CN100364982C - Process for preparing blue light-emitting 2-(2-hydroxy phenyl) benzothiazole chelated beryllium - Google Patents
Process for preparing blue light-emitting 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Download PDFInfo
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- CN100364982C CN100364982C CNB2006100125892A CN200610012589A CN100364982C CN 100364982 C CN100364982 C CN 100364982C CN B2006100125892 A CNB2006100125892 A CN B2006100125892A CN 200610012589 A CN200610012589 A CN 200610012589A CN 100364982 C CN100364982 C CN 100364982C
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- benzothiazole
- beryllium
- btz
- hydroxy phenyl
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- 229910052790 beryllium Inorganic materials 0.000 title claims abstract description 54
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- MVVGSPCXHRFDDR-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=NC2=CC=CC=C2S1 MVVGSPCXHRFDDR-UHFFFAOYSA-N 0.000 title claims description 57
- 238000004519 manufacturing process Methods 0.000 title description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 51
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 32
- DIMYTQPLZWDZFE-UHFFFAOYSA-L beryllium sulfate tetrahydrate Chemical compound [Be+2].O.O.O.O.[O-]S([O-])(=O)=O DIMYTQPLZWDZFE-UHFFFAOYSA-L 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000001953 recrystallisation Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004458 analytical method Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- -1 2-hydroxy phenyl Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 claims description 4
- 238000012916 structural analysis Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000002574 poison Substances 0.000 claims description 3
- 231100000614 poison Toxicity 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 8
- 230000001681 protective effect Effects 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 abstract 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000012512 characterization method Methods 0.000 abstract 1
- 239000002274 desiccant Substances 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract 1
- 229960004889 salicylic acid Drugs 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229960005419 nitrogen Drugs 0.000 description 25
- 238000005516 engineering process Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052614 beryl Inorganic materials 0.000 description 1
- KQHXBDOEECKORE-UHFFFAOYSA-L beryllium sulfate Inorganic materials [Be+2].[O-]S([O-])(=O)=O KQHXBDOEECKORE-UHFFFAOYSA-L 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010010 raising Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- Thiazole And Isothizaole Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention relates to a blue-light emitting 2-(2-oxhydryl phenyl) benzothiazole chelating beryllium Be (BTZ) < 2 > preparing method. The method uses salicylic acid, 2-aminophenyl mercaptan and beryllium sulfate tetrahydrate as raw material, uses toluene and methanol as solvent, uses phosphorus trichloride as a catalyst, uses phosphorus pentoxide as a drying agent, uses absolute ethyl alcohol as crystallizing solvent, uses triethylamine as a pH value regulator, uses nitrogen as protective gas, uses deionized water as beryllium sulfate tetrahydrate solvent, and uses the deionized water and toluene as detergent. A brand-new preparing process flow is adopted; firstly, 2-(2-oxhydryl phenyl) benzothiazole BTZ is synthesized, and then the 2-(2-oxhydryl phenyl) benzothiazole chelating beryllium Be (BTZ) < 2 > is synthesized; finally, a yellow powdery product of highly purified blue-light emitting 2-(2-oxhydryl phenyl) benzothiazole chelating beryllium Be (BTZ) < 2 > is obtained through the dissolving synthesis reaction, the vacuum filtration, the washing, the drying, the recrystallization purification, the detection, the analysis and the characterization of the chemical substance raw material. The preparing method has the advantages of few used equipment, short process flow, high yield which can reach 85% and fine blue-light purity which can reach 0.7491, and is a very ideal method for preparing the blue-light emitting 2-(2-oxhydryl phenyl) benzothiazole chelating beryllium Be (BTZ) < 2 >; the blue-light material can be used for military industry, electronic industry and light emission technical field.
Description
Technical field
The present invention is a kind of preparation method of the benzothiazole chelated beryllium of 2-(2-hydroxy phenyl) of blue light-emitting, belongs to electroluminescent organic material, benzothiazoles organometallic complex and preparation method's technical field.
Background technology
Electroluminescent organic material, the organic molecule metal complex has the luminous efficiency height, be easy to purify, be easy to characteristics such as vacuum evaporation, be widely used in industry and luminous field, organic small molecule material mainly contains oxine class, Schiff bases, benzothiazoles, rare earth metal complex class.
The benzothiazoles metal complex has caused investigator's extensive concern owing to have good luminous property, good electron transport property.
White light is the focus of luminescence technology area research always, and for realizing white light, it is vital preparing stable blue light material.
Benzothiazoles metal complex 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2Under ultraviolet excitation, have extremely strong blue-fluorescence, be easy to evaporation film-forming, have good use value.
Beryllium is one of the lightest metal, be light grey, from beryl, found in 1879, nineteen twenty-eight restores metallic beryllium first, because it has hypertoxicity, in application, be restricted always, nineteen fifties is along with the solution of beryllium poison protection question, the application of beryllium is just developed, and beryllium is applied in sophisticated technology fields such as nuclear power, electronic industry, rocket, universe space flight and aviation industry.
At present, benzothiazole chelated beryllium Be (BTZ)
2Preparation method less, mostly in inquiring into research trial, some testing datas are stable not enough, product purity is lower, production yield rate is not high, some tests, processing method are ripe and desirable not enough, also exist a lot of not enough.
Summary of the invention
Goal of the invention
Purpose of the present invention is exactly at disadvantages of background technology, adopt a kind of new preparation method and synthetic technology, adopt two step preparing processs, elder generation's Synthetic 2-(2-hydroxy phenyl) benzothiazole, the benzothiazole chelated beryllium of resynthesis 2-(2-hydroxy phenyl), purify by preparation solution, washing, filtration, drying, heat temperature raising, chemical reaction, recrystallization, obtain the benzothiazole chelated beryllium product of highly purified 2-(2-hydroxy phenyl).
Technical scheme
The chemical substance material that the present invention uses is Whitfield's ointment, o-amino thiophenol, Beryllium sulfate tetrahydrate, toluene, phosphorus trichloride, Vanadium Pentoxide in FLAKES, triethylamine, dehydrated alcohol, methyl alcohol, deionized water, nitrogen, and its combination matching amount is: with gram, milliliter, centimetre 3 is measure unit
Whitfield's ointment: C
7H
6O
36.3g ± 0.01g
O-amino thiophenol: C
6H
7NS 5ml ± 0.1ml
Toluene: C
6H
5OH 160ml ± 3ml
Phosphorus trichloride: PCl
34ml ± 0.1ml
Vanadium Pentoxide in FLAKES: P
2O
5200g ± 5g
Triethylamine: (C
2H
5)
3N 7ml ± 0.5ml
Dehydrated alcohol: CH
3CH
2OH 80ml ± 3ml
Methyl alcohol: CH
3OH 180ml ± 5ml
Deionized water: H
2O 60ml ± 3ml
Nitrogen: N
230cm
3± 1cm
3
Beryllium sulfate tetrahydrate: BeSO
44H
2O 0.973g ± 0.01g
Preparation method is as follows:
I, selected raw chemical material
Carry out selectedly to producing required raw chemical material, and carry out control of purity:
Whitfield's ointment: solid crystals 〉=96%
O-amino thiophenol: liquid 98%
Toluene: liquid 99.5%
Phosphorus trichloride: liquid 〉=95.5%
Vanadium Pentoxide in FLAKES: solid 99.5%
Triethylamine: liquid 99.0%
Dehydrated alcohol: liquid 〉=99.7%
Methyl alcohol: liquid 99.5%
Deionized water: liquid 99.999%
Nitrogen: gas 99.9%
Beryllium sulfate tetrahydrate: solid 〉=99%
II, preparation 2-(2-hydroxy phenyl) benzothiazole
1), dissolving Whitfield's ointment
(1) in four-hole boiling flask, carries out, and on electric mantle, heat;
(2) at first Whitfield's ointment 6.3g ± 0.01g and o-amino thiophenol 5ml ± 0.1ml are placed four-hole boiling flask, add toluene 80ml ± 3ml, heating and stirring make the Whitfield's ointment dissolving, Heating temperature is 55 ℃ ± 0.5 ℃, dissolution time is 10min ± 2min, feed nitrogen to four-hole boiling flask simultaneously, the nitrogen input speed is 0.5cm
3/ min, input time 10min ± 2min, simultaneously prolong carries out the cooling of water condensation reflux cycle, stops heating after Whitfield's ointment dissolves fully;
2), add catalyzer phosphorus trichloride, combination reaction
(1) dissolving of the Whitfield's ointment in four-hole boiling flask back becomes Whitfield's ointment+o-amino thiophenol+toluene solution;
(2) slowly splash into catalyzer phosphorus trichloride 4ml ± 0.1ml by separating funnel in four-hole boiling flask, the speed of splashing into is 0.67/min, and the time of splashing into is 60min ± 3min;
(3) stir while splashing into;
(4) the current prolong carries out condensing reflux circulation cooling, cools off above simultaneously four-hole boiling flask being fixed on the water tank of 5 ℃ ± 1 ℃ of water temperature;
(5) in the process that drips phosphorus trichloride, will discharge hydrogen chloride gas, and discharge by prolong;
(6) after dripping the catalyzer phosphorus trichloride, begin reaction soln is heated, Heating temperature is 80 ℃ ± 5 ℃, and proceeds to stir, it is thick that solution is;
(7) drip after phosphorus trichloride finishes, continue under heated condition, to stir 150min ± 5min, mixing solutions is reacted completely, clarify to solution;
(8) cooling: clarifying mixing solutions is placed special container, at 20 ℃ ± 3 ℃ of clean environment, normal temperature, naturally cooling;
(9) vacuum filtration: cooled clarification mixing solutions is placed on three layers of qualitative filter paper of B on filter flask top, carry out vacuum filtration, the filter cake of retaining on the filter paper is product 2-(2-hydroxy phenyl) benzothiazole BTZ;
(10) with toluene wash filter cake product: filter cake is placed washing container, add toluene 80ml ± 3ml then, carry out agitator treating with magnetic stirring apparatus;
(11) filter: the mixing solutions after will washing places the funnel on the filter flask, filters with qualitative filter paper, stays the product filter cake;
(12) drying: the product filter cake after will washing, filtering places vacuum drying oven, carries out drying treatment, and temperature is 70 ℃ ± 5 ℃, time of drying 40min ± 3min; Can get product 8.1g;
(13) recrystallization is purified:
With washing, vacuum filtration, dried 2-(2-hydroxy phenyl) benzothiazole BTZ, place there-necked flask, add dehydrated alcohol 80ml ± 3ml, it is dissolved fully, put 720min ± 10min, extremely water white whiskers body material is separated out, have in the B of three layers of qualitative filter paper in solution poured into, B is inserted on the filter flask, and the dehydrated alcohol waste liquid is evacuated in the filter flask, retains the product filter cake on the filter paper;
(14) secondary drying: the product collection behind recrystallization, the vacuum filtration to special container, is placed the bottom storage and the drying of drying basin, and add siccative Vanadium Pentoxide in FLAKES 200g ± 5g;
3), chemical reaction
In being dissolved with the toluene mixing solutions of Whitfield's ointment, o-amino thiophenol, add the catalyzer phosphorus trichloride, will carry out chemical reaction, reaction formula is as follows:
In the formula:
SH---sulphur hydrogen root
NH
2---amino
OH---hydroxyl
O---oxygen
S---sulphur
N---nitrogen
BTZ---2-(2-hydroxy phenyl) benzothiazole
III, Synthetic 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2
1), raw material mixes
2-(2-hydroxy phenyl) benzothiazole BTZ 2.50g ± 0.01g is added in the there-necked flask, add methyl alcohol 60ml ± 1ml then, make its dissolving, obtain 2-(2-hydroxy phenyl) benzothiazole+methanol mixed solution with magnetic stirrer;
2), heat dissolving
There-necked flask placed on the electric mantle heat, Heating temperature is 60 ℃ ± 3 ℃, and be 30min ± 3min heat-up time, heats while stirring, and makes the mixed solution dissolving, stops heating then;
3), execute alkali, adding triethylamine
Splash into triethylamine 7ml ± 0.5ml by separating funnel to there-necked flask, dripping speed is 7/min, and the time of splashing into is 10min ± 0.5min, to regulate the potential of hydrogen of mixing solutions, its acidity-basicity ph value=10, meta-alkalescence;
4), preparation Beryllium sulfate tetrahydrate solution
In special container, put Beryllium sulfate tetrahydrate BeSO
44H
2O 0.973g ± 0.01g adds deionized water 20ml ± 1ml then, with magnetic stirrer 30min ± 2min, makes its dissolving, becomes Beryllium sulfate tetrahydrate BeSO
44H
2The O aqueous solution;
5), drip the Beryllium sulfate tetrahydrate aqueous solution
The Beryllium sulfate tetrahydrate aqueous solution is placed separating funnel, splash into slowly in the there-necked flask, and add 2-(2-hydroxy phenyl) benzothiazole+methanol solution that triethylamine executes behind the alkali and mix, stir while splashing into, the speed of splashing into is 10/min, and the time of splashing into is 20min ± 1min, after dropwising, under 20 ℃ ± 3 ℃ of normal temperature, continue to stir 180min ± 5min, make its reaction, get reaction soln, generate yellow mercury oxide in the reaction soln, chemical equation is as follows:
In the formula:
BeSO
4---beryllium sulfate
Be---beryllium
H
2SO
4---sulfuric acid
6), vacuum filtration
With reacted solution place vacuum filtration bottle top in the suction funnel of three layers of qualitative filter paper is arranged, open the vacuum filtration pump, waste liquid and by product are evacuated in the filter flask, the product filter cake is stayed on the filter paper, i.e. the yellow powder product;
7), washing
The yellow powder product of collecting on the qualitative filter paper places the personal cleansing container, adds deionized water 40ml ± 2ml then, washs 30min ± 3min with magnetic stirrer, becomes mixed solution;
8), secondary vacuum suction filtration
With yellow powder product and the mixed solution of deionized water of washing, place filter flask top in the B of three layers of qualitative filter paper is arranged, unlatching vacuum filtration pump, deionized water and waste liquid are evacuated in the filter flask, yellow powder shape product is stayed on the qualitative filter paper;
9), oven dry
In special container, place vacuum drying oven to dry then the yellow powder product collection of secondary vacuum suction filtration, bake out temperature is 100 ℃ ± 3 ℃, and drying time is 40min ± 3min;
10), recrystallization is purified three times
The yellow powder product that washing, vacuum filtration, oven dry are obtained places there-necked flask, and place on the electric mantle, add methyl alcohol 40ml ± 2ml, stir with magnetic stirring apparatus, Heating temperature is 64.7 ℃ ± 2 ℃, makes the methyl alcohol mixed liquor boiling, constant temperature 30min ± 2min, heat while stirring, stop heating then;
Vacuum filtration: have in the B of three layers of qualitative filter paper in while hot methyl alcohol mixed liquor being poured into, B is inserted on the vacuum filtration bottle, carry out suction filtration with vacuum pump, product is stayed on the qualitative filter paper, and methyl alcohol waste liquid and by product are evacuated in the filter flask;
The recrystallization purification processes repeats three times, and the product on the qualitative filter paper is 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2Yellow powder;
11), oven dry once more
Through the Be of three recrystallization purification processes (BTZ)
2Yellow powder is collected in the special container, places vacuum drying oven, dries once more, and temperature is 80 ℃ ± 3 ℃, and drying time is 60min ± 3min, promptly obtains 2-(2-hydroxy phenyl) the benzothiazole chelated beryllium Be (BTZ) of highly purified blue light-emitting after the oven dry
2Yellow powder.
IV, detection, chemical examination, analysis, sign
To producing 2-(2-hydroxy phenyl) the benzothiazole chelated beryllium Be (BTZ) that obtains
2Yellow powder will carry out detection, analysis, the sign of structural analysis, luminescent properties, purity of color and chromaticity coordinates, carries out structural analysis with infrared spectrometer, carries out luminescent properties and purity of color analysis with spectrum Emanations Analysis instrument.
V, storage
To producing 2-(2-hydroxy phenyl) the benzothiazole chelated beryllium Be (BTZ) that obtains
2Yellow powder places brown transparent round mouth Glass Containers, and airtight lucifuge stores, and places shady and cool dry environment, and storing temp is 20 ℃ ± 3 ℃, waterproof, protection against the tide, fire prevention, sun-proof, anti-soda acid to corrode, and will take beryllium poison safeguard procedures.
Described preparation 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2, be with Whitfield's ointment, o-amino thiophenol, Beryllium sulfate tetrahydrate be raw material, with toluene, methyl alcohol be solvent, be catalyzer with the phosphorus trichloride, be siccative with the Vanadium Pentoxide in FLAKES, with the triethylamine be acidity-basicity ph value conditioning agent, with dehydrated alcohol, methyl alcohol be recrystallization solvent, with the deionized water be Beryllium sulfate tetrahydrate solvent, be washing composition, be shielding gas with deionized water, toluene with rare gas element-nitrogen.
Described preparation 2-(2-hydroxy phenyl) benzothiazole BTZ drips phosphorus trichloride PCl
3The speed of splashing into be 0.67/min, splash into time 60min ± 2min, vigorous stirring, water tank quickens cooling, and 5 ℃ ± 1 ℃ of water tank temperature is after dripping phosphorus trichloride, be warming up to 80 ℃ ± 3 ℃, continue to stir 150min ± 5min, naturally cool to 20 ℃ ± 3 ℃ of normal temperature then.
Described preparation 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2, dripping the Beryllium sulfate tetrahydrate aqueous solution, the speed of splashing into is 10/min, the dropping time is 20min ± 1min, reacts under 20 ℃ ± 3 ℃ of normal temperature, continues to stir 180min ± 5min.
Described preparation 2-(2-hydroxy phenyl) benzothiazole BTZ; the mixing of Whitfield's ointment, o-amino thiophenol, toluene, dissolving, stirring under heated condition, under the nitrogen protection, water condensation carries out under refluxing; Heating temperature is 55 ℃ ± 0.5 ℃; time is 10min ± 2min, and the nitrogen input speed is 0.5cm
3/ min.
Beneficial effect
The present invention compares with background technology has tangible advance, adopted brand-new preparation technology's flow process, earlier carry out selected to used chemical substance, and carry out control of purity, produce in two stages then, at first prepare Synthetic 2-(2-hydroxy phenyl) benzothiazole BTZ, and then Synthetic 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2Product is in preparation process, fs is in being dissolved with the toluene mixing solutions of Whitfield's ointment and o-amino thiophenol, adding the catalyzer phosphorus trichloride makes it carry out chemical reaction, cool off then, vacuum filtration, drying, recrystallization purify, make the water white whiskers body of 2-(2-hydroxy phenyl) benzothiazole BTZ, subordinate phase is with 2-(2-hydroxy phenyl) benzothiazole BTZ, Beryllium sulfate tetrahydrate BeSO
44H
2O is a raw material, with methyl alcohol is solvent, and adds triethylamine and execute alkali, makes its dissolving, reaction, purify three times through vacuum filtration, washing, oven dry, recrystallization, finally obtain 2-(2-hydroxy phenyl) the benzothiazole chelated beryllium Be (BTZ) of the yellow powder shape of highly purified, blue light-emitting
2Product, this preparation method use that equipment is few, technical process is short, productive rate is high, can reach 85%, the blue light high color purity, can reach 0.7497, are very good 2-(2-hydroxy phenyl) the benzothiazole chelated beryllium Be (BTZ) that produces
2Method, this blue light material can be used for war industry, electronic industry and luminescence technology field.
Description of drawings
Fig. 1 is preparation technology's schema
Fig. 2 is Synthetic 2-(2-hydroxy phenyl) benzothiazole BTZ state graph
Fig. 3 is Synthetic 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2State graph
Fig. 4 is 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2The infrared light collection of illustrative plates
Fig. 5 is 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2The blue light color coordinate diagram
Fig. 6 is 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2The photoluminescence collection of illustrative plates
Fig. 7 is 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2The fluorescent exciting spectrogram
Shown in the figure, the piece number inventory is as follows:
1, electric mantle, 2, temperature display, 3, four-hole boiling flask, 4, nitrogengas cylinder, 5, nitrogen valve, 6, nitrogen 7, the nitrogen input tube, 8, separating funnel 9, magnetic stirring apparatus, 10, prolong, 11, water-in, 12, water outlet, 13, soft rubber ball, 14, soft rubber ball, 15, soft rubber ball, 16, soft rubber ball, 17, electric mantle, 18, phosphorus trichloride liquid, 19, nitrogen and hydrogen chloride gas, 20, there-necked flask, 21, temperature display, 22, separating funnel, 23, magnetic stirring apparatus, 24, separating funnel, 25, methyl alcohol+2-(2-hydroxy phenyl) benzothiazole BTZ mixed solution, 26, Beryllium sulfate tetrahydrate+deionized water mixed solution, 27, triethylamine, 28, Whitfield's ointment+o-amino thiophenol+toluene mixing solutions, 29, soft rubber ball, 30, soft rubber ball, 31, soft rubber ball, 32, the air outlet.
Embodiment
The invention will be further described below in conjunction with accompanying drawing:
Shown in Figure 1, be to produce 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2Process flow sheet will carry out in strict accordance with technical process and technology numerical value, according to the order of sequence operation.
Want strict selected to preparing required chemical substance material, and carry out purity, content control, avoid too much impurity to get involved, prevent side reaction, in order to avoid influence degree of purity of production and luminescent properties.
To the chemical substance material that chemical reaction uses, strict and use the electronic scales weighing, guarantee that chemical reaction accurately carries out in molar ratio, to optimize reaction parameter, avoid unnecessary waste.
Dissolving Whitfield's ointment+o-amino thiophenol+toluene is to be to carry out under 55 ℃ ± 0.5 ℃ state in Heating temperature; will be under the whole process protection of nitrogen; because contain amino in the o-amino thiophenol structure, very easily oxidized, rare gas element---nitrogen can effectively be prevented the generation of oxidation.
Vigorous reaction will take place in the adding of catalyzer phosphorus trichloride, need stir fast, and quicken cooling with water tank.
In the process of preparation 2-(2-hydroxy phenyl) benzothiazole BTZ, to carry out vacuum filtration, washing, filtration, drying, the recrystallization of product and purify, obtain 2-(2-hydroxy phenyl) benzothiazole BTZ product.
Synthetic 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2Product is to be raw material, to be solvent with methyl alcohol, deionized water with 2-(2-hydroxy phenyl) benzothiazole BTZ, Beryllium sulfate tetrahydrate, to in 2-(2-hydroxy phenyl) benzothiazole BTZ mixing solutions, execute alkali, add triethylamine, regulate potential of hydrogen, the pH value is 10, meta-alkalescence, splash into the aqueous solution of Beryllium sulfate tetrahydrate then, make it carry out chemical reaction, obtain product, purify three times through vacuum filtration, oven dry, recrystallization, finally obtain 2-(2-hydroxy phenyl) the benzothiazole chelated beryllium Be (BTZ) of product-highly purified blue light-emitting
2Yellow powder.
At preparation 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2The time, the raw chemical material of use is to determine in the numerical range that sets in advance, with gram, milliliter, centimetre
3Be measure unit, when carrying out industrialization and produce, with kilogram, liter, rice
3Be measure unit.
Beryllium sulfate tetrahydrate BeSO
44H
2O is a highly toxic material, must carry out the gas defence protection in the experiment, and operator will wear frog suit in the operation, wear protective glove, wear a gas mask, and experimental installation will have the gas defence function, can not toxicly leak.
Employed four-hole boiling flask, there-necked flask, electric mantle, container, storage vessel, vacuum drying oven, drying basin, vacuum filtration bottle, B, qualitative filter paper, magnetic stirring apparatus, recrystallization equipment for purifying etc. will keep clean in preparation process, must not there be impurity to get involved, in case generate by product.
The catalyzer phosphorus trichloride plays crucial effect in reaction, and can discharge heat, and after dripping catalyzer, to make temperature rise to 80 ℃ ± 5 ℃, reflux and stir 150min ± 5min, the BTZ product that obtains the fluorescent quenching phenomenon can not occur, is optimal reaction temperature.
Shown in Figure 2, it is Synthetic 2-(2-hydroxy phenyl) benzothiazole BTZ state graph, synthesize and in four-hole boiling flask, carry out, the upper right quarter of electric mantle 1 is a temperature display 2, the middle part is a four-hole boiling flask 3, the top of four-hole boiling flask 3 is arranged side by side nitrogen input tube 7 from left to right, separating funnel 8, magnetic stirring apparatus 9, prolong 10, respectively by soft rubber ball 13,14,15,16 fixing seals, nitrogen input tube 7 connects nitrogengas cylinder 4, nitrogen valve 5, inside is nitrogen 6, put phosphorus trichloride liquid 18 in the separating funnel 8, the upper left quarter of prolong 10 is a water-in 11, right lower quadrant is a water outlet 12, top is air outlet 32, nitrogen and hydrogen chloride gas 19, nitrogen input tube 7, separating funnel 8, magnetic stirring apparatus 9, prolong 10 all inserts in the four-hole boiling flask 3, holds Whitfield's ointment+o-amino thiophenol+toluene mixing solutions 28 in the four-hole boiling flask 3.
Shown in Figure 3, be Synthetic 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2State graph, synthesize and in there-necked flask, carry out, the top of electric mantle 17 is there-necked flask 20, the top of there-necked flask 20 is arranged side by side separating funnel 22, magnetic stirring apparatus 23, separating funnel 24 from left to right, respectively by soft rubber ball 29,30,31, fixing seal, in the separating funnel 22 is the Beryllium sulfate tetrahydrate aqueous solution 26, in the separating funnel 24 is triethylamine 27, in the there-necked flask 20 is 2-(2-hydroxy phenyl) benzothiazole BTZ+ methyl alcohol mixed liquor 25, and the upper left quarter of electric mantle 17 is a temperature display 21.
Shown in Figure 4, be 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2Infrared spectrogram, ordinate zou is a transmitance, X-coordinate is a wave number, unit is cm
-1, 3060cm wherein
-1Spike, the stretching vibration peak of corresponding benzene intra-annular C-H, wherein 1547cm
-1, 1493cm
-1, 1426cm
-1Be carbon=carbon stretching vibration peak, 1608cm
-1Be nitrogen-oxygen covalent linkage stretching vibration peak, 668cm
-1, 607cm
-1Vibration peak be the stretching vibration absorption peak of beryllium-oxonium ion key.
Shown in Figure 5, be 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2The blue light color coordinate diagram, the coordinate intersection is 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ) in length and breadth
2Chromaticity coordinates, wherein X=0.1439, Y=0.1720, blue light color purity are 0.7491, are the photic blue light emitting material of high brightness.
Shown in Figure 6, be 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2The blue light photoluminescence collection of illustrative plates that under the ultraviolet excitation of 365nm, obtains, X-coordinate is a wavelength, and unit is nm, and ordinate zou is the relative intensity index, can see 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2The feature glow peak be 465nm.
Shown in Figure 7, be 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2Fluorescence excitation spectrum, X-coordinate is a wavelength, unit is nm, ordinate zou is the relative intensity index, wherein figure line a is for exciting collection of illustrative plates, figure line b is the emission collection of illustrative plates, maximum excitation wavelength is 436nm, the optimum transmit wavelength is 454nm;
Each preparation apparatus is in quasi-operating status;
Selected raw chemical material, and carry out control of purity;
Preparation 2-(2-hydroxy phenyl) benzothiazole BTZ:
Take by weighing Whitfield's ointment 6.3g ± 0.01g, o-amino thiophenol 5ml ± 0.1ml, toluene 80ml ± 3ml carries out mixed dissolution, stirring, heats 55 ℃ ± 0.5 ℃, time 10min ± 2min, nitrogen protection, inflated with nitrogen speed is 0.5cm
3/ min, the water condensation reflux cooling;
Splash into catalyzer phosphorus trichloride PCl
34ml ± 0.1ml, 0.67/min of speed, time 60min ± 3min stirs fast, water tank quickens cooling, and 5 ℃ ± 1 ℃ of water tank temperature discharges hydrogen chloride gas, drips off and is heated to 80 ℃ ± 5 ℃, continue to stir 150min ± 5min, naturally cool to 20 ℃ ± 3 ℃ then, combination reaction;
Vacuum filtration: three layers of qualitative filter paper, the product filter cake splashes into and carries out chemical reaction in the process;
Washing: toluene 80ml ± 3ml, stir;
Filter: qualitative filter paper filters, and retains the product filter cake;
Dry: vacuum drying oven, 70 ℃ ± 5 ℃, 40min ± 3min gets product 8.1g;
Recrystallization is purified: dehydrated alcohol 80ml ± 3ml, and 2-(2-hydroxy phenyl) benzothiazole BTZ 8.1g places 720min ± 10min, separates out water white whiskers body product B TZ in the solution;
Drying basin drying: Vanadium Pentoxide in FLAKES 200g ± 5g, product 2-(2-hydroxy phenyl) benzothiazole BTZ;
Synthetic 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2:
Take by weighing 2-(2-hydroxy phenyl) benzothiazole BTZ 2.5g ± 0.01g, methyl alcohol 60ml ± 1ml, mix in the there-necked flask and stir heating for dissolving, 60 ℃ ± 3 ℃ of temperature, time 30min ± 3min;
Execute alkali: splash into triethylamine 7ml ± 0.5ml, drip 7/min of speed, time 10min ± 0.5min, pH value=10, meta-alkalescence;
Preparation Beryllium sulfate tetrahydrate BeSO
44H
2The O aqueous solution: Beryllium sulfate tetrahydrate 0.973g ± 0.01g, deionized water 20ml ± 1ml stirs 30min ± 2min, becomes mixing solutions;
Drip Beryllium sulfate tetrahydrate BeSO
44H
2The O aqueous solution: in the there-necked flask that fills 2-(2-hydroxy phenyl) benzothiazole BTZ+ methyl alcohol, splash into BeSO
44H
2The O aqueous solution drips 10/min of speed, and time 20min ± 1min reacts under 20 ℃ ± 3 ℃ of normal temperature, continues to stir 180min ± 5min, combination reaction;
Vacuum filtration: three layers of qualitative filter paper, retain yellow powder;
Washing: deionized water 40ml ± 2ml, stir 30min ± 3min;
Secondary suction filtration: carry out in the filter flask, obtain the yellow powder product;
Oven dry: 100 ℃ ± 5 ℃ of vacuum drying ovens, time 40min ± 3min;
Recrystallization is purified three times: yellow powder+methyl alcohol 40ml ± 2ml is heated to 64.7 ℃ ± 2 ℃ of boilings, constant temperature 30min ± 2min;
Vacuum filtration: carry out vacuum filtration behind the recrystallization while hot, retain the yellow powder filter cake;
Secondary drying: 80 ℃ ± 3 ℃ of vacuum drying ovens, time 60min ± 3min obtains 2-(2-hydroxy phenyl) the benzothiazole chelated beryllium Be (BTZ) of highly purified blue light-emitting
2The yellow powder product, thus the whole process for preparing finished.
Claims (2)
1. the preparation method of the benzothiazole chelated beryllium of the 2-of a blue light-emitting (2-hydroxy phenyl) is characterized in that:
Preparation method is as follows:
I, selected raw chemical material
Carry out selectedly to producing required raw chemical material, and carry out control of purity:
Whitfield's ointment: solid crystals 〉=96%
O-amino thiophenol: liquid 98%
Toluene: liquid 99.5%
Phosphorus trichloride: liquid 〉=95.5%
Vanadium Pentoxide in FLAKES: solid 99.5%
Triethylamine: liquid 99.0%
Dehydrated alcohol: liquid 〉=99.7%
Methyl alcohol: liquid 99.5%
Deionized water: liquid 99.999%
Nitrogen: gas 99.9%
Beryllium sulfate tetrahydrate: solid 〉=99%
II, preparation 2-(2-hydroxy phenyl) benzothiazole
1), dissolving Whitfield's ointment
(1) in four-hole boiling flask, carries out, and on electric mantle, heat;
(2) at first Whitfield's ointment 6.3g ± 0.01g and o-amino thiophenol 5ml ± 0.1ml are placed four-hole boiling flask, add toluene 80ml ± 3ml, heating and stirring make the Whitfield's ointment dissolving, Heating temperature is 55 ℃ ± 0.5 ℃, dissolution time is 10min ± 2min, feed nitrogen to four-hole boiling flask simultaneously, the nitrogen input speed is 0.5cm
3/ min, input time 10min ± 2min, simultaneously prolong carries out the cooling of water condensation reflux cycle, stops heating after Whitfield's ointment dissolves fully;
2), add catalyzer phosphorus trichloride, combination reaction
(1) dissolving of the Whitfield's ointment in four-hole boiling flask back becomes Whitfield's ointment+o-amino thiophenol+toluene solution;
(2) slowly splash into catalyzer phosphorus trichloride 4ml ± 0.1ml by separating funnel in four-hole boiling flask, the speed of splashing into is 0.67/min, and the time of splashing into is 60min ± 3min;
(3) stir while splashing into;
(4) the current prolong carries out condensing reflux circulation cooling, cools off above simultaneously four-hole boiling flask being fixed on the water tank of 5 ℃ ± 1 ℃ of water temperature;
(5) in the process that drips phosphorus trichloride, will discharge hydrogen chloride gas, and discharge by prolong;
(6) after dripping the catalyzer phosphorus trichloride, begin reaction soln is heated, Heating temperature is 80 ℃ ± 5 ℃, and proceeds to stir, it is thick that solution is;
(7) drip after phosphorus trichloride finishes, continue under heated condition, to stir 150min ± 5min, mixing solutions is reacted completely, clarify to solution;
(8) cooling: clarifying mixing solutions is placed special container, at 20 ℃ ± 3 ℃ of clean environment, normal temperature, naturally cooling;
(9) vacuum filtration: cooled clarification mixing solutions is placed on three layers of qualitative filter paper of B on filter flask top, carry out vacuum filtration, the filter cake of retaining on the filter paper is product 2-(2-hydroxy phenyl) benzothiazole BTZ;
(10) with toluene wash filter cake product: filter cake is placed washing container, add toluene 80ml ± 3ml then, carry out agitator treating with magnetic stirring apparatus;
(11) filter: the mixing solutions after will washing places the funnel on the filter flask, filters with qualitative filter paper, stays the product filter cake;
(12) drying: the product filter cake after will washing, filtering places vacuum drying oven, carries out drying treatment, and temperature is 70 ℃ ± 5 ℃, and time of drying, 40min ± 3min got product 8.1g;
(13) recrystallization is purified:
With washing, vacuum filtration, dried 2-(2-hydroxy phenyl) benzothiazole BTZ, place there-necked flask, add dehydrated alcohol 80ml ± 3ml, it is dissolved fully, put 720min ± 10min, extremely water white whiskers body material is separated out, have in the B of three layers of qualitative filter paper in solution poured into, B is inserted on the filter flask, and the dehydrated alcohol waste liquid is evacuated in the filter flask, retains the product filter cake on the filter paper;
(14) secondary drying: the product collection behind recrystallization, the vacuum filtration to special container, is placed the bottom storage and the drying of drying basin, and add siccative Vanadium Pentoxide in FLAKES 200g ± 5g;
III, Synthetic 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2
1), raw material mixes
2-(2-hydroxy phenyl) benzothiazole BTZ 2.50g ± 0.01g adds in the there-necked flask, adds methyl alcohol 60ml ± 1ml then, makes its dissolving with magnetic stirrer, obtains 2-(2-hydroxy phenyl) benzothiazole+methanol mixed solution;
2), heat dissolving
There-necked flask placed on the electric mantle heat, Heating temperature is 60 ℃ ± 3 ℃, and be 30min ± 3min heat-up time, heats while stirring, and makes the mixed solution dissolving, stops heating then;
3), execute alkali, adding triethylamine
Splash into triethylamine 7ml ± 0.5ml by separating funnel to there-necked flask, dripping speed is 7/min, and the time of splashing into is 10min ± 0.5min, to regulate the potential of hydrogen of mixing solutions, its acidity-basicity ph value=10, meta-alkalescence;
4), preparation Beryllium sulfate tetrahydrate solution
In special container, put Beryllium sulfate tetrahydrate BeSO
44H
2O 0.973g ± 0.01g adds deionized water 20ml ± 1ml then, with magnetic stirrer 30min ± 2min, makes its dissolving, becomes Beryllium sulfate tetrahydrate BeSO
44H
2The O aqueous solution;
5), drip the Beryllium sulfate tetrahydrate aqueous solution
The Beryllium sulfate tetrahydrate aqueous solution is placed separating funnel, splash into slowly in the there-necked flask, and add 2-(2-hydroxy phenyl) benzothiazole+methanol solution that triethylamine executes behind the alkali and mixes stirring while splashing into, the speed of splashing into is 10/min, the time of splashing into is 20min ± 1min, after dropwising, under 20 ℃ ± 3 ℃ of normal temperature, continue to stir 180min ± 5min, make its reaction, get reaction soln, generate yellow mercury oxide in the reaction soln;
6), vacuum filtration
With reacted solution place vacuum filtration bottle top in the suction funnel of three layers of qualitative filter paper is arranged, open the vacuum filtration pump, waste liquid and by product are evacuated in the filter flask, the product filter cake is stayed on the filter paper, i.e. the yellow powder product;
7), washing
The yellow powder product of collecting on the qualitative filter paper places the personal cleansing container, adds deionized water 40ml ± 2ml then, washs 30min ± 3min with magnetic stirrer, becomes mixed solution;
8), secondary vacuum suction filtration
With yellow powder product and the mixed solution of deionized water of washing, place filter flask top in the B of three layers of qualitative filter paper is arranged, unlatching vacuum filtration pump, deionized water and waste liquid are evacuated in the filter flask, yellow powder shape product is stayed on the qualitative filter paper;
9), oven dry
In special container, place vacuum drying oven to dry then the yellow powder product collection of secondary vacuum suction filtration, bake out temperature is 100 ℃ ± 3 ℃, and drying time is 40min ± 3min;
10), recrystallization is purified three times
The yellow powder product that washing, vacuum filtration, oven dry are obtained places there-necked flask, and place on the electric mantle, add methyl alcohol 40ml ± 2ml, stir with magnetic stirring apparatus, Heating temperature is 64.7 ℃ ± 2 ℃, makes the methyl alcohol mixed liquor boiling, constant temperature 30min ± 2min, heat while stirring, stop heating then;
Vacuum filtration: have in the B of three layers of qualitative filter paper in while hot methyl alcohol mixed liquor being poured into, B is inserted on the vacuum filtration bottle, carry out suction filtration with vacuum pump, product is stayed on the qualitative filter paper, and methyl alcohol waste liquid and by product are evacuated in the filter flask;
The recrystallization purification processes repeats three times, and the product on the qualitative filter paper is 2-(2-hydroxy phenyl) benzothiazole chelated beryllium Be (BTZ)
2Yellow powder;
11), oven dry once more
Through the Be of three recrystallization purification processes (BTZ)
2Yellow powder is collected in the special container, places vacuum drying oven, dries once more, and temperature is 80 ℃ ± 3 ℃, and drying time is 60min ± 3min, promptly obtains 2-(2-hydroxy phenyl) the benzothiazole chelated beryllium Be (BTZ) of highly purified blue light-emitting after the oven dry
2Yellow powder;
IV, detection, chemical examination, analysis, sign
To producing 2-(2-hydroxy phenyl) the benzothiazole chelated beryllium Be (BTZ) that obtains
2Yellow powder will carry out detection, analysis, the sign of structural analysis, luminescent properties, purity of color and chromaticity coordinates, carries out structural analysis with infrared spectrometer, carries out luminescent properties and purity of color analysis with spectrum Emanations Analysis instrument;
V, storage
To producing 2-(2-hydroxy phenyl) the benzothiazole chelated beryllium Be (BTZ) that obtains
2Yellow powder places brown transparent round mouth Glass Containers, and airtight lucifuge stores, and places shady and cool dry environment, and storing temp is 20 ℃ ± 3 ℃, waterproof, protection against the tide, fire prevention, sun-proof, anti-soda acid to corrode, and will take beryllium poison safeguard procedures.
2. the preparation method of the benzothiazole chelated beryllium of the 2-of blue light-emitting according to claim 1 (2-hydroxy phenyl) is characterized in that: described preparation 2-(2-hydroxy phenyl) benzothiazole BTZ, dropping phosphorus trichloride PCl
3Speed be 0.67/min, splash into time 60min ± 2min, vigorous stirring, water tank quickens cooling, 5 ℃ ± 1 ℃ of water tank temperature after dripping phosphorus trichloride, is warming up to 80 ℃ ± 3 ℃, continues to stir 150min ± 5min, naturally cools to 20 ℃ ± 3 ℃ then.
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| CN103012479A (en) * | 2012-12-25 | 2013-04-03 | 东莞有机发光显示产业技术研究院 | A kind of phosphorus-based electron transport material and its preparation method and application |
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| US20050170211A1 (en) * | 2004-02-02 | 2005-08-04 | Sharp Kabushiki Kaisha | Organic electroluminescent element |
| CN1658723A (en) * | 2005-01-26 | 2005-08-24 | 天津理工大学 | A kind of white organic electroluminescence device and preparation method thereof |
| CN1711000A (en) * | 2005-07-19 | 2005-12-21 | 天津理工大学 | Flexible white organic electroluminescent device and its preparation method |
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| US20050170211A1 (en) * | 2004-02-02 | 2005-08-04 | Sharp Kabushiki Kaisha | Organic electroluminescent element |
| CN1658723A (en) * | 2005-01-26 | 2005-08-24 | 天津理工大学 | A kind of white organic electroluminescence device and preparation method thereof |
| CN1711000A (en) * | 2005-07-19 | 2005-12-21 | 天津理工大学 | Flexible white organic electroluminescent device and its preparation method |
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