CN1743406A - Polyarylether non-conjugated electroluminescent material containing oxadiazole unit and its preparation method - Google Patents
Polyarylether non-conjugated electroluminescent material containing oxadiazole unit and its preparation methodDownload PDFInfo
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- CN1743406A CN1743406ACN 200510015284CN200510015284ACN1743406ACN 1743406 ACN1743406 ACN 1743406ACN 200510015284CN200510015284CN 200510015284CN 200510015284 ACN200510015284 ACN 200510015284ACN 1743406 ACN1743406 ACN 1743406A
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Abstract
Description
[technical field]: the present invention relates to unitary polyarylether non conjugated electroluminescent mater of Han oxadiazole and preparation method thereof.
[background technology]: from 1987 Deng Qingyun (C W Tang) reported oxine aluminium (Alq3) low pressure, the organic electroluminescent phenomenon under the direct drive since, organic electroluminescence device (OLED) has caused domestic and international scientific research personnel's extensive concern as a kind of new technology of flat.Compare with other flat panel display, OLED has low-voltage driving, high brightness, full color, active illuminating, total solidsization, the visual angle is wide and easily make comprehensive advantages such as flexible screen.Therefore, the electroluminescent organic material of seeking the novel texture of excellent performance has crucial meaning.Traditional polymer luminescent material has: polyphenyl class (PP), polyphenylene ethylene class (PPV), polythiophene class (PTH), poly-fluorenes class (PF) and corresponding multipolymer thereof.Their structural common features are interlaced two key πDian Zis or the accurate one dimension that has been made up delocalized conjugacy in the polymer molecular chain and molecular chain by the big πDian Zi stream of aromatic hydrocarbons.The conjugacy of polymer luminescent material is to the luminescence process of device, has crucial influence as the transmission in electronics and hole etc.The full conjugate polymkeric substance is difficult to obtain the material of blue light-emitting because the conjugation degree is big.In order to reduce the conjugation degree, improve the processing characteristics of conjugated polymers, in conjugated system, embed non-conjugated segment and form conjugation/non-conjugated random copolymers, can reduce the conjugate length of conjugated system, thereby regulate its emission wavelength.People adopt not coplanar method that the conjugated luminophore is separated usually, or with the not conjugation segment isolation (as polyester, polymeric amide and polyimide family macromolecule) of conjugated luminophore; Perhaps use not conjugated structure segment with the conjugation of the whole molecule of conjugated luminophore isolation barrier.Select suitable luminescence center so again, just can determine the emission wavelength of whole molecule.Therefore the characteristics of luminescence of non-conjugated base polymer electroluminescent material and the research of electroluminescent device thereof report seldom studies this type of material and device has very important significance.
[summary of the invention]: the objective of the invention is to solve the full conjugate polymkeric substance owing to conjugated degree is difficult to obtain the shortcoming of the material of blue light-emitting greatly, unitary polyarylether non conjugated electroluminescent mater of a kind of novel Han oxadiazole and preparation method thereof is provided.This type of electroluminescent organic material can produce blue light, is soluble in usual vehicle, can adopt thermal evaporation or spin coating method to prepare luminescent device.
The unitary polyarylether non conjugated electroluminescent mater of Han oxadiazole provided by the invention has following structure:
In the said structure formula: R1, R2Be alkoxyl group, the alkoxyl group chain length is 1-18; Substituting group can be identical, also can be different.Aromatic ring Ar is
X and y are two kinds of structural unit ratio content, and satisfy 0≤x≤1; 0≤y≤1, x+y=1, n=1-100.
The preparation method of the non-conjugated type electroluminescent material of the unitary polyarylether of Han oxadiazole provided by the invention relates generally to the monomeric synthetic and Han oxadiazole unit cell of the unitary key of Han oxadiazole and bifunctional monomer (dihydroxyphenyl propane, sulfone are for dihydroxyphenyl propane or the sulfone mixture for dihydroxyphenyl propane and 1-(4-fluorophenyl sulfuryl-4-fluorobenzene)) in mixed solvent (N,N-DIMETHYLACETAMIDE: carry out the nucleophilic substitution polyreaction under the catalysis at salt of wormwood toluene=1: 1) under 110-165 ℃.
Described nucleophilic substitution polyreaction is under nitrogen protection; add bifunctional monomer's (dihydroxyphenyl propane; sulfone is for dihydroxyphenyl propane or the sulfone mixture for dihydroxyphenyl propane and 1-(4-fluorophenyl sulfuryl-4-fluorobenzene)) (mol ratio is 1: 1: 2-6) in the mixed solvent of N,N-DIMETHYLACETAMIDE and toluene (1: 1) for Han oxadiazole unit cell and salt of wormwood; react 1-1.5 hour stopped reaction down at 110-165 ℃; after boiling off solvent; with resistates with the dissolving of a spot of tetrahydrofuran (THF) after; pour purifying in the methyl alcohol into; filter; with filter cake vacuum-drying 24h, obtain the non-conjugated type electroluminescent material of the unitary polyarylether of described Han oxadiazole.
Described Han oxadiazole unit cell is the compound with following general formula:
Wherein, R1, R2Be alkoxyl group, the alkoxyl group chain length is 1-18; Substituting group can be identical, also can be different.X is a halogen.
The synthetic method of this compound is as follows: with R1, R2The terephthaldehyde's acetoacetic ester and the hydrazine hydrate that replace, the 48h that in ethanol, refluxes, product after purifying, with to the halogeno-benzene formyl chloride at room temperature reaction 3h in chloroform and triethylamine.Product after purifying with phosphorus oxychloride back flow reaction 3h, product separates through silica gel column chromatography and obtains.
Described bifunctional monomer is
The dihydroxyphenyl propane sulfone is for dihydroxyphenyl propane
Perhaps sulfone is for the mixture of dihydroxyphenyl propane and 1-(4-fluorophenyl sulfuryl-4-fluorobenzene).Because sulfone is for sulfuryl (SO in the dihydroxyphenyl propane2) existence can cause the product polymerization degree very low, for Tiao Jie oxadiazole unit in polymkeric substance ratio and obtain high molecular weight polymers, sulfone needs in advance and 1-(4-fluorophenyl sulfuryl-4-fluorobenzene) for dihydroxyphenyl propane
The prepared in reaction intermediate product
, this intermediate product continues the reaction of Yu Han oxadiazole unit cell again, can obtain high molecular weight polymers.
Advantage of the present invention and positively effect: introduce the oxadiazole unit the non-conjugated electroluminescent organic material that the polyarylether main chain has synthesized a kind of novel texture.This type of electroluminescent organic material can produce blue light, has remedied existing polymer materials blue light-emitting kind deficiency on the low side, has very important significance for theories.
[embodiment]:
Embodiment 1 contains the synthetic of oxadiazole unit cell [2,5-two (2-ethyl-hexyloxy)-1,4-pair-{ 2,2 '-[5-(right-the fluoro phenyl)]-1,3,4-oxadiazole base } benzene]
(1) 2,5-two [(2-ethyl)-hexyloxy]-1,4-benzoyl hydrazine synthetic
Under nitrogen protection, in there-necked flask, add 100ml dehydrated alcohol and 10g (0.2mol) hydrazine hydrate N2H4H2O.Add 2 of 11.9665g (0.025mol), 5-two [(2-ethyl)-hexyloxy]-1,4-diethyl terephthaldehyde acetoacetic ester, back flow reaction 48h stopped reaction in batches.Boil off solvent after being cooled to room temperature, resistates 150ml extracted with diethyl ether is washed to neutrality with ether layer, uses anhydrous sodium sulfate drying, leave standstill, filter, filtrate is revolved steaming, resistates uses column chromatography (eluent: sherwood oil: ethyl acetate=10: 1), get white crystal, productive rate 61.02%.Fusing point: 67.5-68.5 ℃
Ultimate analysis: C 63.47; H 10.34; N 12.51 (theoretical value: C24H42N4O4: C 63.97; H 9.39; N12.43)
(2) 2,5-two [(2-ethyl)-hexyloxy]-1,4-two [2,2 '-(to fluorobenzoyl)]-benzoyl hydrazine synthetic
Under nitrogen protection; in there-necked flask, add 2 of 11.2654 g (0.025mol); 5-two [(2-ethyl)-hexyloxy]-1; 4-benzoyl hydrazine, 2.53g (0.025mol) triethylamine and 100ml chloroform; the mixture that dropping contains 10ml chloroform and 6.9750g (0.05mol) parachlorobenzoyl chloride at room temperature stirs stopped reaction after 3 hours.Reactant is poured in the mixture of ice and water of 100ml, stirred, with the water washing chloroform twice of 100ml, use anhydrous sodium sulfate drying, standing over night is filtered, and revolves to steam and removes chloroform, and resistates normal hexane recrystallization obtains white crystal, productive rate 80.50%.Fusing point: 220 ℃.
Ultimate analysis: C 65.85; H 6.98; N 8.09 (theoretical value: C38H48F2N4O6: C 65.69; H 6.96; N 8.06)
(3) 2,5-two [(2-ethyl)-hexyloxy]-1,4-two-{ 2,2 '-[5-(to fluorophenyl)]-1,3,4-oxadiazole } benzene
Under nitrogen protection, in there-necked flask, add 2 of 4.1688g (0.006mol), 5-two [(2-ethyl)-hexyloxy]-1, the phosphorus oxychloride of 4-two [2,2 '-(to fluorobenzoyl)]-benzoyl hydrazine and 20ml.Reflux is stopped reaction after 3 hours.Be chilled in the mixture of ice and water of reactant carefully being poured after the room temperature into 200ml and stir, with the ethyl acetate extraction of 100ml 2 times, the washing organic layer is to neutral, use anhydrous sodium sulfate drying, standing over night is filtered, revolve to steam and remove ethyl acetate, resistates separates (eluent: sherwood oil: ethyl acetate=10: 1), obtain light yellow needle-like crystal, productive rate 88.21% with silica gel column chromatography.Fusing point: 159-160 ℃ ultimate analysis: C69.16; H6.71; N8.56 (theoretical value: C38H44F2N4O4: C 69.28; H 6.73; N8.50)
13Nucleus magnetic resonance (the CDCl of C3): δ 165.789,163.776 (C1), 116.464 (C2), 116.288 (C2 '), 129.242 (C3), 129.175 (C3 '), 120.300,120.276 (C4 '), 163.406 (C5), 164.493 (C6), 165.798 (C7), 114.327 (C8), 150.895 (C9), 11.003 (C13), 13.953 (C17), 22.828 (C16), 23.872 (C12), 28.886 (C15), 30.452 (C14), 39.181 (C11), 72.241 (C10) ppm.
Can confirm to have following structure thus:
Synthetic (being abbreviated as PE-1) of the unitary polyarylether non conjugated electroluminescent mater of embodiment 2 Han oxadiazoles
Under nitrogen protection; in there-necked flask, add 0.1732g (0.7589mmol) dihydroxyphenyl propane (2; the 2-double mutual-hydroxy phenenyl oxide), 2 of 0.50g (0.7589mmol); 5-two [(2-ethyl)-hexyloxy]-1; 4-two-{ 2; 2 '-[5-(to fluorophenyl)]-1,3,4-oxadiazole } benzene and 0.25g (1.81mmol) salt of wormwood is in the mixed solvent of 20ml N,N-DIMETHYLACETAMIDE/toluene (1: 1).At 165 ℃ of following 1 hour stopped reaction of reaction, steam desolventize after, with resistates with a spot of tetrahydrofuran (THF) dissolving after, pour purifying in the 200ml methyl alcohol into, filtration with filter cake vacuum 24h, obtains the unitary polyarylether non conjugated electroluminescent mater of Han oxadiazole.Light yellow solid, productive rate 92.1%.Results of elemental analyses: C 74.68; H 6.95; N 6.67 (theoretical value: C53H58N4O6: C 75.15; H 6.90; N 6.61)
Synthetic (being abbreviated as PE-2) of the unitary polyarylether non conjugated electroluminescent mater of embodiment 3 Han oxadiazoles
Under nitrogen protection; in there-necked flask, add 0.1897g (0.7589mmol) sulfone for 2 of dihydroxyphenyl propane, 0.50g (0.7589mmol); 5-two [(2-ethyl)-hexyloxy]-1; 4-two-{ 2; 2 '-[5-(to fluorophenyl)]-1; 3,4-oxadiazole } benzene and 0.25g (1.81mmol) salt of wormwood is in the mixed solvent of 20ml N,N-DIMETHYLACETAMIDE/toluene (1: 1).Experimental procedure is with embodiment 2, light yellow solid, productive rate 45.50%.
Results of elemental analyses: C 68.18; H 6.02; N 6.55; S 3.33.(theoretical value: C50H52N4O8S:C 69.10; H6.03; N 6.45; S 3.69)
Synthetic (being abbreviated as PE-3) of the unitary polyarylether non conjugated electroluminescent mater of embodiment 4 Han oxadiazoles
Under nitrogen protection; in there-necked flask, add the sulfone of 0.7589mmol for 2 of the mixture (mol ratio 1: 1) of dihydroxyphenyl propane and 1-(4-fluorophenyl sulfuryl-4-fluorobenzene), 0.50g (0.7589mmol); 5-two [(2-ethyl)-hexyloxy]-1; 4-two-{ 2; 2 '-[5-(to fluorophenyl)]-1; 3,4-oxadiazole } benzene and 0.25g (1.81mmol) salt of wormwood is in the mixed solvent of 20ml N,N-DIMETHYLACETAMIDE and toluene (1: 1).Experimental procedure gets light yellow solid, productive rate 60.0% with embodiment 2.
Embodiment 5 electroluminescent device performances
Performance: the solid fluorescence of polymkeric substance, device architecture are the maximum glow peak of the electroluminescent device of ITO/polymer/Ca/Ag, it is as shown in the table for high-high brightness:
| Polymkeric substance | The Mn molecular weight | The Mw molecular weight | UV (nm) | PL (nm) | Open bright voltage (V) | High-high brightness (cd/m2) |
| PE-1 PE-2 PE-3 | 8.2×103 1.8×103 3.4×104 | 3.3×104 3.3×103 1.3×105 | 374 374 397 | 439 438 572 | 30 30 10 | 20(40V) 37(32V) 102(19V) |
Claims (5)
1. one kind contains the non-conjugated electroluminescent organic material of the unitary polyarylether type of oxadiazole, has following structure:
In the said structure formula: R1, R2Be alkoxyl group, the alkoxyl group chain length is 1-18; Substituting group can be identical, also can be different; Aromatic ring Ar is
Wherein x and y are two kinds of structural unit ratio content, and satisfy 0≤x≤1; 0≤y≤1, x+y=1, n=1-100.
2. described preparation method who contains the non-conjugated electroluminescent organic material of the unitary polyarylether type of oxadiazole of claim 1; it is characterized in that the nucleophilic substitution polyreaction is under nitrogen protection; (mol ratio is 1: 2-6) in the mixed solvent of N,N-DIMETHYLACETAMIDE and toluene (1: 1) to add bifunctional monomer's Han oxadiazole unit cell and salt of wormwood; react 1-1.5 hour stopped reaction down at 110-165 ℃; after boiling off solvent; with resistates with the dissolving of a spot of tetrahydrofuran (THF) after; pour purifying in the methyl alcohol into; filter; with filter cake vacuum-drying, obtain the unitary polyarylether type of the described Han oxadiazole of claim 1 non conjugated electroluminescent mater.
3. the preparation method of the non-conjugated electroluminescent organic material of the unitary polyarylether type of Han oxadiazole according to claim 2 is characterized in that described Han oxadiazole unit cell is the compound with following general formula:
Wherein, R1, R2Be alkoxyl group, the alkoxyl group chain length is 1-18; Substituting group can be identical, also can be different; X is a halogen;
The synthetic method of this compound is as follows: with R1, R2The terephthaldehyde's acetoacetic ester and the hydrazine hydrate that replace, the 48h that in ethanol, refluxes, product after purifying, with to the halogeno-benzene formyl chloride at room temperature reaction 3h in chloroform and triethylamine, product after purifying with phosphorus oxychloride back flow reaction 3h, product separates through silica gel column chromatography and obtains.
4. the preparation method of the non-conjugated electroluminescent organic material of the unitary polyarylether type of Han oxadiazole according to claim 2 is characterized in that described bifunctional monomer is:
Dihydroxyphenyl propane, sulfone is for dihydroxyphenyl propane
Perhaps sulfone is for the mixture of dihydroxyphenyl propane and 1-(4-fluorophenyl sulfuryl-4-fluorobenzene).
5. the preparation method of the non-conjugated electroluminescent organic material of the unitary polyarylether type of Han oxadiazole according to claim 4 is characterized in that, because sulfone is for sulfuryl (SO in the dihydroxyphenyl propane2) existence can cause the product polymerization degree very low, for Tiao Jie oxadiazole unit in polymkeric substance ratio and obtain high molecular weight polymers, sulfone needs in advance and 1-(4-fluorophenyl sulfuryl-4-fluorobenzene) for dihydroxyphenyl propane
The prepared in reaction intermediate product
This intermediate product continues Yu Han oxadiazole unit cell again and obtains the non-conjugated electroluminescent organic material of the unitary polyarylether type of the described Han oxadiazole of claim 1 according to the reaction of the method for claim 2.
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| WO2011141714A1 (en)* | 2010-05-14 | 2011-11-17 | Cambridge Display Technology Limited | Organic light-emitting polymer and device |
| CN101402855B (en)* | 2008-07-17 | 2012-07-25 | 大连理工大学 | Polyarylether rare-earth complexes luminous material and preparing process thereof |
| CN101743261B (en)* | 2007-07-13 | 2013-04-03 | 昭和电工株式会社 | High molecular compound containing triazine ring and organic light-emitting device using the high molecular compound |
| CN108663346A (en)* | 2018-06-21 | 2018-10-16 | 天津理工大学 | L-cysteine fluorescence probe and preparation method and application based on conjugated polymer/metal ion complex |
- 2005
- 2005-09-29CNCN 200510015284patent/CN1743406A/enactivePending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101743261B (en)* | 2007-07-13 | 2013-04-03 | 昭和电工株式会社 | High molecular compound containing triazine ring and organic light-emitting device using the high molecular compound |
| CN101402855B (en)* | 2008-07-17 | 2012-07-25 | 大连理工大学 | Polyarylether rare-earth complexes luminous material and preparing process thereof |
| WO2011141714A1 (en)* | 2010-05-14 | 2011-11-17 | Cambridge Display Technology Limited | Organic light-emitting polymer and device |
| GB2493892A (en)* | 2010-05-14 | 2013-02-20 | Cambridge Display Tech Ltd | Organic light-emitting polymer and device |
| CN102947962A (en)* | 2010-05-14 | 2013-02-27 | 剑桥显示技术有限公司 | Organic light-emitting polymer and device |
| GB2484253B (en)* | 2010-05-14 | 2013-09-11 | Cambridge Display Tech Ltd | Organic light-emitting composition and device |
| US8981354B2 (en) | 2010-05-14 | 2015-03-17 | Cambridge Display Technology Limited | Organic light-emitting polymer and device |
| CN102947962B (en)* | 2010-05-14 | 2015-09-30 | 剑桥显示技术有限公司 | Organic luminescence polymer and device |
| GB2493892B (en)* | 2010-05-14 | 2016-05-11 | Cambridge Display Tech Ltd | Monomers for forming light-emitting or charge-transporting polymers |
| CN108663346A (en)* | 2018-06-21 | 2018-10-16 | 天津理工大学 | L-cysteine fluorescence probe and preparation method and application based on conjugated polymer/metal ion complex |
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