CN104789213A - Rare earth terbium complex and preparation method thereof - Google Patents
Rare earth terbium complex and preparation method thereof Download PDFInfo
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- CN104789213A CN104789213A CN201510192188.9A CN201510192188A CN104789213A CN 104789213 A CN104789213 A CN 104789213A CN 201510192188 A CN201510192188 A CN 201510192188A CN 104789213 A CN104789213 A CN 104789213A
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- rare earth
- terbium
- sodium carbonate
- polar solvent
- earth compounding
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 88
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 50
- 229910052771 Terbium Inorganic materials 0.000 title claims description 44
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 title claims description 38
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000010668 complexation reaction Methods 0.000 title description 2
- -1 rare earth salt Chemical class 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002798 polar solvent Substances 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 58
- 238000013329 compounding Methods 0.000 claims description 46
- 229960001138 acetylsalicylic acid Drugs 0.000 claims description 27
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- GWYXTVGANSBRNB-UHFFFAOYSA-N terbium(iii) oxide Chemical compound O=[Tb]O[Tb]=O GWYXTVGANSBRNB-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 150000007529 inorganic bases Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 9
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000000695 excitation spectrum Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 238000002189 fluorescence spectrum Methods 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002329 infrared spectrum Methods 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 241000551547 Dione <red algae> Species 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 150000001217 Terbium Chemical class 0.000 claims description 2
- 229940068372 acetyl salicylate Drugs 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910001038 basic metal oxide Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 150000003997 cyclic ketones Chemical class 0.000 claims description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000005303 weighing Methods 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003407 synthetizing effect Effects 0.000 description 1
- 238000001161 time-correlated single photon counting Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a preparation method of a composite rare earth complex, which comprises the steps of weighing an inorganic alkaline matter, adding a polar solvent, performing dispersion, adding rare earth salt and ligand, performing a reaction under stirring, performing filtering, obtaining the composite rare earth complex, optionally performing drying, and obtaining the composite rare earth complex. According to the method, the composite rare earth complex is successfully synthesized and extracted in the polar solvent by using the inorganic alkaline matter for a rare earth binary complex which is difficultly deposited in the polar solvent, so that the difficult-to-deposit rare earth binary complex is effectively deposited out, and the cost of a rare earth fluorescent material is lowered.
Description
Technical field
The invention belongs to rare earth luminescent material technical field, relate to a kind of novel composite luminescent material, particularly a kind of using mineral alkali as kernel, extexine in conjunction with rare earth compounding compound rare earth compounding with and preparation method thereof.
Background technology
Rare earth compounding, as a kind of luminescent material, owing to having, emission peak is narrow, quantum yield is high, launch peak position not the movement with the change of part feature and be widely used in luminescence display, fluorescent probe, the field such as false proof.
But due to rising steadily of rare earth price, rare earth compounding receives certain restriction in the application in some fields.Document once reported that certain methods improved the luminescent properties of rare earth compounding, as utilized the terbium doped sapphire whisker of rare earth in patent CN 102504817 A, the method for coated with silica rare earth compounding in CN 102153576 A, is utilized to realize the optimization of rare-earth complexes luminous material performance and the reduction of cost.But the adsorptive power that rare earth compounding is attached to nano-silica surface is more weak, easily departs from the course of processing of material and reassemble.Most of rare earth compounding although coated with silica rare earth compounding can reduce costs effectively, is not applicable to all rare earth compoundings, because there occurs decomposition reaction in the process of hydrolyzing tetraethoxy orthosilane.
On the other hand, some rare earth compounding because solubleness is comparatively large, is thus difficult to be precipitated out in polar solvent.In order to there is precipitation, the employing Ligands had in prior art, but due to the introducing of Ligands, reduce the fluorescence property of rare earth compounding.
Summary of the invention
In order to solve the problem, present inventor has performed and study with keen determination, found that: for the rare earth complex not easily forming precipitation in polar solvent, by using inorganic base substance, successfully synthesize in polar solvent and be extracted the mixture of rare earth complex and inorganic base substance, the cost of rare-earth luminescent material is reduced on the one hand by introducing cheap inorganic base substance, on the other hand the rare earth complex being difficult to precipitate is precipitated out effectively, thus completes the present invention.
The object of the present invention is to provide following aspect:
First aspect, the invention provides a kind of method preparing compound rare earth compounding, it is characterized in that, the method comprises the following steps:
(1) take inorganic base substance, add polar solvent, dispersion;
(2) add rare-earth salts and part, react under stirring;
(3) filtration obtains compound rare earth compounding, optionally carries out drying, thus obtains compound rare earth compounding.
Second aspect, the compound rare earth compounding that the present invention also provides the method according to above-mentioned first aspect obtained.
Below in detail the present invention is described in detail.
According to a first aspect of the invention, provide a kind of method preparing compound rare earth compounding, it is characterized in that, the method comprises the following steps:
Step 1, takes inorganic base substance, adds polar solvent, dispersion.
The alkaline matter adopted in the present invention is inorganic base substance, is generally solid form, and it can not dissolve completely in polar solvent, is therefore just dispersed in polar solvent.
According to the preferred embodiment of the present invention, the inorganic base substance of described solid can be common solid alkali, such as basic metal or alkaline earth metal hydroxides or salt, the salt of preferred as alkali or alkaline-earth metal, can be strong acid salt or salt of weak acid, such as sodium sulfate, sodium carbonate, sodium-acetate or water glass, it is generally anhydrous form, such as anhydrous sodium carbonate, anhydrous sodium sulphate, sodium acetate, anhydrous or anhydrous sodium metasilicate, preferred salt of weak acid, such as anhydrous sodium carbonate, sodium acetate, anhydrous or anhydrous sodium metasilicate, be more preferably anhydrous sodium carbonate.
The polar solvent adopted in the present invention can be polar organic solvent, and above-mentioned inorganic base substance is insoluble to wherein, but can dissolve rare earth compounding.
According to the preferred embodiment of the present invention, described polar solvent can be that alcoholic solvent is as lower alcohols such as methyl alcohol, ethanol, propyl alcohol or butanols, ketones solvent is as aliphatic ketone or cyclic ketones such as acetone, methylethylketone, pimelinketone, ether solvent is as the aliphatic ether such as ether, oxyethane or cyclic ethers, and esters solvent is as ethyl formate, ethyl acetate etc., preferred employing methyl alcohol, ethanol, acetone, pimelinketone, ether, ethyl acetate, more preferably adopt ethanol, acetone, ethyl acetate, most preferably adopt dehydrated alcohol.
The amount ratio of solid alkali and polar solvent is 0.1:150g/ml ~ 10:150g/ml, preferred 0.5:150g/ml ~ 8:150g/ml, more preferably 1:150g/ml ~ 7:150g/ml, such as, in 15ml polar solvent, 0.1g, 0.2g, 0.3g, 0.4g, 0.5g, 0.6g, 0.7g solid alkali is added.
In the present invention, do not do special restriction to the time of system dispersion, being dispersed in can make solid alkali is preferred in polar solvent, preferably 5 minutes ~ 2.5 hours, is more preferably 10 minutes ~ 2 hours, as 1 hour.
Step 2, adds rare-earth salts and part, reacts under stirring.
In the present invention, described rare-earth salts is that lanthanide series metal (Ln) is as the inorganic salt of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium etc., be preferably hydrochloride, preferably can the lanthanide series metal of emitting fluorescence as the hydrochloride of terbium, europium, dysprosium, gadolinium, be particularly preferably terbium chloride.
According to the present invention, described rare-earth salts can be commercial goods, is also obtained by Preparation.For terbium chloride, prepared by terbium sesquioxide and strong acid example hydrochloric acid.Specifically, take terbium sesquioxide, dissolve, add strong acid and reductive agent, then add diluted acid and clarify to solution.Under heating condition, while stirring except desolventizing, to occur wait there being epitaxial and after being paved with liquid level, cooling, crystallization, namely obtains product chlorinated terbium, can be dried for subsequent use.
In the present invention, above-mentioned terbium sesquioxide can be terbium sesquioxide, also can be terbium peroxide, is preferably terbium peroxide.
The strong acid that the present invention selects is selected from chloride strong acid, and be preferably concentrated hydrochloric acid, diluted acid is selected from chloride diluted acid, is preferably dilute hydrochloric acid.
The reductive agent that the present invention selects is preferably hydrogen peroxide, and the mass fraction of hydrogen peroxide is preferably 30%.
The solvent of the present invention to terbium sesquioxide place liquid-phase system is not particularly limited to, and preferably uses pure water, deionized water and/or distilled water, is preferably deionized water.
The present inventor finds to heat and can shorten reaction times of terbium sesquioxide and strong acid, and reaction is carried out more fully, the temperature of reaction is 30 DEG C ~ 100 DEG C, preferably 40 DEG C ~ 95 DEG C., more preferably 50 DEG C ~ 92 DEG C.
The present invention selects the solvent removing terbium sesquioxide place liquid-phase system before cooling, crystallization, the present invention is not particularly limited to the mode except desolventizing, in prior art, any one all can use, as normal temperature volatilization, normal heating, underpressure distillation etc. except the mode of desolventizing.
The present inventor finds that having impurity salt in reaction system occurs, under filtration condition, can obtain pure crystal, the present invention is not particularly limited to the mode of filtering, and as suction filtration, natural filtration, is preferably suction filtration.
In the present invention, described part (L) can be unidentate ligand, also can be polydentate ligand, as bitooth ligand, oxalate denominationby, 2,2'-dipyridyl, 1,10-phenanthroline (phen), diones part are as methyl ethyl diketone (acac), acetylsalicylic acid radical ion (aspirin) etc., preferably 1,10-phenanthroline (phen), methyl ethyl diketone (acac) and acetylsalicylic acid radical ion, be more preferably acetylsalicylic acid radical ion (aspirin).Correspondingly, the rare earth compounding of gained can be LnL
6(when L is unidentate ligand) or LnL
3(when L is bitooth ligand), as Tb (aspirin)
3.
The time that the system formed for solid alkali, rare-earth salts and part carries out reacting is not particularly limited to, and is preferably 20 minutes ~ 3 hours, is more preferably 30 minutes ~ 2.5 hours, as 2 hours.
Step 3, filters and obtains compound rare earth compounding, optionally carry out drying, thus obtain compound rare earth compounding.
According to the present invention, the reaction system of step 2 is carried out filtering namely obtain compound rare earth compounding, preferably drying is carried out to it, drying temperature is not particularly limited to, and is preferably 50 DEG C ~ 120 DEG C, as 80 DEG C, time of drying is not also particularly limited to, and is preferably 2 hours ~ 24 hours, as 12 hours.
According to the present invention, rare earth compounding LnL
6or LnL
3(as Tb (aspirin)
3) and solid alkali as there is stronger interaction between anhydrous sodium carbonate, therefore, it is possible to be effectively adsorbed on solid alkali surface and be filtered out.Be not bound by any theory, its reason may be the carboxylic acid reaction of the surface molecules of anhydrous sodium carbonate particle as alkali and part, and part and anhydrous sodium carbonate particle surface molecules spacing are furthered, thus adsorptive power strengthens.Therefore, the rare earth compounding of generation will be adsorbed on as solid alkali particle surfaces such as anhydrous sodium carbonates consumingly, causes reducing with the part number of rare-earth ion coordination, such as, form Tb (aspirin)
x, wherein x<3.
According to aforesaid method of the present invention finally obtained compound rare earth compounding, its fluorescence spectrum and infrared spectra have the characteristic peak being different from rare earth compounding.When solid alkali is anhydrous sodium carbonate, rare earth compounding be terbium and acetylsalicylate formed title complex time, its fluorescence emission spectrum shows, this compound rare earth compounding is there is emission peak near 420nm, 550nm, 590nm, 625nm at wavelength; Its fluorescence excitation spectrum shows, this compound rare earth compounding is there is excitation spectrum peak within the scope of 250-350nm at wavelength; Infrared spectra shows, it is 1749cm in wave number
-1, 881cm
-1, 702cm
-1, 1400-1600cm
-1place's existing characteristics absorption peak.
According to preparation method and the corresponding compound rare earth compounding of compound rare earth compounding provided by the invention, show following beneficial effect:
(1) fluorescence lifetime of this compound rare earth compounding improves greatly, can be widely used in display and print field as luminescent material;
(2) method preparing this compound rare earth compounding has started the technology of novel synthetizing phosphor powder, not only can reduce the cost of fluorescent material as kernel by introducing cheap solid alkali (as anhydrous sodium carbonate), and can will be difficult to the rare earth compounding of precipitation (as title complex (Tb (aspirin) x that terbium and acetylsalicylic acid are formed, wherein x be 3 or <3) be effectively precipitated out, be conducive to suitability for industrialized production;
(3) this compound rare earth compounding and preparation method thereof environmental protection, non-environmental-pollution.
Accompanying drawing explanation
Fig. 1 illustrates the utilizing emitted light spectrogram (λ of rare earth compounding after different mass anhydrous sodium carbonate surface is formed that embodiment 1-7 obtains
ex=334nm);
Fig. 2 illustrates the fluorescent emission intensity graph of a relation of the rare-earth terbium complex that anhydrous sodium carbonate consumption and embodiment 1-7 obtain;
Fig. 3 illustrates the exciting light spectrogram (λ of rare-earth terbium complex after different mass anhydrous sodium carbonate surface is formed that embodiment 1-7 obtains
em=545nm);
Fig. 4 illustrates the infrared spectrogram of rare-earth terbium complex after different mass anhydrous sodium carbonate surface is formed that embodiment 1-7 obtains;
Fig. 5 illustrates the variation relation figure of mean fluorecence life-span with anhydrous sodium carbonate consumption of the rare-earth terbium complex that embodiment 1-7 obtains;
Fig. 6 a, 6b, 6c, 6d, 6e illustrate the fluorescent microscopy images (amplify 100 times) of rare-earth terbium complex after different mass anhydrous sodium carbonate surface is formed that embodiment 1-5 obtains respectively.
Embodiment
Below by embodiment, the present invention is described in detail, and the features and advantages of the invention will illustrate along with these and become more clear, clear and definite, but the present invention is not limited to these exemplary illustrations.
Measuring method
infrared measurement:
Use pressing potassium bromide troche in 4000-400cm
-1in the upper mensuration of Fourier transformation infrared spectrometer (WQF-IR 510).
fluorescence spectrometry:
Adopt FM4NIR TCSPC fluorescence spectrophotometer (French JY company), adopt the light that the spectral filter elimination of 350nm is produced by light source for instrument.Incident and transmitting slit is 1nm, adopts the light damping plate of 10 times to reduce the intensity of light source simultaneously.
fluorescence lifetime measures:
Use the LED excitation light source of 370nm, gather 20000 photons, fluorescence lifetime curve adopts second order life-span approximating method.
fluorescence microscopy:
Use Olympus TL4, camera model is KP73IX53, exposure intensity 800, magnification 200 times, and the time shutter is 2 seconds, and excitation light source is the royal purple light of 460-530nm.
Embodiment
In the present embodiment terbium sesquioxide used purchased from the brilliant pure reagent company limited in Shanghai, dehydrated alcohol purchased from Shanghai Zhen Qi chemical reagent company limited, anhydrous sodium carbonate purchased from upper seamount Pu Chemical Co., Ltd., acetylsalicylic acid purchased from Beijing Century AudioCodes Bioisystech Co., Ltd.
embodiment 1
In beaker, weigh 10g terbium sesquioxide, pour 80ml deionized water into, then slow alternate dropwise addition concentrated hydrochloric acid and hydrogen peroxide in beaker, then drip appropriate hydrochloric acid reaction and clarify to solution.Evaporating solvent while stirring under 90 DEG C of conditions, occurs wait there being epitaxial and after being paved with liquid level, reaction system cooled, have mass crystallization to separate out, obtain terbium chloride after going out crystallization with Büchner funnel suction filtration, in moisture eliminator, drying at room temperature is for subsequent use.
Take the beaker that 0.1 anhydrous sodium carbonate is placed in 100mL, add 15mL dehydrated alcohol and sonic oscillation disperses one hour in ultrasonic instrument.
Then take the dried terbium chloride of 0.5mmol and 1.5mmol acetylsalicylic acid adds in beaker, beaker is placed on magnetic stirring apparatus and stirs 2h.
Finally obtain solid sample with Büchner funnel suction filtration, products therefrom puts into baking oven dry 12h at the temperature of 80 DEG C, obtains compound rare-earth terbium complex finally, and its sign is shown in following experimental example 1-6.
embodiment 2-7
Repeat embodiment 1, difference is only that the quality changing anhydrous sodium carbonate is respectively 0.2g, 0.3g, 0.4g, 0.5g, 0.6g, 0.7g, obtains its sign of compound rare-earth terbium complex respectively and sees following experimental example 1-6.
embodiment 8-15
Repeat embodiment 1-7 respectively, difference is only to adopt commercially available terbium chloride as raw material, the compound rare-earth terbium complex of final acquisition, its utilizing emitted light spectrogram, exciting light spectrogram, infrared spectrogram, fluorescent microscopy images, fluorescent emission intensity, mean fluorecence life experiment result and embodiment 1-7 are similar.
Comparative example
comparative example 1
In beaker, weigh 10g terbium sesquioxide, pour 80ml deionized water into, then slow alternate dropwise addition concentrated hydrochloric acid and hydrogen peroxide in beaker, then drip appropriate hydrochloric acid reaction and clarify to solution.Evaporating solvent while stirring under 90 DEG C of conditions, occurs wait there being epitaxial and after being paved with liquid level, reaction system cooled, have mass crystallization to separate out, obtain terbium chloride after going out crystallization with Büchner funnel suction filtration, in moisture eliminator, drying at room temperature is for subsequent use.
Take the dried terbium chloride of 0.5mmol and 1.5mmol acetylsalicylic acid adds in beaker, add 15mL dehydrated alcohol and sonic oscillation disperses one hour in ultrasonic instrument, then beaker is placed on magnetic stirring apparatus and stirs 2h, but do not have solid to separate out.
Experimental example
experimental example 1
Fig. 1 is the utilizing emitted light spectrogram (λ after the rare earth compounding of embodiment 1-7 acquisition adsorbs on different mass anhydrous sodium carbonate
ex=334nm).
As can be seen from the figure the emission peak of terbium ion four features, illustrates that terbium coordination compound has been formed and can effectively absorb UV-light and passes to terbium ion.Sodium carbonate amount is the sample of 0.2-0.7g, all sees a wide emission peak near 420nm, and this is the emission peak belonging to part aspirin.And part aspirin and Tb
3+there is extraordinary matching, if part and Tb
3+all define terbium coordination compound, the emission peak of part be can't see.This demonstrate some ligands and do not participate in coordination, but be adsorbed on sodium carbonate surface with the form of independent ligand, this is because terbium coordination compound needs in the surperficial cause formed of sodium carbonate.
experimental example 2
Fig. 2 is the fluorescent emission intensity graph of a relation of the rare-earth terbium complex that anhydrous sodium carbonate consumption and embodiment 1-7 obtain.As can be seen from the figure, along with increasing of anhydrous sodium carbonate consumption, the fluorescent emission intensity of terbium coordination compound is totally on a declining curve.This is caused by the decline in the surperficial terbium coordination compound density formed of sodium carbonate.
experimental example 3
Fig. 3 is the exciting light spectrogram (λ of rare-earth terbium complex after different mass anhydrous sodium carbonate surface is formed that embodiment 1-7 obtains
em=545nm).As we can see from the figure, the excitation spectrum diagram shape difference of seven kinds of products is comparatively large, 0.1 and 0.2g anhydrous sodium carbonate consumption to obtain the excitation spectrum peak shape of product wider, 0.3-0.7g anhydrous sodium carbonate consumption obtain product excitation spectrum peak shape obviously narrow.Which illustrate the structure of different anhydrous sodium carbonate consumptions on terbium coordination compound and there is larger impact.
Experimental example 4
Fig. 4 is the infrared spectrogram of rare-earth terbium complex after different mass anhydrous sodium carbonate surface is formed that embodiment 1-7 obtains.When using 0.1g anhydrous sodium carbonate as alkali, can see mainly terbium coordination compound and the acetysalicylic charateristic avsorption band of part in infrared spectrogram, peak shape is relatively more sharp-pointed, 1749cm
-1locate strong absorption peak and illustrate have the acetysalicylic carbonyl of part to exist.At 881cm
-1and 702cm
-1obvious anhydrous sodium carbonate charateristic avsorption band is not seen at place, but, at 1400-1600cm
-1place can see that significantly strong broad peak occurs, this is the charateristic avsorption band of anhydrous sodium carbonate, illustrates that terbium coordination compound forms mixture with anhydrous sodium carbonate.Along with increasing of anhydrous sodium carbonate consumption, 1400-1600cm
-1the wide strong peak at place becomes more and more stronger, 881cm
-1and 702cm
-1the peak at place also becomes more and more stronger, and the peak of terbium coordination compound and part is more and more weak.
experimental example 5
The time lifetime of the rare-earth terbium complex that embodiment 1-7 obtains after different mass anhydrous sodium carbonate surface is formed is respectively 1.30ms, 1.48ms, 1.46ms, 1.61ms, 1.41ms, 1.65ms, 1.74ms, and Fig. 5 illustrates the variation relation figure of mean fluorecence life-span with anhydrous sodium carbonate consumption.As can be seen from the figure, terbium coordination compound Tb (aspirin)
xthe mean fluorecence life-span totally in rising trend with the increase of anhydrous sodium carbonate consumption.The consumption which illustrating anhydrous sodium carbonate have impact on terbium coordination compound Tb (aspirin)
xfluorescence lifetime, the consumption indicated along with anhydrous sodium carbonate changes, and terbium coordination compound molecular structure there occurs certain change.Along with increasing of anhydrous sodium carbonate consumption, be distributed in the TbCl that anhydrous sodium carbonate surface is reacted with it
36H
2o and aspirin molecular amounts also changes thereupon, therefore can cause formed terbium coordination compound Tb (aspirin)
xx changing.Fig. 5 contrasts Fig. 2 can find out terbium coordination compound Tb (aspirin)
xthe mean fluorecence life-span larger, its fluorescent emission intensity can be more weak.
experimental example 6
Fig. 6 a, 6b, 6c, 6d and 6e illustrate the fluorescent microscopy images (amplify 100 times) of rare-earth terbium complex after different mass anhydrous sodium carbonate surface is formed that embodiment 1-5 obtains respectively, respectively corresponding use 0.1g, 0.2g, 0.3g, 0.4g and 0.5gNa
2cO
3situation.And Na
2cO
3then almost fluorescence is can't see for during 0.6g and 0.7g.As can be seen from the figure, along with Na
2cO
3increasing of consumption, the green fluorescence produced by the optical excitation of fluorescent microscope light source royal purple weakens gradually.As can be seen from the figure, anhydrous sodium carbonate completely the green fluorescence that produces by terbium coordination compound cover, describe anhydrous sodium carbonate surface and combine closely with Tb (aspirin) x.Why fluorescence weakens gradually along with increasing of anhydrous sodium carbonate consumption, because Tb (aspirin) the x molecular amounts on anhydrous sodium carbonate surface reduces gradually causes.But we can see, the Changing Pattern and the fluorescence intensity change rule difference shown in Fig. 2 that show the brightness of fluorescence in photo are very large.This is because the optical source wavelength of fluorescent microscope and emmission spectrum excitation wavelength used be not caused by the same area.
More than in conjunction with embodiment and exemplary example to invention has been detailed description, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that when not departing from spirit and scope of the invention, can carry out multiple equivalencing, modification or improvement to technical solution of the present invention and embodiment thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. prepare a method for compound rare earth compounding, it is characterized in that, the method comprises the following steps:
(1) take inorganic base substance, add polar solvent, dispersion;
(2) add rare-earth salts and part, react under stirring;
(3) filtration obtains compound rare earth compounding, optionally carries out drying, thus obtains compound rare earth compounding.
2. method according to claim 1, is characterized in that,
In step 1, described inorganic base substance is solid form, is dispersed in polar solvent, be preferably basic metal or alkaline earth metal hydroxides or salt, the salt of preferred as alkali or alkaline-earth metal, such as sodium sulfate, sodium carbonate, sodium-acetate or water glass, be more preferably anhydrous sodium carbonate.
3. method according to claim 1 and 2, is characterized in that,
In step 1, described polar solvent is alcoholic solvent, as lower alcohols such as methyl alcohol, ethanol, propyl alcohol or butanols, ketones solvent is as aliphatic ketone or cyclic ketones such as acetone, methylethylketone, pimelinketone, ether solvent is as the aliphatic ether such as ether, oxyethane or cyclic ethers, and esters solvent is as ethyl formate, ethyl acetate etc., preferably adopts methyl alcohol, ethanol, acetone, pimelinketone, ether, ethyl acetate, more preferably ethanol, acetone, ethyl acetate, most preferably dehydrated alcohol;
The amount ratio of solid alkali and polar solvent is 0.1:150g/ml ~ 10:150g/ml, preferred 0.5:150g/ml ~ 8:150g/ml, more preferably 1:150g/ml ~ 7:150g/ml, such as, in 15ml polar solvent, 0.1g, 0.2g, 0.3g, 0.4g, 0.5g, 0.6g, 0.7g solid alkali is added.
4., according to the method one of claims 1 to 3 Suo Shu, it is characterized in that,
In step 2, described rare-earth salts is the inorganic salt of lanthanide series metal, preferably salt hydrochlorate, and more preferably the hydrochloride of terbium, europium, dysprosium, gadolinium, is particularly preferably terbium chloride.
5. method according to claim 4, is characterized in that,
In step 2, described terbium chloride is prepared as follows by terbium sesquioxide and strong acid:
Take terbium sesquioxide, dissolve, add strong acid and reductive agent, then add diluted acid and clarify to solution; Under heating condition, while stirring except desolventizing, to occur and after being paved with liquid level wait there being epitaxial, cooling, crystallization, namely obtains product chlorinated terbium;
Described terbium sesquioxide can be terbium sesquioxide, also can be terbium peroxide, is preferably terbium peroxide;
Described strong acid is selected from chloride strong acid, and be preferably concentrated hydrochloric acid, diluted acid is selected from chloride diluted acid, is preferably dilute hydrochloric acid;
Described reductive agent is preferably hydrogen peroxide, and the mass fraction of hydrogen peroxide is preferably 30%.
6., according to the method one of claim 1 to 5 Suo Shu, it is characterized in that,
In step 2, described part (L) is unidentate ligand or polydentate ligand, as bitooth ligand, oxalate denominationby, 2,2'-dipyridyl, 1,10-phenanthroline (phen), diones part are as methyl ethyl diketone (acac), acetylsalicylic acid radical ion (aspirin) etc., preferably 1,10-phenanthroline (phen), methyl ethyl diketone (acac) and acetylsalicylic acid radical ion, be more preferably acetylsalicylic acid radical ion (aspirin).
7., according to the method one of claim 1 to 6 Suo Shu, it is characterized in that,
In step 2, the time that the system that solid alkali, rare-earth salts and part are formed carries out reacting is 20 minutes ~ 3 hours, is more preferably 30 minutes ~ 2.5 hours, as 2 hours.
8., according to the method one of claim 1 to 7 Suo Shu, it is characterized in that,
In step 3, the reaction system of step 2 is carried out filtering namely obtain compound rare earth compounding, preferably drying is carried out to it.
9. the compound rare earth compounding obtained according to the method one of claim 1 to 8 Suo Shu, said method comprising the steps of:
(1) take inorganic base substance, add polar solvent, dispersion;
(2) add rare-earth salts and part, react under stirring;
(3) filtration obtains compound rare earth compounding, optionally carries out drying, thus obtains compound rare earth compounding.
10. compound rare earth compounding according to claim 9, when solid alkali is anhydrous sodium carbonate, rare earth compounding be terbium and acetylsalicylate formed title complex time, obtain compound rare-earth terbium complex, its fluorescence emission spectrum is there is emission peak near 420nm, 550nm, 590nm, 625nm at wavelength; Its fluorescence excitation spectrum is there is excitation spectrum peak within the scope of 250-350nm at wavelength; Its infrared spectra is 1749cm in wave number
-1, 881cm
-1, 702cm
-1, 1400-1600cm
-1place's existing characteristics absorption peak.
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