CN101402855A - Polyarylether rare-earth complexes luminous material and preparing process thereof - Google Patents
Polyarylether rare-earth complexes luminous material and preparing process thereof Download PDFInfo
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- CN101402855A CN101402855A CNA200810012430XA CN200810012430A CN101402855A CN 101402855 A CN101402855 A CN 101402855A CN A200810012430X A CNA200810012430X A CN A200810012430XA CN 200810012430 A CN200810012430 A CN 200810012430A CN 101402855 A CN101402855 A CN 101402855A
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Abstract
The invention belongs to the field of polymer materials and relates to a luminescent material of a novel PAE rare earth composition as well as a preparation method thereof. The PAE rare earth composition is obtained by taking the PAE each structure unit of the main chain of which is provided with a carboxyl as a macromolecular ligand and taking the organic micromolecular compounds like BPT as a co-ligand to be coordinated and composed with one or a plurality of rare earth ions. The luminescent material of the PAE rare earth composition has excellent dissolvability in a plurality of normally used solvents, can be produced into solid powder, can also be produced into a transparent film, can give out bright fluorescence of different colors under the irradiation of UV-lights and can be applied to the fields like optical display, anti-fake labels or rare earth polymer optical amplifiers, and the like.
Description
Technical field
The invention belongs to polymeric material field, relate to class polyarylether rare-earth complexes luminous material and preparation method thereof.
Background technology
Rare earth element has characteristics such as light, electricity, magnetic and catalysis because of the singularity of its electronic structure, with it as luminescence center, widespread use in inorganic and luminous organic material.Yet, the difficult machine-shaping of rare earth inorganic materials, price height, there are problems such as poor stability, film forming difficulty in rare earth organic molecule title complex, these effects limit the further application of rare earth luminescent material.Polymkeric substance itself have abundant raw material, synthetic convenient, forming process easily, many advantages such as strong shock resistance, in light weight and cost be low, if can rare earth be incorporated in the polymer matrix, can obtain the functional materials that a class has wide application prospect.
Wolff in 1963 and Pressley have carried out the research of rare earth polymer aspect first, and they have studied Eu (TTA)
3Fluorescence and laser property in polymethylmethacrylate (PMMA) have been started the frontier of rare earth and the compound research of polymkeric substance.The short-cut method that rare earth ion is introduced in the macromolecular material is to mix, and promptly the mode of organic molecule rare earth compounding by solution or melt blending is doped in and obtains doping type rare earth polymer (doping-type rare-earth polymers) in the polymkeric substance.But this method prepares the mixture middle-weight rare earths and high molecular consistency is poor, and rare earth is assembled cluster and easily caused quenching of fluorescence, influences luminous intensity and life-span.And the bonding type rare earth polymer (bonding-typerare-earth polymers) that the rare earth ion Direct Bonding prepares on polymer chain can be overcome above-mentioned deficiency to a certain extent, the fluorescent material middle-weight rare earths ion distribution that makes is even, when ree content is higher, still can keep higher fluorescence intensity, and have the processibility and the transparency preferably.Therefore, the bonding type rare earth polymer that has the excellent processability of good luminous performance of rare earth element and macromolecular material concurrently is the functional materials that a class has application potential, has caused people's extensive concern.With the polyacrylic acid is that macromolecular ligand and rare-earth ion coordination can prepare the bonding type rare earth high polymer material, but the second-order transition temperature of polyacrylic resin and heat-resistant stability are not high.
Summary of the invention
The objective of the invention is polyarylether rare-earth complexes luminous material that proposes a kind of Heat stability is good, convenient processing and preparation method thereof.
Technical scheme of the present invention is: the rare complex luminescent material of going up of polyarylether is a macromolecular ligand by the polyarylether of being with carboxyl, and organic molecule makes with rare earth ion coordination in suitable organic solvent as being total to part.
The structural formula of the above-mentioned polyarylether macromolecular ligand that has a carboxyl is as follows:
Substituent R in the formula
1To R
4Can be hydrogen atom, halogen atom, nitro, or C
1To C
20Identical or different fat alkane and derivative thereof, or C
6To C
12Identical or different aromatic hydrocarbon and derivative thereof; A is C=O (polyaryletherketone) or SO
2(polyether sulphone).
The above-mentioned structural formula that has active carboxylic acid's group polyaryletherketone or a polyether sulphone is as follows:
Wherein, A is C=O (PEK-L) or SO
2(PES-L).
The above-mentioned structural formula that has active carboxylic acid's group polyaryletherketone or a polyether sulphone is as follows:
Wherein, A is C=O (DMPEK-L) or SO
2(DMPES-L).
The above-mentioned structural formula that has active carboxylic acid's group polyaryletherketone or a polyether sulphone is as follows:
Wherein, A is C=O (IMPEK-L) or SO
2(IMPES-L).
Above-mentioned contain the carboxyl polyarylether and can use separately, also can severally arbitrarily contain the carboxyl polyarylether and mix with arbitrary proportion and use.
Organic molecule part used in the present invention is organic acid R-COOH, and wherein R is C
1To C
18Halo or not halogenated fat or aromatic group; Or be phenanthroline, oxine, methyl ethyl diketone, benzoyl acetone, α-thenoyltrifluoroacetone, benzoyltrifluoroacetone, 2,2 '-dipyridyl, 2,2 ': 6 ', 2 "-terpyridyl, trioctyl-phosphine oxide, tributyl phosphate, hexaoxacyclooctadecane-6-6 or 15-crown ether-5; Or be any several mixture in the above-mentioned part.
Rare earth used in the present invention is one or more the mixture in europium, terbium, samarium, erbium, dysprosium, ytterbium, holmium, thulium, neodymium, lanthanum, the cerium.
Preparation polyarylether rare-earth complexes luminous material method provided by the invention, preparation process is: will contain the carboxyl polyarylether, the organic molecule part, rare earth oxide, muriate or nitrification thing, in organic solvent, be mixed in proportion, the mol ratio of the carboxyl of polyarylether and organic molecule part is 1.0: 0-0: 1.0, the carboxyl of polyarylether and the mol ratio of rare earth ion are 1.0: 0-0: 1.0, in 0 ℃ of-100 ℃ of temperature range mechanical stirring 0.5-24 hour then, resulting solution can directly be filmed or spinning, also can be with the sedimentation in sinking agent of this solution, wash three times, obtain the pulverulent solids product after the drying, productive rate 90-95%.
Among the above-mentioned preparation method, described solvent is dimethyl sulfoxide (DMSO), N, dinethylformamide, N, the mixture of one or more solvents in N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, tetrahydrofuran (THF) or the acetone, its consumption are 0.5-200 milliliter solvent/gram (polyarylether, organic molecule part and rare earth compound).Described sinking agent is one or more the mixture in ethanol, methyl alcohol or the water.
The fluorescence spectrum of polyarylether rare-earth complexes luminous material of the present invention adopts U.S. PTI-700 type fluorescence lifetime determinator to measure.
The present invention adopts polyarylether as matrix resin, measure its second-order transition temperature more than 200 ℃ with the DSC method, each structural unit of this type of resin backbone have can with the carboxylic group of rare-earth ion coordination, and, after introducing the alkyl substituent of different types of quantity on the molecular chain phenyl ring, improved the solubility property of polymkeric substance greatly, polymkeric substance that makes even also solubilized in acetone.
The invention has the beneficial effects as follows: the prepared polyarylether rare-earth complexes material of the present invention has high thermostability, can send bright-coloured multiple color fluorescence under the UV-irradiation, and can be processed into pressed powder, film or fiber easily, have purposes widely in display material, anti-counterfeiting mark material and rare earth high polymer light amplification material field.
Description of drawings
The photo of Fig. 1 PEK-L/ europium rare earth compounding powder under the 365nm UV-irradiation
Fluorescence spectrum figure under Fig. 2 PEK-L/ europium rare earth compounding 367nm ultraviolet excitation
The photo of Fig. 3 IMPES-L/ terbium rare earth compounding film under the 365nm UV-irradiation
Fluorescence spectrum under Fig. 4 IMPES-L/ terbium rare earth compounding 367nm ultraviolet excitation
The photo of Fig. 5 DMPEK-L/ europium rare earth compounding film under the 365nm UV-irradiation
Fluorescence spectrum under Fig. 6 DMPEK-L/ europium rare earth compounding 367nm ultraviolet excitation
Embodiment
The invention will be further described below by embodiment, but do not influence protection scope of the present invention:
Add 1.8 gram PEK-L, 1.5 gram phenanthrolines, 1.3 gram europium nitrate and 60 milliliters of N in the 250ml flask of mechanical stirrer successively with being equipped with, dinethylformamide (DMF), at room temperature stirred 12 hours, stopped reaction, in ethanol, precipitate then, filter the back with distilled water rinsing 3 times repeatedly, obtain pressed powder PEK-L/ europium rare earth compounding (seeing Fig. 1 and Fig. 2) after the drying, productive rate 94.8%.
1.3 gram oxines, 0.9 gram Terbium trinitrate and 50 milliliters of N,N-dimethylacetamide solution (DMAc) are placed the 250ml there-necked flask that prolong, thermometer and mechanical stirrer are housed.Be warming up to 40 ℃, stirring reaction was reduced to room temperature after 5 hours, added the DMAc solution (1.9 gram IMPES-L are dissolved in 10 milliliters of DMAc) of IMPES-L again, continued to react stopped reaction after 10 hours.With the solution casting film-forming on the sheet glass of cleanliness levels that obtains, earlier 60 ℃ of dryings 6 hours, transferred in 100 ℃ the vacuum drying oven 5mmHg drier 10 hours down, obtaining thickness is the IMPES-L/ terbium rare earth compounding film (seeing Fig. 3 and Fig. 4) of 12um.
In the 250ml there-necked flask, 1.7 gram DMPEK-L are dissolved among the 40ml DMF, add 1.4 gram diphenylpropane-1,3-dione(DPPO)s and 1.1 gram europium nitrates, stir stopped reaction after 6 hours under the room temperature, with the solution casting film-forming on the sheet glass of cleanliness levels that obtains, earlier 60 ℃ of dryings 6 hours, transferred in 100 ℃ the vacuum drying oven 5mmHg drier 10 hours down, obtaining thickness is the DMPEK-L/ europium rare earth compounding film (seeing Fig. 5 and Fig. 6) of 16um.
Claims (11)
1, polyarylether rare-earth complexes luminous material is characterized in that, title complex is that macromolecular ligand, organic molecule are made part altogether by the polyarylether of band carboxyl, obtains with rare-earth ion coordination is synthetic.
2, polyarylether rare-earth complexes luminous material according to claim 1 is characterized in that, the polyarylether macromolecular ligand of described band carboxyl is:
Substituent R in the formula
1To R
4Can be hydrogen atom, halogen atom, nitro, or C
1To C
20Identical or different fat alkane and derivative thereof, or C
6To C
12Identical or different aromatic hydrocarbon and derivative thereof; A is C=O (polyaryletherketone) or SO
2(polyether sulphone).
3, polyarylether rare-earth complexes luminous material according to claim 2 is characterized in that, the polyarylether macromolecular ligand of described band carboxyl is:
Wherein, A is C=O (PEK-L) or SO
2(PES-L).
4, polyarylether rare-earth complexes luminous material according to claim 2 is characterized in that, the polyarylether macromolecular ligand of described band carboxyl is:
Wherein, A is C=O (DMPEK-L) or SO
2(DMPES-L).
5, polyarylether rare-earth complexes luminous material according to claim 2 is characterized in that, the polyarylether macromolecular ligand of described band carboxyl is:
Wherein, A is C=O (IMPEK-L) or SO
2(IMPES-L).
6, polyarylether rare-earth complexes luminous material according to claim 1 is characterized in that, the polyarylether of described band carboxyl can use separately, also can any several mixing use.
7, polyarylether rare-earth complexes luminous material according to claim 1 is characterized in that, described organic molecule part altogether is organic acid R-COOH, and wherein R is C
1To C
18Halo or not halogenated fat or aromatic group, or be phenanthroline, oxine, methyl ethyl diketone, benzoyl acetone, α-thenoyltrifluoroacetone, benzoyltrifluoroacetone, 2,2 '-dipyridyl, 2,2 ': 6 '; 2 "-terpyridyl, trioctyl-phosphine oxide, tributyl phosphate, hexaoxacyclooctadecane-6-6 or 15-crown ether-5, or be any several mixture in the above-mentioned part.
8, the rare complex luminescent material of going up of polyarylether according to claim 1 is characterized in that, described rare going up is one or more the mixture in europium, terbium, samarium, erbium, dysprosium, ytterbium, holmium, thulium, neodymium, lanthanum or the cerium.
9, the method for preparing the described polyarylether rare-earth complexes luminous material of claim 1-6, the steps include: to contain the carboxyl polyarylether, the organic molecule part, rare earth oxide, muriate or nitrification thing, in organic solvent, be mixed in proportion, the mol ratio of the carboxyl of polyarylether and organic molecule part is 1.0: 0-0: 1.0, the carboxyl of polyarylether and the mol ratio of rare earth ion are 1.0: 0-0: 1.0, in 0 ℃ of-100 ℃ of temperature range mechanical stirring 0.5-24 hour then, resulting solution can directly be filmed or spinning, maybe with the sedimentation in sinking agent of this solution, again through washing three times, obtain the pulverulent solids product after the drying, productive rate 90-95%.
10, the method for preparing the described polyarylether rare-earth complexes luminous material of claim 1-6 according to claim 9, it is characterized in that, described solvent is dimethyl sulfoxide (DMSO), N, dinethylformamide, N, the mixture of one or more solvents in N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, tetrahydrofuran (THF) or the acetone, its consumption are 0.5-200 milliliter solvent/gram (polyarylether, organic molecule part and rare earth compound).
11, the method for preparing the described polyarylether rare-earth complexes luminous material of claim 1-6 according to claim 9 is characterized in that, described sinking agent is one or more the mixture in ethanol, methyl alcohol or the water.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391496A (en) * | 2011-08-31 | 2012-03-28 | 上海大学 | Polyarylether light-emitting material with main chain containing naphthalimide and synthesis method thereof |
| CN102775981A (en) * | 2012-07-17 | 2012-11-14 | 中北大学 | Luminescent material of naphthoic acid functionalized polymer and rare earth complex and preparation method of luminescent material |
| CN103938288A (en) * | 2014-04-10 | 2014-07-23 | 北京石油化工学院 | Preparation of fatty acid phase change energy storage luminescent material and nanofibers of material |
| CN104804026A (en) * | 2015-03-02 | 2015-07-29 | 嘉兴学院 | Carboxyl-terminated hyperbranched polyester rare earth complex as well as preparation method and application thereof |
| CN108047458A (en) * | 2018-01-13 | 2018-05-18 | 江西师范大学 | The preparation method of the unlimited coordination polymer nano-particle of europium-thioyl trifluoroacetone and its film |
| CN108359344A (en) * | 2018-01-19 | 2018-08-03 | 大连理工大学 | A kind of preparation method of high hydrophobicity high temperature resistant fluoresent coating |
| CN110408028A (en) * | 2019-07-26 | 2019-11-05 | 电子科技大学 | A kind of novel ionomer Polysulfone microspheres and preparation method thereof |
| CN111592880A (en) * | 2020-05-14 | 2020-08-28 | 深圳大学 | Photoluminescent rare earth coordination polyimide optical material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3723389A (en) * | 1971-10-27 | 1973-03-27 | Allied Chem | Thermoplastic aromatic poly(ether-sulfones) |
| CN1162460C (en) * | 2001-08-14 | 2004-08-18 | 上海交通大学 | Polyester sulphone with lateral carboxylate group and its prepn |
| CN1743406A (en) * | 2005-09-29 | 2006-03-08 | 天津理工大学 | Polyarylether non conjugated electroluminescent mater containing oxadiazole units |
| DE102006026431A1 (en) * | 2006-06-07 | 2007-12-13 | Archimica Gmbh | Preparing an alkyl compound, useful e.g. in agrochemical industries, comprises reaction of a phenyl-halogen compound with an alcoholate compound or an alcohol compound and a base in presence of a copper-containing catalyst and a ligand |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391496A (en) * | 2011-08-31 | 2012-03-28 | 上海大学 | Polyarylether light-emitting material with main chain containing naphthalimide and synthesis method thereof |
| CN102775981A (en) * | 2012-07-17 | 2012-11-14 | 中北大学 | Luminescent material of naphthoic acid functionalized polymer and rare earth complex and preparation method of luminescent material |
| CN102775981B (en) * | 2012-07-17 | 2014-08-06 | 中北大学 | Luminescent material of naphthoic acid functionalized polymer and rare earth complex and preparation method of luminescent material |
| CN103938288A (en) * | 2014-04-10 | 2014-07-23 | 北京石油化工学院 | Preparation of fatty acid phase change energy storage luminescent material and nanofibers of material |
| CN104804026A (en) * | 2015-03-02 | 2015-07-29 | 嘉兴学院 | Carboxyl-terminated hyperbranched polyester rare earth complex as well as preparation method and application thereof |
| CN108047458A (en) * | 2018-01-13 | 2018-05-18 | 江西师范大学 | The preparation method of the unlimited coordination polymer nano-particle of europium-thioyl trifluoroacetone and its film |
| CN108047458B (en) * | 2018-01-13 | 2021-02-26 | 江西师范大学 | Preparation method of europium-thenoyl trifluoroacetone infinite coordination polymer nano particle and film thereof |
| CN108359344A (en) * | 2018-01-19 | 2018-08-03 | 大连理工大学 | A kind of preparation method of high hydrophobicity high temperature resistant fluoresent coating |
| CN110408028A (en) * | 2019-07-26 | 2019-11-05 | 电子科技大学 | A kind of novel ionomer Polysulfone microspheres and preparation method thereof |
| CN110408028B (en) * | 2019-07-26 | 2021-09-24 | 电子科技大学 | Ionic crosslinked polysulfone microspheres and preparation method thereof |
| CN111592880A (en) * | 2020-05-14 | 2020-08-28 | 深圳大学 | Photoluminescent rare earth coordination polyimide optical material and preparation method thereof |
| CN111592880B (en) * | 2020-05-14 | 2022-08-26 | 深圳大学 | Photoluminescent rare earth coordination polyimide optical material and preparation method thereof |
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