CN113817461B - Rare earth doped high-molecular fluorescent material and preparation method thereof - Google Patents
Rare earth doped high-molecular fluorescent material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a rare earth doped high polymer fluorescent material, which is mainly characterized in that the composition and the proportion of rare earth ions and ligands are changed, the stability and the dispersity of a rare earth fluorescent luminous body are enhanced by adopting a siloxane coating method, and finally an effective interaction is formed with a high polymer matrix, so that the multi-spectral conversion (mainly blue light and red light dual-band emission) of the rare earth doped high polymer material to ultraviolet light is realized, and the application of the rare earth doped high polymer material in the fields of light conversion films and the like can be met.
Description
Technical Field
The invention relates to the technical field of polymer fluorescent materials, in particular to a rare earth doped polymer fluorescent material with dual-waveband light emission and a preparation method thereof.
Background
According to the measurement of photosynthesis of plants, a blue light region with a wavelength range of about 440nm and a red region with a wavelength range of about 680nm are maximum absorption spectrum regions of chlorophyll a in plants, and a wavelength range of 400-650 nm is maximum absorption spectrum regions of chlorophyll b, c, carotenoid and the like. In an effective photosynthetic radiation light area of sunlight, the absorptivity of plants to purple-blue light (380-480 nm) is 95%, and the absorptivity of plants to orange-red light (620-680 nm) is 90%. The light conversion function of the light conversion agricultural greenhouse film is that on the basis of retaining light which is useful for the growth of crops, ultraviolet light which is useless or harmful to the growth and development of the crops in sunlight is effectively converted into blue-violet light and red-orange light which are required by the photosynthesis of the crops through the action of a light conversion agent, so that the utilization rate of the crops to the sunlight and the efficiency of the photosynthesis are effectively improved, the growth and development of the crops and the absorption of nutrients are promoted, and the content of chlorophyll in leaves and the quality of agricultural products are improved.
The light conversion agent has various types, and the light conversion agent has different types according to different principles, and due to the specific electronic arrangement and energy level structure of the rare earth element, the rare earth luminescent material has the unique advantages of high luminescent quantum efficiency, good color purity, long fluorescence life and the like. Compared with the rare earth inorganic compound light conversion agent, the rare earth complex light conversion agent is easy to disperse in a high polymer matrix, thereby improving the compatibility with the high polymer matrix material. In recent years, with the rapid development of light conversion films as a functional film in the commercial field, more and more research reports of rare earth light conversion agents and light conversion films have appeared, for example, chinese patents CN10696710B, CN106945365B, CN105385014B, and CN101434724B disclose the preparation and use methods of rare earth light conversion agents or light conversion films, respectively. The general service life of these light conversion films is not long enough, and the light conversion films are easily oxidized under illumination, and the oxidation resistance is weak, and the range of the absorption spectrum and the emission spectrum is narrow, and most of them mainly use single red light or blue light to convert light, and can not reach the full coverage of the favorable spectrum range of crops, so the polymer fluorescent material used for the light conversion films is adjusted and improved to realize the multi-spectrum conversion of ultraviolet light.
Disclosure of Invention
The invention aims to at least solve the problems of short light stabilization time, weak oxidation resistance and only single-wave emission of a light conversion agent in the prior art, and aims to provide a rare earth doped high-molecular fluorescent material capable of emitting light in a double waveband and a preparation method thereof.
In order to achieve the above object, the present invention employs a rare earth complex as a light conversion agent. The light conversion agent can convert ultraviolet light into red light and blue light and has the characteristic of dual-waveband emission. The general structural formula of the light conversion agent is (Ln) 1 ) p (Ln 2 ) q A m B n Rare earth organic complexes of, ln 1 ，Ln 2 Representing different rare earth ions, A represents a ligand 1, B represents a ligand 2, p is more than or equal to 0 and less than or equal to 1, q is more than or equal to 0 and less than or equal to 1, m is more than or equal to 0.1 and less than or equal to 3, n is more than or equal to 0.1 and less than or equal to 3;
ln is respectively selected from any one or two of cerium, neodymium, samarium, europium, terbium, erbium, thulium and ytterbium, preferably europium, cerium and samarium; a is 1- (3-hydroxy-4-carboxyphenyl) -4-carboxy-5-methyl-1H-1, 2, 3-triazole, and the structure is shown in formula I:
b is a 2-hydroxy-5-sulfonic benzoic acid compound, and the structure is shown as formula II:
in the formula II R 1 、R 2 、R 3 Each independently is hydrogen atom, alkyl, alkoxy, nitro, cyano, halogen substituted alkyl;
the alkyl is preferably C 1 -C 4 Including methyl, ethyl, propyl, isopropyl, butyl, isobutyl;
the alkoxy group is preferably C 1 -C 4 Linear alkoxy of (a), including methoxy, ethoxy, propoxy, butoxy;
the halogen-substituted alkyl group is preferably a trifluoromethyl group, a pentafluoroethyl group;
the preparation method of the organic compound B is obtained by one-step reaction of a formula III and sulfuric acid under the heating condition, wherein the sulfonic group is on a 5-position.
R in formula III 1 、R 2 、R 3 The groups are as defined above.
The preparation method of the rare earth doped polymer fluorescent material comprises the following steps:
(1) Adding the A ligand and the B ligand into ethanol according to different proportions for dissolving, slowly dropwise adding an ethanol solution of rare earth salt into the mixed solution, refluxing for 30min after dropwise adding, then dropwise adding a 3M sodium hydroxide solution into the mixed solution for regulating the pH value to 6.5-7, and refluxing for 4h. Filtering, washing with ethanol and deionized water, and vacuum drying at 60 deg.C for 28 hr to obtain complex.
(2) Preparing a polyvinylpyrrolidone solution, adjusting the pH of the solution to 2-3 by using glacial acetic acid, then adding methyltriethoxysilane, stirring for 3h, then adding the rare earth complex obtained in the step (1) with the particle size of 0.1-1 mu m, dispersing the solution by using ultrasound, adjusting the pH of the solution to 8-10 by using sodium hydroxide, stirring for 24h at 55 +/-5 ℃, filtering after the reaction is finished, washing by using deionized water, and drying in vacuum to obtain the rare earth complex microsphere coated by the oxysilane.
(3) And (3) uniformly mixing the microspheres prepared in the step (2) with high polymer resin according to the proportion of 5-10% in a high mixing machine, and extruding and granulating by using a double-screw extruder, wherein the high polymer resin is one or two of polyethylene, polypropylene, polyvinyl chloride and polyethylene-vinyl acetate.
The principle of the invention is as follows:
as the ligand A containing the azacyclo-phenyl carboxylic acids, a benzene ring and triazole in the structure can form a pi-pi interaction hyperconjugated system, and the ligand A has a plurality of coordination points, the ligand A can participate in the self-assembly of bimolecules with a 2-hydroxy-5-sulfonic-benzoic acid ligand B containing a plurality of coordination points under the action of deprotonation of carboxyl on the triazole, and the bimolecular ligand assembled by utilizing the interaction between molecules can emit part of blue light peculiar to the ligand A under the excitation of ultraviolet light and can convert the ultraviolet light into red orange light, so that the characteristic of emitting red light and blue light in a double-waveband is realized. The rare earth fluorescent material is prepared by coating methyltriethoxysilane on the outside of a rare earth complex formed by ligands A and B, and siloxane is used as an oxygen barrier layer to isolate oxygen, so that the luminescent center is prevented from being oxidized and decomposed in an excited state, and the service life and the durability of the fluorescent material are greatly improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The high molecular fluorescent material prepared by the invention can convert ultraviolet light into blue light and red orange light, has the characteristic of dual-waveband emission, and effectively converts the ultraviolet light harmful to the growth and development of crops into the blue light and the red orange light required by photosynthesis, thereby improving the utilization rate of the crops to sunlight.
(2) The preparation method of the rare earth doped high polymer fluorescent material is simple and quick to operate, siloxane is coated outside the rare earth complex and used as an oxygen barrier layer to isolate oxygen, so that the complex is effectively prevented from being oxidized and decomposed in an excited state, and the oxidation resistance and the durability of the complex are improved.
(3) The rare earth doped polymer fluorescent material provided by the invention can effectively absorb ultraviolet light of 200-400nm and emit fluorescence of red light and blue light double-waveband, and the fluorescent material has strong oxidation resistance, durability and long light stabilization time, and has important application prospect when being applied to the field of light conversion films.
Drawings
FIG. 1 shows emission spectra of rare earth-doped polymer phosphors prepared in examples 9 to 12 and comparative example 1.
Detailed Description
The present invention will be further described with reference to specific examples, and the starting materials and reagents used in the examples and comparative examples are commercially available in the conventional manners or can be obtained by a method known in the art, unless otherwise specified.
Example 1
Europium complex [ Eu (A) 1.5 (B 1 ) 1.5 ]The synthesis of (2):
A、B 1 the structure represented is as follows:
mixing (3.0 mmol) A and (3.0 mmol) B 1 Adding 30mL of ethanol into a 100mL three-necked bottle, stirring at room temperature to dissolve, slowly dropwise adding (2.0 mmol) 10mL of ethanol solution of europium trichloride hexahydrate into the mixed solution, refluxing for 30min after the dropwise adding is finished, then dropwise adding 3M sodium hydroxide solution into the reaction solution, adjusting the pH to 6.5-7, and refluxing for 4h. Filtering, washing with ethanol and deionized water, and vacuum drying at 60 deg.C for 28 hr to obtain light yellow powder.
Example 2
Europium complex [ Eu (A) 1.5 (B 2 ) 1.5 ]The synthesis of (2):
A、B 2 the representative structures are shown below:
mixing (3.0 mmol) A and (3.0 mmol) B 2 Adding 30mL of ethanol into a 100mL three-necked bottle, stirring at room temperature to dissolve, slowly dropwise adding (2.0 mmol) 10mL of ethanol solution of europium trichloride hexahydrate into the mixed solution, refluxing for 60min after dropwise adding, then dropwise adding 4M sodium hydroxide solution into the reaction solution, adjusting the pH to 6.5-7, and refluxing for 6h. Filtering, washing with ethanol and deionized water, and vacuum drying at 90 deg.C for 24 hr to obtain gray powder.
Example 3
Samarium Complex [ Sm (A) 1.5 (B 3 ) 1.5 ]The synthesis of (2):
A、B 3 the representative structures are shown below:
mixing (3.0 mmol) A and (3.0 mmol) B 3 Adding 30mL of ethanol into a 100mL three-necked bottle, stirring at room temperature to dissolve, slowly dropwise adding (2.0 mmol) 10mL of ethanol solution of samarium trichloride hexahydrate into the mixed solution, refluxing for 30min after dropwise adding, then dropwise adding 1M of sodium hydroxide solution into the reaction solution, adjusting the pH to 6.5-7, and refluxing for 8h. Filtering, washing with ethanol and deionized water, and vacuum drying at 50 deg.C for 48 hr to obtain yellow powder.
Example 4
Samarium Complex [ Sm (A) 1.5 (B 4 ) 1.5 ]The synthesis of (2):
A、B 4 the representative structures are shown below:
mixing (3.0 mmol) A and (3.0 mmol) B 4 Adding 30mL of ethanol into a 100mL three-necked bottle, stirring at room temperature to dissolve, slowly dropwise adding (2.0 mmol) 10mL of ethanol solution of samarium trichloride hexahydrate into the mixed solution, refluxing for 80min after dropwise adding, then dropwise adding 3M sodium hydroxide solution into the reaction solution, adjusting the pH to 6.5-7, and refluxing for 10h. Filtering, washing with ethanol and deionized water, vacuum drying at 60 deg.C for 12 hr,a light grey powder was obtained.
Example 5
Europium complex [ Eu (A) 2.7 (B 2 ) 0.3 ]The synthesis of (2):
A、B 2 the representative structures are shown below:
mixing (5.4 mmol) A and (0.6 mmol) B 2 Adding 30mL of ethanol into a 100mL three-necked bottle, stirring at room temperature to dissolve, slowly dropwise adding (2.0 mmol) 10mL of ethanol solution of europium trichloride hexahydrate into the mixed solution, refluxing for 100min after dropwise adding, then dropwise adding 4M sodium hydroxide solution into the reaction, adjusting the pH to 6.5-7, and refluxing for 10h. Filtering, washing with ethanol and deionized water, and vacuum drying at 60 deg.C for 25 hr to obtain gray powder.
Example 6
Samarium Complex [ Sm (A) 0.5 (B 2 ) 2.5 ]The synthesis of (2):
A、B 2 the structure represented is as follows:
a (1.0 mmol) and B (5.0 mmol) 2 Adding 30mL of ethanol into a 100mL three-necked bottle, stirring at room temperature to dissolve, slowly dropwise adding (2.0 mmol) 10mL of ethanol solution of samarium trichloride hexahydrate into the mixed solution, refluxing for 80min after dropwise adding, then dropwise adding 3M sodium hydroxide solution into the reaction solution, adjusting the pH to 6.5-7, and refluxing for 12h. Filtering, washing with ethanol and deionized water, and vacuum drying at 90 deg.C for 10 hr to obtain brown powder.
Example 7
Cerium europium complex [ Ce 0.5 Eu 0.5 (A) 1.5 (B 2 ) 1.5 ]The synthesis of (2):
A、B 2 the representative structures are shown below:
mixing (3.0 mmol) A and (3.0 mmol) B 2 Adding 30mL of ethanol into a 100mL three-necked bottle, stirring at room temperature to dissolve, respectively dropwise adding 5mL (1.0 mmol) of europium trichloride hexahydrate ethanol solution and 5mL (1.0 mmol) of cerium trichloride hexahydrate ethanol solution into the mixed solution, refluxing for 120min after dropwise adding, then dropwise adding 3M sodium hydroxide solution into the reaction solution, adjusting the pH to 6.5-7, and refluxing for 12h. Filtering, washing with ethanol and deionized water, and vacuum drying at 90 deg.C for 24 hr to obtain off-white powder.
Example 8
Cerium samarium Complex [ Ce 0.8 Sm 0.2 (A) 2.2 (B 4 ) 0.8 ]The synthesis of (2):
A、B 2 the structure represented is as follows:
a (1.0 mmol) and B (5.0 mmol) 4 Adding 30mL of ethanol into a 100mL three-necked bottle, stirring at room temperature to dissolve, respectively dropwise adding 4mL (0.4 mmol) of samarium trichloride hexahydrate ethanol solution and 10mL (1.6 mmol) of cerium trichloride hexahydrate ethanol solution into the mixed solution, refluxing for 30min after dropwise adding, then dropwise adding 1M sodium hydroxide solution into the reaction solution, adjusting the pH value to 6.5-7, and refluxing for 4h. Filtering, washing with ethanol and deionized water, and vacuum drying at 60 deg.C for 12 hr to obtain dark gray powder.
Example 9
Preparation example 2 europium Complex-doped Polymer fluorescent Material MS 1
Weighing 5.0g of polyvinylpyrrolidone, adding 1500mL of deionized water, adjusting the pH of the solution to 2-3 by using 1M glacial acetic acid, then adding 500g of methyltriethoxysilane, stirring for 3h, then adding 0.5g of the europium complex of the embodiment 2 with the particle size of about 400nm, ultrasonically dispersing the solution for 20min, adjusting the pH of the solution to 8-10 by using 4M sodium hydroxide solution, stirring for 24h at 55 +/-5 ℃, and finishing the reactionFiltering, washing with deionized water, vacuum drying at 55 ℃ for 24h to obtain europium complex microspheres, uniformly mixing the europium complex microspheres with polyethylene according to the proportion of 6.0% in a high-speed mixer, and extruding and granulating by using a double-screw extruder to obtain the europium complex doped high-molecular fluorescent material MS of the embodiment 2 1 。
Example 10
Preparation example 4 samarium Complex-doped Polymer fluorescent Material MS 2
Weighing 8.0g of polyvinylpyrrolidone, adding 2000mL of deionized water, adjusting the pH of the solution to 2-3 by using 2M glacial acetic acid, then adding 600g of methyltriethoxysilane, stirring for 5h, then adding 0.8g of the samarium complex of example 4 with the particle size of about 510nm, dispersing the solution by ultrasound for 20min, adjusting the pH of the solution to 8-10 by using a 4M sodium hydroxide solution, stirring for 24h at 75 +/-5 ℃, filtering after the reaction is finished, washing by using deionized water, drying in vacuum for 24h at 55 ℃ to obtain samarium complex microspheres, finally uniformly mixing the samarium complex microspheres with polyvinyl chloride and polyethylene-vinyl acetate in a high-speed mixer according to the proportion of 5.0%, and extruding and granulating by using a double-screw extruder to obtain the samarium complex doped high-molecular fluorescent material MS of example 4 2 。
Example 11
Preparation example 7 cerium europium Complex doped Polymer fluorescent Material MS 3
Weighing 10.0g of polyvinylpyrrolidone, adding 2500mL of deionized water, adjusting the pH of the solution to 2-3 by using 3M glacial acetic acid, then adding 1000g of methyltriethoxysilane, stirring for 5h, then adding 1.0 g of the cerium-europium complex of example 7 with the particle size of about 460nm, ultrasonically dispersing the solution for 60min, adjusting the pH of the solution to 8-10 by using 6M sodium hydroxide solution, stirring for 24h at 65 +/-5 ℃, filtering after the reaction is finished, washing by using deionized water, vacuum-drying for 48h at 65 ℃ to obtain cerium-europium complex microspheres, uniformly mixing the cerium-europium complex microspheres and polyethylene-vinyl acetate in a high-speed mixer according to the proportion of 7.5%, and extruding and granulating by using a double-screw extruder to obtain the cerium-europium complex doped high-molecular fluorescent material MS of example 7 3 。
Example 12
Preparation example 8 cerium samarium Complex-doped PolymerFluorescent material MS 4
Weighing 5.0g of polyvinylpyrrolidone, adding 1500mL of deionized water, adjusting the pH of the solution to 2-3 by using 1M of glacial acetic acid, then adding 500g of methyltriethoxysilane, stirring for 10h, then adding 0.5g of the samarium complex of embodiment 8 with the particle size of about 290nm, dispersing the solution by ultrasound for 60min, adjusting the pH of the solution to 8-10 by using 3M of sodium hydroxide solution, stirring for 24h at 85 +/-5 ℃, filtering after the reaction is finished, washing by using deionized water, and drying in vacuum at 55 ℃ for 24h to obtain samarium complex microspheres, uniformly mixing the samarium complex microspheres and polypropylene in a high-speed mixer according to the proportion of 9.0%, and extruding and granulating by using a double-screw extruder to obtain the samarium complex doped high-molecular fluorescent material MS of embodiment 8 4 。
Comparative example 1
Preparation of europium Complex [ Eu (DBM) 3 (phen)]Doped polymer fluorescent material MS 5 ：
After (6.0 mmol) Dibenzoylmethane (DBM) and (2.0 mmol) 1, 10-phenanthroline (phen) are stirred and dissolved with 30mL ethanol at room temperature, a 10mL ethanol solution of 2.0mmol europium trichloride hexahydrate is slowly dripped into the mixed solution, reflux is carried out for 30min after dripping is finished, then a 3M sodium hydroxide solution is dripped into the mixed solution, the PH is adjusted to 6.5-7, and reflux is carried out for 4h. Filtering, washing with ethanol and deionized water, and vacuum drying at 60 deg.C for 28 hr to obtain light yellow powder [ Eu (DBM) 3 Phen]. Weighing 5.0g polyvinylpyrrolidone, adding 1500mL deionized water, adjusting pH of the solution to 2-3 with 1M glacial acetic acid, adding 500g methyltriethoxysilane, stirring for 3h, and adding 0.5g [ Eu (DBM) with particle size of about 380nm 3 Phen]Dispersing the solution by ultrasonic treatment for 20min, adjusting the pH value of the solution to 8-10 by using a 4M sodium hydroxide solution, stirring for 24h at 55 +/-5 ℃, filtering after the reaction is finished, washing by using deionized water, drying for 24h at 55 ℃ in vacuum, uniformly mixing the obtained microspheres and polyethylene in a high-speed mixer according to the proportion of 6.0%, and extruding and granulating by using a double-screw extruder to obtain [ Eu (DBM) 3 (phen)]Doped polymer fluorescent material MS 5 。
FIG. 1 is a schematic view of emission spectra of rare earth doped polymer fluorescent materials prepared in examples 9 to 12 and comparative example 1. It can be seen that the rare earth doped polymer fluorescent materials prepared in examples 9-12 can obtain blue light and red light dual-band emission under the excitation of 254nm or 365nm ultraviolet light.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments, and many simple modifications can be made to the technical solution of the present invention within the technical concept of the present invention, and these simple modifications and combinations should be regarded as the disclosure of the present invention, and all fall into the protection scope of the present invention.
Claims (4)
1. A rare earth doped polymer fluorescent material is characterized in that: the fluorescent material comprises a rare earth complex and methyltriethoxysilane, wherein the methyltriethoxysilane is coated outside the rare earth complex to form microspheres, and the microspheres and high polymer resin are uniformly mixed to form a high polymer fluorescent material;
the rare earth complex converts ultraviolet light into red light and blue light for dual-band emission, and the general structural formula of the rare earth complex is (Ln) 1 ) p (Ln 2 ) q A m B n Said Ln 1 、Ln 2 Representing different rare earth ions, A represents a ligand 1, B represents a ligand 2, p is more than or equal to 0 and less than or equal to 1, q is more than or equal to 0 and less than or equal to 1, m is more than or equal to 0.1 and less than or equal to 3, n is more than or equal to 0.1 and less than or equal to 3;
the ligand A is 1- (3-hydroxy-4-carboxyphenyl) -4-carboxy-5-methyl-1H-1, 2, 3-triazole, and the structure is shown as the formula I:
the ligand B is a 2-hydroxy-5-sulfonic benzoic acid compound, and the structure is shown as the formula II:
in the formula II, R is 1 、R 2 、R 3 Each independently is a hydrogen atom, an alkyl group, an alkoxy group, a nitro group,Cyano or halogen-substituted alkyl;
the Ln 1 And Ln 2 Is selected from one or two of cerium, neodymium, samarium, europium, terbium, erbium, thulium and ytterbium.
2. The rare-earth doped polymer fluorescent material as claimed in claim 1, wherein Ln is present in 1 And Ln 2 Is europium, cerium or samarium.
3. The method for preparing the rare earth doped polymer fluorescent material according to claim 1, wherein the steps of the method are as follows:
(1) Adding the A ligand and the B ligand into ethanol according to different proportions for dissolving, slowly dropwise adding an ethanol solution of rare earth salt into the mixed solution, refluxing for 30min after dropwise adding, then dropwise adding a 3M sodium hydroxide solution into the mixed solution to adjust the pH value to 6.5-7, refluxing for 4h, filtering, washing with ethanol and deionized water, and carrying out vacuum drying at 60 ℃ for 28h to obtain a rare earth complex;
(2) Preparing a polyvinylpyrrolidone solution, adjusting the pH of the solution to 2-3 by using glacial acetic acid, adding methyltriethoxysilane, stirring for 3 hours, adding the rare earth complex obtained in the step (1) with the particle size of 0.1-1 mu m, and dispersing the solution by using ultrasound; adjusting the pH value of the solution to 8-10 by using sodium hydroxide, stirring for 24 hours at 55 +/-5 ℃, filtering after the reaction is finished, washing by using deionized water, and drying in vacuum to obtain rare earth complex microspheres coated by oxysilane;
(3) And (3) uniformly mixing the microspheres prepared in the step (2) with high polymer resin in a high mixing machine according to the proportion of 5-10%, wherein the high polymer resin is one or two of polyethylene, polypropylene, polyvinyl chloride and polyethylene-vinyl acetate.
4. The use of the rare earth doped polymer fluorescent material according to claim 1 in a light conversion film.
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