earth ions with the organic polymer ligand. The organic polymer ligand needs to meet the following requirements: (a) the light absorption intensity of the ligand is good; (b) the efficiency of energy transfer between the ligand and the rare earth is high; (c) the emission state has proper energy and moderate service life. At present, the three most widely used ligands are beta-diketone, organic carboxylic acid and supermolecule macrocyclic.
Aggregation-induced emission (AIE) refers to a photophysical phenomenon in which a fluorescent chromophore emits little or no light in the solution state, while fluorescence is significantly enhanced in the solid or aggregated state. The rare earth metal polymer material with AIE activity can be widely applied by combining AIE and rare earth metal characteristic luminescence.
Disclosure of Invention
The invention aims to provide a preparation method of a polymer with aggregation-induced rare earth luminescence characteristics, and the prepared metal polymer has a stable structure, amphipathy and high brightness, and has excellent characteristic luminescence in a solid state.
The invention adopts the technical scheme that the preparation method of the polymer with the aggregation-induced rare earth luminescence property specifically comprises the following steps:
step 2, synthesizing a complex polymer according to the product obtained in the step 1;
and 3, preparing terbium metal polymer according to the product obtained in the step 2.
The invention is also characterized in that:
the specific process of the step 1 is as follows:
mixing 1-chloro-4-vinylbenzene and 1- (6-acetyl-4-hydroxy-pyridin-2-yl) -ethanone in a molar ratio of 1:1, dissolving in tetrahydrofuran, stirring the mixture at room temperature, and reacting for 24-48 hours to obtain 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone; then adding pyridine 2 times as much as 1-chloro-4-vinylbenzene and iodine crystals in equal ratio to 1-chloro-4-vinylbenzene for continuous reaction, and stirring the mixture for 30-60 minutes to form a light yellow solid 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone; then adding crotonaldehyde which is equal to 1-chloro-4-vinylbenzene, adding ammonium acetate which is 5 times of that of 1-chloro-4-vinylbenzene into the reaction solution for three times, and refluxing the solution for 12-24 hours; filtering and collecting the obtained light yellow solid which is 4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine.
The specific steps of the step 2 are as follows:
mixing and stirring the product obtained in the step 1 and azobisisobutyronitrile according to a molar ratio of 4:1, adding tetrahydrofuran and N, N-dimethylacrylamide which are equivalent to 1.2 times and 160 times of the azodiisobutyronitrile into the mixture, stirring for 0.5-1.5 hours, sealing the mixture into a reaction kettle, reacting for 4-6 hours at 100 ℃, terminating the reaction to obtain orange blocky particles, dissolving the orange blocky particles into acetone for precipitation, filtering, and drying to obtain orange powder: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine }.
The specific process of the step 3 is as follows:
preparing a tetrahydrofuran solution of terbium chloride hexahydrate, then adding a product in the step 2, which contains three times of terbium chloride hexahydrate, into the tetrahydrofuran solution of terbium chloride hexahydrate, adding 20mL of water, heating the mixture to 60 ℃, stirring for 3-5 hours, then recovering to normal temperature, continuously stirring overnight to finish the reaction, precipitating the mixture with diethyl ether, filtering, and drying to obtain off-white powder, namely terbium metal polymer: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridyl } terbium.
The dosage of the tetrahydrofuran solution of the terbium chloride hexahydrate in the step 3 is 0.03 mmol-0.05 mmol.
The invention has the following beneficial effects:
(1) the method for preparing the terbium metal polymer is simple and easy to operate;
(2) the terbium metal polymer prepared by the invention has stable structure and amphipathy;
(3) the terbium metal polymer obtained by the invention can emit green light, and the light emitting behavior of the terbium metal polymer can be adjusted in an N, N-dimethylformamide/1, 4-dioxane solution.
Drawings
FIG. 1 is a graph showing fluorescence emission of terbium metal macromolecules with different concentrations in N, N-Dimethylformamide (DMF) obtained in example 1 in a method for preparing a macromolecule with aggregation-induced rare earth luminescence property according to the present invention;
FIG. 2 is a diagram showing fluorescence emission of terbium metal polymer obtained in example 1 after adding 1, 4-dioxane (Diox) as a poor solvent with different volumes in a method for preparing a polymer with aggregation-induced rare earth luminescence property according to the present invention; tb can be observed at 545nm with increasing Diox volume fraction (e.g. 1:5) in the DMF/Diox system3+The ions gradually increase the green emission.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a polymer with aggregation-induced rare earth luminescence characteristics, which specifically comprises the following steps:
mixing 1-chloro-4-vinylbenzene and 1- (6-acetyl-4-hydroxy-pyridin-2-yl) -ethanone in a molar ratio of 1:1, dissolving in tetrahydrofuran, stirring the mixture at room temperature, and reacting for 24-48 hours to obtain 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone; then adding pyridine 2 times as much as 1-chloro-4-vinylbenzene and iodine crystals in equal ratio to 1-chloro-4-vinylbenzene for continuous reaction, and stirring the mixture for 30-60 minutes to form a light yellow solid 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone; then adding crotonaldehyde which is equal to 1-chloro-4-vinylbenzene, adding ammonium acetate which is 5 times of that of 1-chloro-4-vinylbenzene (each time at an interval of 30 minutes) into the reaction solution in three times, and refluxing the solution for 12-24 hours; filtering and collecting the obtained light yellow solid which is 4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine.
Step 2, synthesizing ligand macromolecules;
mixing the product obtained in the step 1 and azobisisobutyronitrile in a molar ratio of 4:1, stirring for 3 hours at 45 ℃, adding tetrahydrofuran and N, N-dimethylacrylamide which are equivalent to 1.2 times and 160 times of the equivalents of the azobisisobutyronitrile into the mixture, stirring for 0.5-1.5 hours, sealing the mixture in a reaction kettle, reacting for 4-6 hours at 100 ℃, terminating the reaction to obtain orange blocky particles, dissolving the orange blocky particles in acetone for precipitation, filtering, and drying to obtain orange powder: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine }.
Preparing 5mL (0.03 mmol-0.05 mmol) of a tetrahydrofuran solution of terbium chloride hexahydrate, then adding a product in the step 2 containing three times of terbium chloride hexahydrate into the solution, adding 20mL of water, heating the mixture to 60 ℃, stirring for 3-5 hours, recovering the normal temperature, continuing stirring overnight to finish the reaction, precipitating the mixture with diethyl ether, filtering, and drying to obtain off-white powder, namely terbium metal polymer: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridyl } terbium.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
20mmol of 1-chloro-4-vinylbenzene and 20mmol of 1- (6-acetyl-4-hydroxy-pyridin-2-yl) -ethanone were mixed and dissolved in 20mL of tetrahydrofuran, and the mixture was stirred at room temperature for 24 hours to obtain 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone. The reaction was continued with the addition of 40mmol of pyridine and 20mmol of iodine crystals, the mixture was stirred for 30 minutes to give a pale yellow solid of 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone, 20mmol of crotonaldehyde were added, 0.1mol of ammonium acetate were added in three portions (each 30 minutes apart) to the reaction solution, and the solution was refluxed for 12 hours. Filtering and collecting the obtained light yellow solid which is 4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine. Taking 0.2mmol of 4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine and 0.05mmol azobisisobutyronitrile are mixed and stirred at 45 ℃ for 3 hours, then 0.06mmol tetrahydrofuran and 8mmol N, N-dimethylacrylamide are added to the mixture and stirred for 0.5 hours, then the mixture is sealed in a reaction kettle and reacted at 100 ℃ for 4 hours, and the reaction is terminated, orange block particles are obtained, and the orange block particles are dissolved in 50mL acetone for precipitation, filtered and dried to obtain orange yellow powder: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine }. A5 mL solution of tetrahydrofuran containing 0.03mmol of terbium chloride hexahydrate was prepared, and then 0.09mmol of poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine }, and then 20mL of water. Heating the mixture to 60 ℃, stirring for 3 hours, recovering to normal temperature, continuing to stir overnight to finish the reaction, dissolving the mixture in 100mL of diethyl ether, precipitating, filtering and drying to obtain off-white powder, namely terbium metal polymer: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridyl } terbium.
FIG. 1 is a diagram showing fluorescence emission of terbium metal polymer obtained in this example in N, N-Dimethylformamide (DMF) at different concentrations; the terbium metal macromolecule is excited and emits green light at 545 nm. When the concentration of the terbium metal polymer is 4mg/mL, the emitted signal is stronger, and the emission almost disappears at low concentration (0.1mg/mL), namely, obvious aggregation-induced emission effect is displayed. FIG. 2 is a diagram showing fluorescence emission of terbium metal polymer after different volumes of 1, 4-dioxane (Diox) as a poor solvent were added to a low concentration (0.1mg/mL) of terbium metal polymer N, N-Dimethylformamide (DMF); increasing the volume fraction of Diox in the DMF/Diox system (e.g., 1:5) allows for a gradual enhancement of the green emission of terbium ions at 545nm to be observed.
Example 2
25mmol of 1-chloro-4-vinylbenzene and 25mmol of 1- (6-acetyl-4-hydroxy-pyridin-2-yl) -ethanone were mixed and dissolved in 20mL of tetrahydrofuran, and the mixture was stirred at room temperature to react for 36 hours, thereby obtaining 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone. The reaction was continued with the addition of 50mmol of pyridine and 25mmol of iodine crystals and the mixture was stirred for 45 minutes to form 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone as a pale yellow solid. An additional 25mmol of crotonaldehyde were added, 0.125mol of ammonium acetate (each time at 30 min intervals) were added in three portions to the reaction solution, and the solution was refluxed for a further 18 h. Filtering and collecting the obtained light yellow solid which is 4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine. Taking 0.3mmol of 4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine product and 0.075mmol azobisisobutyronitrile were mixed and stirred at 45 ℃ for 3 hours, then 0.09mmol tetrahydrofuran and 12mmol N, N-dimethylacrylamide were added to the mixture and stirred for 1 hour, then sealed in a reaction vessel and reacted at 100 ℃ for 5 hours, after which the reaction was terminated, giving orange-colored massive particles, which were precipitated in 50mL acetone, filtered and dried to give an orange-yellow powder: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine }. A5 mL solution of tetrahydrofuran containing 0.04mmol of terbium chloride hexahydrate was prepared, and then 0.12mmol of poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine }, and then 20mL of water. Heating the mixture to 60 ℃, stirring for 4 hours, recovering to normal temperature, continuing stirring overnight, finishing the reaction, dissolving the mixture in 100mL of diethyl ether, precipitating, filtering and drying to obtain off-white powder, namely terbium metal polymer: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridyl } terbium.
Example 3
30mmol of 1-chloro-4-vinylbenzene and 30mmol of 1- (6-acetyl-4-hydroxy-pyridin-2-yl) -ethanone were mixed and dissolved in tetrahydrofuran, and the mixture was stirred at room temperature for 48 hours to obtain 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone. The reaction was continued with the addition of 60mmol of pyridine and 30mmol of iodine crystals and the mixture was stirred for 60 minutes to form 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone as a pale yellow solid. A further 30mmol of crotonaldehyde are added, 0.15mol of ammonium acetate are added in three portions (each time at intervals of 30 minutes) to the reaction solution and the solution is refluxed for a further 24 hours. Filtering and collecting the obtained light yellow solid which is 4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine. Taking 0.4mmol of 4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine product and 0.01mmol azobisisobutyronitrile are mixed and stirred at 45 ℃ for 3 hours, then 0.012mmol tetrahydrofuran and 0.16mmol N, N-dimethylacrylamide which are equivalent to 1.2 times equivalent and 160 times equivalent of azobisisobutyronitrile are added into the mixture and stirred for 1.5 hours, then the mixture is sealed in a reaction kettle and reacted at 100 ℃ for 6 hours, and then the reaction is terminated, orange block particles are obtained, dissolved in 50mL acetone for precipitation, filtered and dried to obtain orange yellow powder: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine }. A5 mL solution of tetrahydrofuran containing 0.05mmol of terbium chloride hexahydrate was prepared, and then 0.15mmol of poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridine }, and then 20mL of water. Heating the mixture to 60 ℃, stirring for 5 hours, recovering to normal temperature, continuing to stir overnight, ending the reaction, dissolving the mixture in 100mL of diethyl ether, precipitating, filtering and drying to obtain off-white powder, namely terbium metal polymer: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2 "] terpyridyl } terbium.
Claims (1)
1. A method for preparing a polymer with aggregation-induced rare earth luminescence characteristics is characterized by comprising the following steps: the method specifically comprises the following steps:
step 1, preparing 4' - (4-isopropenyl-phenoxy) - [2,2';6',2' ' ] terpyridine;
step 2, synthesizing a complex polymer according to the product obtained in the step 1;
step 3, preparing terbium metal polymer according to the product obtained in the step 2;
the specific process of the step 1 is as follows:
mixing 1-chloro-4-vinylbenzene and 1- (6-acetyl-4-hydroxy-pyridin-2-yl) -ethanone in a molar ratio of 1:1, dissolving in tetrahydrofuran, stirring the mixture at room temperature, and reacting for 24-48 hours to obtain 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone; then adding pyridine 2 times as much as 1-chloro-4-vinylbenzene and iodine crystals in equal ratio to 1-chloro-4-vinylbenzene for continuous reaction, and stirring the mixture for 30-60 minutes to form a light yellow solid 1- [ 4-isopropenyl-6- (2-pyridin-1-yl-acetyl) -pyridin-2-yl ] -2-pyridin-1-yl-ethanone; then adding crotonaldehyde which is equal to 1-chloro-4-vinylbenzene, adding ammonium acetate which is 5 times of that of 1-chloro-4-vinylbenzene into the reaction solution for three times, and refluxing the solution for 12-24 hours; filtering and collecting the obtained light yellow solid which is 4' - (4-isopropenyl-phenoxy) - [2,2';6',2' ' ] terpyridine;
the specific process of the step 2 is as follows:
mixing and stirring the product obtained in the step 1 and azobisisobutyronitrile according to a molar ratio of 4:1, adding tetrahydrofuran and N, N-dimethylacrylamide which are equivalent to 1.2 times and 160 times of the azodiisobutyronitrile into the mixture, stirring for 0.5-1.5 hours, sealing the mixture into a reaction kettle, reacting for 4-6 hours at 100 ℃, terminating the reaction to obtain orange blocky particles, dissolving the orange blocky particles into acetone for precipitation, filtering, and drying to obtain orange powder: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2']Terpyridine };
the specific process of the step 3 is as follows: preparing a tetrahydrofuran solution of terbium chloride hexahydrate, then adding a product in the step 2, which contains three times of terbium chloride, into the tetrahydrofuran solution of terbium chloride hexahydrate, adding 20mL of water, heating the mixture to 60 ℃, stirring for 3-5 hours, recovering the normal temperature, continuing to stir overnight to finish the reaction, precipitating the mixture with diethyl ether, filtering, and drying to obtain off-white powder, namely terbium metal polymer: poly { N, N-dimethylacrylamide } -co- {4'- (4-isopropenyl-phenoxy) - [2,2';6',2']Terpyridine } terbium;
the dosage of terbium chloride hexahydrate in the step 3 is 0.03 mmol-0.05 mmol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06166727A (en) * | 1992-07-22 | 1994-06-14 | Hiroyoshi Shirai | Water-soluble polymer having terpyridyl group and polymer complex and catalyst coordinating the polymer |
| CN103374132A (en) * | 2013-07-12 | 2013-10-30 | 中科院广州化学有限公司 | Preparation and application of metal ion directly induced fluorescent supramolecular gel |
| CN109796602A (en) * | 2019-01-30 | 2019-05-24 | 陕西科技大学 | A kind of rare earth to shine at near-infrared folds the preparation method of nanometer polymer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06166727A (en) * | 1992-07-22 | 1994-06-14 | Hiroyoshi Shirai | Water-soluble polymer having terpyridyl group and polymer complex and catalyst coordinating the polymer |
| CN103374132A (en) * | 2013-07-12 | 2013-10-30 | 中科院广州化学有限公司 | Preparation and application of metal ion directly induced fluorescent supramolecular gel |
| CN109796602A (en) * | 2019-01-30 | 2019-05-24 | 陕西科技大学 | A kind of rare earth to shine at near-infrared folds the preparation method of nanometer polymer |
Non-Patent Citations (1)
| Title |
|---|
| Water soluble Ln(III)-based metallopolymer with AIE-active and ACQ-effect lanthanide behaviors for detection of nanomolar pyrophosphate;Zhang Zhao et al.;《SENSORS AND ACTUATORS B-CHEMICAL》;20181122;第282卷(第2019期);第1000-1001页第2.1-2.2部分，SI部分，方案1 * |
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