CN1743408A - Sigma-pi conjugated organic polymer material, and its preparing method and use - Google Patents
Sigma-pi conjugated organic polymer material, and its preparing method and use Download PDFInfo
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- CN1743408A CN1743408A CN 200510029514 CN200510029514A CN1743408A CN 1743408 A CN1743408 A CN 1743408A CN 200510029514 CN200510029514 CN 200510029514 CN 200510029514 A CN200510029514 A CN 200510029514A CN 1743408 A CN1743408 A CN 1743408A
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Abstract
This invention relates to an organic/polymer electroluminescent material for improving the electron and hole injection and transmission balance performance and increasing stability of the material and its preparation method. Units with electronic transmission structure and cavity transmission performance have fine cavity transmission performance such as polysilane, polugernane and satnnanes. The substitution of introduction of alkyl group can reduce the form of aggregates among molecules. The structure is favorable to increasing the glass-transition temperature of the material.
Description
Technical field
The invention belongs to the organic polymer material technical field, being specifically related to one all has the balance transmission ability to electronics and hole roughly the same the time, and contains regular relatively organic/polymer materials of unique p-type structure (as polysilane, poly-germane, poly-stannane etc.), structure and its production and application.
Background technology
Organic/polymer electroluminescent device (Organic/Polymer Light-Emitting Device, the change that fast development OLED/PLED) has brought revolution for the technique of display field.Advantages such as the indicating meter made from it has high image quality, and screen size can arbitrarily be adjusted, and energy consumption is low, and light weight and approaching adopts the flexible macromolecule substrate collapsible, and tooling cost is low have been represented the development trend in following technique of display field.
1987, C.W.Tang etc. successfully developed a kind of Organic Light Emitting Diode (OLED), did hole transmission layer (HTL) with aniline-TPD, and aluminium and 8-hydroxy-quinoline complex compound-ALQ are as luminescent layer (EML).Its operating voltage is less than 10V, and brightness is up to 1000cd/m
2Nineteen ninety, people's reported first such as the breadboard J.H.Burroughes of the Cavendish of univ cambridge uk with PPV (poly (p-phenylene vinylene), the polymeric film electroluminescent device of p-phenylene vinylene's preparation, obtained the blue green light output of direct-current biasing driving less than 14V, its quantum yield is 0.05%.Subsequently, the D.Braum of California, USA university and A.J.Heeger have reported that in 1992 its trigger voltage is 3V, has obtained the luminous of effective green and orange-yellow two kinds of colors with the photodiode of PPV and derivative preparation thereof.These breakthrough progress make this field become a research focus in recent years.
From 1987 till now, OLED technical development very rapid, especially the stability of device is greatly improved, and reaches practical requirement basically.Wherein the transformation period of green light material has reached 2～50,000 hours, and the transformation period of blue light material is also above 30,000 hours.And aspect luminous efficiency, OLED then is higher than the level of PDP and TFT-LCD far away.Aspect the colorize of device, proposed to comprise that three primary colours method, white light add multiple schemes such as colour filter embrane method, blue light energy transformation method, and had many companies to release the OLED sample that full color shows.
Organic electroluminescence device belongs to the two injection type luminescent devices of current carrier, is that injected electrons and hole are compound and luminous by radiation deexcitation generation in organism.Therefore, the injection balance in electronics and hole realizes that to device higher luminous efficiency is very important.Now, in order to solve electronics, this problem of hole transport balance, people have introduced electron transfer layer (ETL) or hole transmission layer (HTL) in organic electroluminescence device, formed the multilayer device structure, and use the material of low work content to make negative electrode.Though these methods can improve quantum yield to a certain extent, also have many problems.For example, the multilayer device structure has very big difficulty on technology of preparing, and low work function materials is extremely responsive for the variation of atmospheric gas pressure, extremely difficult compression.So producing the intrinsic structure for the PLEDs that develops efficient stable just has the polymkeric substance of equilibrated electron hole transmission performance just to seem highly significant.
Summary of the invention
The objective of the invention is to propose a kind of injection and output balance quality that can improve material electronics and hole, improve organic/polymer materials of material thermostability and spectrum stability and its production and application.
Organic/polymer materials that the present invention proposes, be in the structure of material, introduce fluorenes or oligomerization fluorenes or poly-fluorenes, perhaps introduce 1,3, structures such as 4-oxadiazole, substituted aniline, pyridine, benzoglyoxaline, naphthalene, triazole, thiazole, quinoline, anthracene or azophenlyene are as electric transmission section (n section), and the structure that introducing has the hole transport performance is as hole transport section (p section), and these structures with hole transport performance have polysilane, poly-germane, poly-stannane etc.
The present invention said organic/structure of polymer electroluminescence material is shown below:
Wherein, the M representative has the n-type structural unit of electronic transmission performance; The p-type structural unit that the G representative has the hole transport performance, n represents monomeric repetition number, n 〉=1; M represents the number of whole repeating unit, m 〉=1; R
1, R
2, R
3And R
4Refer to that some are identical or different, be used for the deliquescent group of strongthener, as alkyl C
nH
2n+1(n=1～12; As methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl etc.); Long-chain alkoxy base (as 2-ethyl hexyl oxy, octyloxy etc.); Unsaturated alkyl chain or fragrant hydrocarbon chain are as: vinyl, allyl group, to styryl, hydroxy butyl vinyl ether base, hydroxyethyl vinyl ether group; Also can be the group that contains aryl and long chain hydrocarbon groups, such as: phenyl, (4-octyloxy) phenyl, (4-(2-ethyl hexyl oxy)) phenyl etc.
The material that the present invention proposes is a kind of sigma-pi conjugated organic polymer material.
The preparation method of above-mentioned materials is as follows:
With two ends is that the M that halogen replaces is a raw material, be dissolved in earlier in-78 ℃ the tetrahydrofuran (THF), add butyllithium then, reaction forms the R-Li structure and then is translated into corresponding dihalo-substituted monomer with exsiccant dihalo-dialkyl silane monomer or dihalo-dialkyl group germane monomer or dihalo-dialkyl group stannane monomer reaction again.With this monomer and a certain amount of dihalo-dialkyl silane monomer or dihalo-dialkyl group germane monomer or dihalo-dialkyl group stannane monomer reacting by heating certain hour in the backflow system of non-polar solvent and key metal, perhaps obtain product with the ultrasonic reaction certain hour.Product is refining with Virahol, ethanol and methanol extraction respectively.Obtain corresponding silicon-containing polymer or germanium containing polymer or stanniferous polymkeric substance.
In the aforesaid method, the amount of (1) adding sodium is 1.2 times of theoretical amount, and concentration of reactants is 0.1～0.5mol/L; (2) the reacting by heating time is 2～36 hours, and the ultrasonic reaction time is 0.5～12 hour; (3) non-polar solvent comprises one or more the mixture in normal hexane, toluene, dimethylbenzene, sherwood oil, tetracol phenixin, hexanaphthene, dodecane and the cyclooctane etc.; (4) basic metal comprises one or more the mixture in lithium, sodium, potassium, the magnesium etc.
Compound involved in the present invention mainly is used as the preparation of organic polymer electroluminescent device.In addition, material involved in the present invention also can be in the widespread use that has of other field, such as the organic integration circuit, and organic field effect tube, OTFT, organic solar batteries, the application in organic laser diode or the like field.
Description of drawings
Fig. 1 is solution and the solid uv-absorbing and the fluorescence spectrum spectrogram of model molecule.
Wherein, solution is to use sherwood oil (60-90 ℃) as solvent, strength of solution＜1 * 10
-5Mol/L; Fluorescence spectrum uses the UV-light of 380nm to excite.
Embodiment
By the following examples the present invention is further specified, rather than limit the scope of the invention.
One, synthon:
In containing-78 ℃ of tetrahydrofuran solutions of 8.48g (51.1mmol) fluorenes, 120mL is added dropwise to the butyllithium (hexane solution of 2.5M of 42.92mL (107.31mmol); Aldrich).Mixture stirs 45min down at-78 ℃, adds the bromooctane of 22.70g (117.53mmol) again, and solution was raised to stirring at room 3 hours.Mixture is poured in the water and with the ether extraction, organic layer is with the salt water washing and use dried over mgso, removal of solvent under reduced pressure, excessive bromooctane underpressure distillation remove (44 ℃/0.3mmHg).Obtain 9 of 19.75g light brown, the 9-dioctyl fluorene.[fusing point: 34-37 ℃.
13C NMR (75MHz, CDCl
3): ‰ (ppm) 150.63,141.15,126.98,126.70,122.78,119.64,55.01,40.46,31.84,30.11,29.26,29.05,23.77,22.64,14.09.
1H NMR (300MHz, CDCl
3): ‰ (ppm) 7.82 (dd, 2H, J=4.3Hz), 7.42 (m, 6H), 2.12 (m, 4H, J=3.8Hz), 1.35-1.24 (m, 20H), 0.96 (t, 6H, J=7.1Hz), 0.79 (m, 4H, J=3.8Hz). ultimate analysis Calcd for C
29H
42: 390.651.Found:390.598.]
9, (15.01g 38.42mmol) is dissolved in the CHCl of 0 ℃ of 58mL to the 9-dioctyl fluorene
3And the iron trichloride of adding 96mg (0.59mmol) and the liquid bromine of 4.14mL (80.52mmol).Reaction is carried out in the dark, and solution is raised to room temperature and continues reaction 3 hours.Reaction solution is poured in the water also with Sulfothiorine flush away bromine russet, water layer CHCl
3Extracting twice merges organic layer obtains 21.07g (＞99%) light brown with dried over mgso product.[fusing point: 44-47 ℃.
13C NMR (75MHz, CDCl
3): ‰ (ppm) 152.44,138.94,130.04,126.07,121.38,120.96,55.56,40.02,31.63,29.78,29.04,29.01,23.51,22.47,13.94.
1H NMR (300MHz, CDCl3): ‰ (ppm) 7.53 (d, 2H, J=7.7Hz), 7.46 (d, 2H, J=1.8Hz), 7.44 (d, 2H, J=1.1Hz), 1.91 (m, 4H, J=3.7Hz), 1.26-1.05 (m, 20H), 0.83 (t, 6H, J=3.6Hz), 0.58 (m, 4H, J=3.5Hz) .]
Embodiment 2, and the oligomerization fluorenes of synthetic two ends band halogen (reference Y Geng, A Trajkovska, D Katsis, et al.JAm Chem Soc 2002,124,8337-8347.)
Two, synthetic model molecular compound:
Embodiment 3, and the structure of model molecule is shown below:
2, the 7 dibromo dioctyl fluorene that take by weighing 1.0924g (0.002mol) are dissolved in-78 ℃ the tetrahydrofuran (THF), add n-Butyl Lithium/normal hexane (0.004mol) reaction 30min of 2.5mL 1.6M then.Then, add 0.512g dichloro dialkyl silane monomer (0.004mol) at room temperature reaction 180min.Remove the lithium salts of generation with porous-film, n-butyl bromide is removed in underpressure distillation and solvent obtains 1.023g (yield 89%) product.This product and 0.228g (0.00178mol) dichlorodimethylsilane monomer dropping are gone into to be immersed in reaction obtained pale brown look liquid in 1 hour in the vial of the backflow system that contains 10mL toluene/0.046g sodium in 60 ℃ of ultrasonic wave washing troughs.It is poured in the 100mL methyl alcohol centrifugation polymkeric substance.Resulting polymers is removed insolubles with the Virahol dissolving again.Obtain 0.481g (yield 47%) polymkeric substance at last.M
n＝4600，M
w/M
n＝1.37。
The uv-absorbing of the solution of model molecule P1 and fluorescence spectrum spectrogram are referring to accompanying drawing.
Embodiment 4, and the structure of model molecule is shown below:
The dioctyl oligomerization fluorenes that takes by weighing the two ends band iodo of 2.838g (0.002mol) is dissolved in-78 ℃ the tetrahydrofuran (THF), adds n-Butyl Lithium/normal hexane (0.004mol) reaction 30min of 2.5mL 1.6M then.Then, add 2.36g dichloromethyl phenyl germane monomer (0.01mol) at room temperature reaction 180min.Remove the lithium salts of generation with porous-film, butyl iodide and solvent are removed in underpressure distillation.The product that obtains added reaction obtained pale brown look liquid in 1 hour in the vial that is immersed in the backflow system that contains 10mL/0.046g sodium in 60 ℃ of ultrasonic wave washing troughs.It is poured in the 100mL methyl alcohol centrifugation polymkeric substance.Resulting polymers is removed insolubles with the Virahol dissolving again.Obtain 2.19g (yield 55%) polymkeric substance at last.M
n＝7400，M
w/M
n＝1.44。
Three, the preparation of organic polymer electroluminescent device:
Embodiment 5, preparation organic polymer electroluminescent device
The ITO transparent conducting glass is after cleaning, model compound P1 is dissolved in sherwood oil (60-90 ℃) (5%, mass concentration), method with Spin-coating is evenly coated on the ito substrate, control thickness 150-200nm, then, vacuum evaporation magnesium and aluminium are made electrode, can be made into the individual layer electroluminescent device.
The ITO transparent conducting glass is after cleaning, evaporation CuPc and NPB successively thereon, then with the petroleum ether solution that evenly is coated with one deck model compound, evaporating Al Q behind the dry solidification, deposit magnesium again and silver is made electrode, can be made into structure is the multilayer electroluminescent device of ITO/CuPc/NPB/P-1/AlQ/Mg:Ag.
Embodiment 6, the preparation organic film FET
With tin indium oxide ITO as source electrode and drain electrode, after utilizing photoetching to prepare the source electrode and drain electrode that channel length is 50 μ m, model compound P1 among the embodiment 3 is used as semiconductor layer, method with spin coating forms a skim thereon, vacuum moulding machine polytetrafluoroethylene floor and silver electrode can be prepared into organic film FET respectively as insulation layer and grid successively again.
Claims (7)
1, a kind of organic/polymer materials, it is characterized in that introducing in the structure fluorenes or oligomerization fluorenes or poly-fluorenes, perhaps introduce 1,3,4-oxadiazole, substituted aniline, pyridine, benzoglyoxaline, naphthalene, triazole, thiazole, quinoline, anthracene or azophenlyene structure are as the electric transmission section, introducing has the polysilane of hole transport performance, poly-germane, poly-stannane as the hole transport section, and its structure is shown below:
Wherein, the M representative has the n-type structural unit of electronic transmission performance; The p-type structural unit that the G representative has the hole transport performance, n represents monomeric repetition number, n 〉=1; M represents the number of whole repeating unit, m 〉=1; R
1, R
2, R
3And R
4Refer to that some are identical or different, be used for the deliquescent group of strongthener, comprising: alkyl C
nH
2n+1(n=1～12), the long-chain alkoxy base, unsaturated alkyl chain or fragrant hydrocarbon chain perhaps contain the group of aryl and long chain hydrocarbon groups.
2, according to claim 1 organic/polymer materials, it is characterized in that said n-type structure with electronic transmission performance is fluorenes or oligomerization fluorenes or poly-fluorenes, perhaps 1,3,4-oxadiazole, substituted aniline, pyridine, benzoglyoxaline, naphthalene, triazole, thiazole, quinoline, anthracene or azophenlyene.
3, according to claim 1 organic/polymer materials, it is characterized in that G in the said p-type structure with hole transport performance is a kind of in polysilane, poly-germane or the poly-stannane.
4, according to claim 1 organic/polymer materials, it is characterized in that described alkyl C
nH
2n+1Be methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl or dodecyl; Described long-chain alkoxy base is 2-ethyl hexyl oxy, octyloxy; Described unsaturated alkyl chain or fragrant hydrocarbon chain be vinyl, allyl group, to styryl, hydroxy butyl vinyl ether base or hydroxyethyl vinyl ether group; The described group that contains aryl and long chain hydrocarbon groups is a phenyl, (4-octyloxy) phenyl or (4-(2-ethyl hexyl oxy)) phenyl.
5, a kind of preparation method as the said compound of claim 1 is characterized in that concrete steps are as follows:
(1) silicon-containing polymer is synthetic
Is that the M that halogen replaces is a raw material with two ends, is dissolved in earlier in-78 ℃ the tetrahydrofuran (THF) that add butyllithium then, reaction forms the R-Li structure, then again with exsiccant dihalo-dialkyl silane monomer reaction, be translated into corresponding dihalo-substituted monomer; The reacting by heating in non-polar solvent and alkali-metal backflow system with this monomer and dihalo-dialkyl silane monomer is perhaps used ultrasonic reaction, obtains product; Product is refining with Virahol, ethanol and methanol extraction respectively;
(2) germanium containing polymer is synthetic
Is that the M that halogen replaces is a raw material with two ends, is dissolved in earlier in-78 ℃ the tetrahydrofuran (THF) that add butyllithium then, reaction forms the R-Li structure, then again with exsiccant dihalo-dialkyl group germane monomer reaction, be translated into corresponding dihalo-substituted monomer; The reacting by heating in the backflow system of non-polar solvent and key metal with this monomer and a certain amount of dihalo-dialkyl group germane monomer is perhaps used ultrasonic reaction, obtains product; Product is refining with Virahol, ethanol and methanol extraction respectively;
(3) the stanniferous polymkeric substance is synthetic
Is that the M that halogen replaces is a raw material with two ends, is dissolved in earlier in-78 ℃ the tetrahydrofuran (THF) that add butyllithium then, reaction forms the R-Li structure, then is translated into corresponding dihalo-substituted monomer with exsiccant dihalo-dialkyl group stannane monomer reaction again; The reacting by heating in the backflow system of non-polar solvent and key metal with this monomer and a certain amount of dihalo-dialkyl group stannane monomer is perhaps used ultrasonic reaction, obtains product; Product is refining with Virahol, ethanol and methanol extraction respectively.
6, preparation method according to claim 5 is characterized in that:
(1) amount that adds sodium is 1.2 times of theoretical amount, and concentration of reactants is 0.1～0.5mol/L;
(2) the reacting by heating time is 2～36 hours, and the ultrasonic reaction time is 0.5～12 hour;
(3) non-polar solvent is one or more the mixture in normal hexane, toluene, dimethylbenzene, sherwood oil, tetracol phenixin, hexanaphthene, dodecane and the cyclooctane;
(4) basic metal is one or more the mixture in lithium, sodium, potassium, the magnesium.
7, a kind of organic according to claim 1/application of polymer materials in electroluminescent device, organic field effect tube, organic photovoltaic battery, organic laser, organic light-guide fiber, organic chemistry and biosensor and organic nano information storage.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775273A (en) * | 2012-07-05 | 2012-11-14 | 北京大学 | Bifurcate alkyl chain and preparation and application thereof in organic conjugated molecules |
| US11508910B2 (en) | 2016-12-06 | 2022-11-22 | Raynergy Tek Incorporation | Organic semiconducting compounds |
-
2005
- 2005-09-08 CN CN 200510029514 patent/CN1743408A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775273A (en) * | 2012-07-05 | 2012-11-14 | 北京大学 | Bifurcate alkyl chain and preparation and application thereof in organic conjugated molecules |
| US9209405B2 (en) | 2012-07-05 | 2015-12-08 | Peking University | Compound with branching alkyl chains, method for preparing the same, and use thereof in photoelectric device |
| US9611216B2 (en) | 2012-07-05 | 2017-04-04 | Boe Technology Group Co., Ltd. | Compound with branching alkyl chains, method for preparing the same, and use thereof in photoelectric device |
| US11508910B2 (en) | 2016-12-06 | 2022-11-22 | Raynergy Tek Incorporation | Organic semiconducting compounds |
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