CN107759774A - Main chain contains S, the D A type polymer of S dioxydibenze bithiophenes and preparation method and application - Google Patents

Main chain contains S, the D A type polymer of S dioxydibenze bithiophenes and preparation method and application Download PDF

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CN107759774A
CN107759774A CN201710992461.5A CN201710992461A CN107759774A CN 107759774 A CN107759774 A CN 107759774A CN 201710992461 A CN201710992461 A CN 201710992461A CN 107759774 A CN107759774 A CN 107759774A
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dioxo
main chain
type polymer
dibenzothiophenes
polymer
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CN107759774B (en
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应磊
彭沣
胡黎文
黄飞
曹镛
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Dongguan volt ampere Photoelectric Technology Co., Ltd
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South China Institute of Collaborative Innovation
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Abstract

The invention discloses a kind of main chain to contain S, the D A type polymer of S dioxydibenze bithiophenes and preparation method and application.The present invention is copolymerized using electrical S, S dioxydibenze bithiophene units and electron-donating unit is inhaled, and is formed D A structural molecules, is obtained the main chain and contain S, the D A type polymer of S dioxydibenze bithiophenes.In the present invention, S, 2,8 carbon atoms of S dioxydibenze bithiophene units and electron-donating nitrogenous heteroaromatic unit are larger by C N key connections, D A unit torsion angles, advantageously reduce the conjugated degree of polymer molecule, realize that HOMO and LUMO electron clouds efficiently separate, reduction singlet triplet is poor, promotes to alter more process between intramolecular inverse system, singlet exciton generation ratio is improved, is advantageous to the raising of device efficiency.Such main chain contains S, and the D A type polymer of S dioxydibenze bithiophenes has good dissolubility, available for the luminescent layer for preparing polymer LED.

Description

Main chain contain S, the D-A type polymer of S- dioxo-dibenzothiophenes and preparation method thereof with Using
Technical field
The invention belongs to organic photoelectric technical field, and in particular to a kind of main chain contains S, the D-A of S- dioxo-dibenzothiophenes Type polymer and preparation method and application.
Background technology
The polymer prepared using conjugated polymer PPV has been delivered in nineteen ninety, univ cambridge uk's all one's life laboratory Membrane electro luminescent device, so as to formally pull open the prelude of polymer LED (PLED) research.Lighted with small molecule Diode is compared, and polymer LED has the advantage that：(1) big face can be prepared by the methods of printing, inkjet printing Product film；(2) conjugated polymer electronics cloud structure, glow color can be adjusted by the change and modification of chemical constitution；(3) Conjugated polymer can avoid crystallizing by modification, improve device stability.
PLED devices are made up of negative electrode, anode and the organic layer of centre, and organic layer generally comprises electron transfer layer, luminescent layer And hole transmission layer, electronics and hole inject from negative and positive the two poles of the earth respectively first, and are migrated respectively in functional layer, Ran Hou electricity Son and hole form exciton in place, and exciton is migrated within the specific limits, last excitonic luminescence.
Main chain contains S, and the polymer luminescent material of S- dioxo-dibenzothiophenes is star's material of PLED research fields.Poplar Big and Martin R.Bryce problems be combined into it is a series of be based on S, the high efficiency electroluminescent of S- dioxo-dibenzothiophenes gathers Compound [Chem.Mater.2008,20,4499-4506；Advanced Functional Materials,2013,23,4366- 4376；Macromolecules,2010,43,4481-4488；J.Mater. Chem.C,2014,2,5587–5592].But Traditional Polymeric fluorescent material can only utilize 25% singlet exciton, and 75% triplet excitons energy passes through noradiative transition Move and lose, this causes the maximum internal quantum efficiency of traditional Polymeric fluorescent material there was only 25%, limits its electroluminescent Efficiency.Therefore, further to improve the electroluminescent properties of Polymeric fluorescent material, it is a kind of excellent to improve singlet exciton ratio First method.
Thermal activation delayed fluorescence is the luminous mechanism of new generation [Nature, 2012,492,234-240] risen in recent years, Mainly pass through D-A type Molecular Design so that intramolecular HOMO and LUMO electron cloud efficiently separates, and reduces singlet-three Line state energy level difference so that triplet excitons can improve light emitting molecule by being converted to singlet exciton on anti-intersystem crossing Singlet exciton generates ratio, and then obtains the internal quantum efficiency of maximum 100%.
The content of the invention
Lacked for traditional polymer luminescent material singlet exciton generation ratio is limited, maximum internal quantum efficiency is relatively low Point, primary and foremost purpose of the invention be to provide a kind of polymer luminescent material with delayed fluorescence characteristic, and specially main chain contains The D-A type polymer of S, S- dioxo-dibenzothiophene.The main polymer chain, which contains, inhales electrical S, S- dioxo-dibenzothiophenes Unit, connected with electron-donating D units by weak conjugation so that intramolecular HOMO and LUMO electron cloud efficiently separates, singlet-three Line state energy level difference is smaller, triplet excitons under thermal excitation can more than be converted to singlet exciton, improve singlet exciton generation Ratio, this kind of polymer have typical thermal activation delayed fluorescence characteristic.
Another object of the present invention is to provide the main chain to contain S, the D-A type polymer of S- dioxo-dibenzothiophenes Preparation method.
It is still another object of the present invention to provide the main chain to contain S, and the D-A type polymer of S- dioxo-dibenzothiophenes exists Application in the luminescent layer of polymer LED.
The object of the invention is achieved through the following technical solutions：
A kind of main chain contains S, the D-A type polymer of S- dioxo-dibenzothiophenes, shown in chemical structural formula such as formula (1)：
In formula, the molar fraction of x unit components, meet：0<x≤0.5；N is repeat unit, n=10~1000； R1For The cycloalkyl of hydrogen atom, the alkyl of carbon number 1~30 or carbon number 1~30；Ar1For nitrogenous aromatic heterocycle, Ar2For The aromatic hydrocarbyl of carbon number 6~60 or the aromatic heterocycle of carbon number 3~60.
Further, the nitrogenous aromatic heterocycle Ar1Selected from following chemical structural formula or following chemical structural formula One or more of derivative：
Wherein, * is represented and S, S- dioxo-dibenzothiophene are connected, and * * are represented and Ar2It is connected；R2For hydrogen atom, carbon atom The alkyl of number 1~30 or the cycloalkyl of carbon number 1~30；R3For the alkyl or cycloalkyl of carbon number 1~30, carbon number 6~30 alkyl or alkoxy substituted phenyl.
Further, the Ar2In derivative selected from following chemical structural formula or following chemical structural formula it is a kind of with On：
Wherein, * is represented and S, S- dioxo-dibenzothiophene are connected, R4For the alkyl or cycloalkyl of carbon number 1~30, The alkyl or alkoxy substituted phenyl of carbon number 6~30.
Prepare the main chain described in any of the above-described and contain S, the method for the D-A type polymer of S- dioxo-dibenzothiophenes, including Following steps：
The S that 2,8- positions are substituted, S- dioxo-dibenzothiophene and nitrogenous aromatic heterocycle Ar1By copper catalysis or Palladium chtalyst carries out C-N couplings, obtains D-A type polymer reaction monomer, D-A type polymer reaction monomer and Ar2Pass through Suzuki Reaction, Buchwald-Hartwig reactions or Ullmann reactions are prepared the main chain and contain S, S- dioxo-dibenzothiophenes D-A type polymer.
Further, the temperature of the Suzuki reactions is 60~90 DEG C, and the time is 12~48 hours；Described The temperature of Buchwald-Hartwig and Ullmann reactions is 80-120 DEG C, and the time is 12-48 hours.
Further, the Suzuki catalysts are tetrakis triphenylphosphine palladium or palladium etc.；Described Buchwald-Hartwig catalysts are palladium or three (dibenzalacetone) two palladium etc.；Described Ullmann reactions Catalyst for copper or cuprous iodide etc..
Described main chain contains S, and the D-A type polymer of S- dioxo-dibenzothiophenes is preparing polymer LED hair Application in photosphere, concrete application step include：The main chain is contained into S, the D-A type polymer of S- dioxo-dibenzothiophenes is used Organic solvent dissolves, and by spin coating, inkjet printing or printing film forming, obtains the luminescent layer of the polymer LED.
Further, the organic solvent includes dimethylbenzene, chlorobenzene or methyltetrahydrofuran.
Described main chain is contained into S, the D-A type polymer of S- dioxo-dibenzothiophenes is applied to prepare polymer light-emitting two The luminescent layer of pole pipe, the anti-intersystem crossing of triplet excitons can be utilized, improve singlet exciton generation ratio, be advantageous to improve and gather The electroluminescent properties of polymer LEDs；Meanwhile S is contained based on the main chain, the D-A type of S- dioxo-dibenzothiophenes is gathered The light emitting diode of compound can be used for the display of flat-panel monitor.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) present invention will inhale electrical S, and S- dioxo-dibenzothiophene units are incorporated into main polymer chain, S, S- bis- 2, the 8- positions carbon atom of oxygen-dibenzothiophene unit and electron-donating nitrogenous heteroaromatic unit are by C-N key connections, while D-A Torsion angle between unit is larger, can reduce effective conjugate length of polymer molecule, is advantageously implemented HOMO and LUMO electricity Sub- cloud efficiently separates, and reduction singlet-triplet is poor, promotes to alter more process between intramolecular inverse system, improves singlet Exciton generates ratio, is advantageous to the raising of device efficiency.
(2) S is contained in the present invention, the D-A type polymer of S- dioxo-dibenzothiophenes has thermal activation delayed fluorescence characteristic, Polymer device internal quantum efficiency can be brought up to 100%.
(3) main chain of the invention contains S, and the D-A type polymer of S- dioxo-dibenzothiophenes can be electron-donating by adjusting Cellular construction and ratio, transmitting of the polymer spectra in whole visible-range is realized, favourable prepare is based on the base of RGB three The color monitor of color.
(4) main chain of the invention contains S, the D-A type polymer of S- dioxo-dibenzothiophenes, has double carriers transmission special Property and good dissolubility, device preparation technology can be simplified, can as luminescent layer obtain greater efficiency single polymer layer Luminescent device.
Brief description of the drawings
Fig. 1 is polymer P 2 in electrochemical oxidation curve；
Fig. 2 is polymer P 2 in ITO/PEDOT:Electroluminescent light under PSS/PVK/ polymer/CsF/Al device architectures Spectrogram.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited In this, all equivalent changes and modifications done according to scope of the present invention patent, it should all belong to covering scope of the invention.
Embodiment 1：Compound M1 preparation
(1) preparation of compound 1
2,8-, bis- bromo- S, S- dioxo-dibenzothiophenes (3.74g, 10mmol), aniline are added in 100ml two-mouth bottles (2.79g, 30mmol), sodium tert-butoxide (4.81g, 50mmol), three (dibenzalacetone) two palladium (458mg, 0.5mmol), three Tert-butyl group phosphine (101mg, 0.5mmol) and 50ml toluene, under condition of nitrogen gas, it is heated to 100 DEG C and reacts 12 hours.Reaction finishes, Product is extracted with dichloromethane, washs organic phase with saturated sodium-chloride water solution, decompression boils off solvent, crude product petroleum ether： Dichloromethane=3：1 (v/v) mixed solvent makees the purification of eluant, eluent column chromatography, obtains white solid 1.60g, yield 40%, (matter Spectrum：398.2).
(2) compound M1 preparation
Compound 1 (398.5g, 10mmol) is added in 300ml two-mouth bottles, to bromo-iodobenzene (8.49g, 30mmol), uncle Sodium butoxide (4.81g, 50mmol), acid chloride (112mg, 0.5mmol), tri-butyl phosphine (101mg, 0.5mmol) and 150ml first Benzene, under condition of nitrogen gas, it is heated to 60 DEG C and reacts 6 hours.Reaction finishes, and product is extracted with dichloromethane, with saturated sodium-chloride water Three times, decompression boils off solvent, crude product petroleum ether to solution washing organic phase：Dichloromethane=4：1 (v/v) mixed solvent is made Eluant, eluent column chromatography purifies, then is recrystallized with tetrahydrofuran, obtains white solid 3.70g, yield 52%, (mass spectrum：707.9).
Shown in chemical equation such as formula (2)：
Embodiment 2：Compound M2 preparation
2,8-, bis- iodo- S, S- dioxo-dibenzothiophenes (4.68g, 10mmol), 3- bromine clicks are added in 100ml two-mouth bottles Azoles (6.15g, 25mmol), potassium carbonate (6.9g, 50mmol), cuprous iodide (95mg, 0.5mmol) and 50ml toluene, nitrogen bar Under part, it is heated to 100 DEG C and reacts 12 hours.Reaction finishes, and extracts product with dichloromethane, is washed with saturated sodium-chloride water solution Organic phase, decompression boil off solvent, crude product petroleum ether：Dichloromethane=4：1 (v/v) mixed solvent makees eluant, eluent column chromatography Purification, obtains white solid 2.59g, yield 37%, (mass spectrum：704.0).
Shown in chemical equation such as formula (3)：
Embodiment 3
Compound M3 preparation
Under nitrogen atmosphere, 3,6- dibromos carbazole (3.25g, 10mmol), 2- bromic ethers are added into 300ml two-mouth bottle For hexane (2.90g, 15mmol)), potassium carbonate (4.14g, 30mmol)) and 150ml N, N- dimethylformamides, at 80 DEG C Stirring reaction 12 hours.After cooling with dichloromethane extract product, saturated sodium-chloride water solution wash five times until water layer clarify, It is evaporated under reduced pressure and removes dichloromethane, crude product petroleum ether makees the purification of eluent column chromatography, obtains colourless transparent liquid 3.94g, produces Rate 90%, (mass spectrum：437.1).
Compound M4 preparation
Under nitrogen protection, M3 (4.37g, 10mmol), connection boric acid pinacol ester are added into 300ml two-mouth bottle (6.35g, 25mmol), [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.49g, 0.5mmol), potassium acetate (3.92g, 40mmol) and 120ml dioxane, it is heated to 80 DEG C and reacts 12 hours.It is evaporated under reduced pressure after completion of the reaction and removes two The ring of oxygen six, product is extracted with dichloromethane, saturated sodium-chloride water solution washs three times, is evaporated under reduced pressure and removes dichloromethane, thick production Thing petroleum ether：Ethyl acetate=10：1 (v/v) mixed solvent makees the purification of eluent column chromatography, obtains white solid 3.63g, Yield 68%, (mass spectrum：513.4).
Shown in chemical equation such as formula (4)：
Embodiment 4
Compound M5 preparation
Paradibromobenzene (2.36g, 10mmol), aniline (2.79g, 30mmol), sodium tert-butoxide are added in 100ml two-mouth bottles The palladium (458mg, 0.5mmol) of (4.81g, 50mmol), three (dibenzalacetone) two, tri-butyl phosphine (101mg, 0.5mmol) With 50ml toluene, under condition of nitrogen gas, it is heated to 110 DEG C and reacts 12 hours.Reaction is finished, and product is extracted with dichloromethane, with full Organic phase is washed with sodium-chloride water solution, decompression boils off solvent, crude product petroleum ether：Dichloromethane=4：1 (v/v) mixing Solvent makees the purification of eluant, eluent column chromatography, then with ethyl alcohol recrystallization, obtains white plates crystal 0.66g, yield 25%, (mass spectrum： 260.2)。
Shown in chemical equation such as formula (5)：
Embodiment 5
The preparation of polymer P 1
Nitrogen protection under, by M1 (42.5mg, 0.06mmol), M3 (104.9mg, 0.24mmol), M4 (159.4mg, 0.3mmol) it is dissolved in 10ml toluene, adds tetraethyl aqueous hydroxylamine solution (1ml, wt%=25%) and four (triphenyls Phosphine) palladium (6mg)；Be heated to 80 DEG C reaction 24 hours after, add phenyl boric acid (20mg) block 6 hours, add bromobenzene (0.2ml) End-blocking 6 hours；Reaction stops, and after cooling, by organic phase precipitating in methanol (200ml), filtering, after drying, crude product is successively Extracted with methanol, acetone, n-hexane, dissolve polymer with toluene, using toluene as eluent, column chromatography is carried out with neutral alumina Purification；The toluene solution of concentrated polymer, precipitating is in methanol solution again, and filtering is dry, obtains the polymerization of yellow fine-fibrous Thing.GPC：Mn=21KDa, PDI=1.86.
Shown in chemical equation such as formula (6)：
Embodiment 6
The preparation of polymer P 2
Nitrogen protection under, by M2 (84.5mg, 0.12mmol), M3 (78.7mg, 0.18mmol), M4 (159.4mg, 0.3mmol) it is dissolved in 10ml toluene, adds tetraethyl aqueous hydroxylamine solution (1ml, wt%=25%), palladium (1mg) With tricyclohexyl phosphine (2mg)；It is heated to 80 DEG C to react 24 hours, then adds phenyl boric acid (20mg) and block 6 hours, add bromine Benzene (0.2ml) blocks 6 hours；Reaction stops, after cooling, by organic phase precipitating in methanol (200ml), and filtering, after drying, slightly Product is successively extracted with methanol, acetone, n-hexane, is dissolved polymer with toluene, using toluene as eluent, is entered with neutral alumina Row column chromatography purifies；The toluene solution of concentrated polymer, precipitating is in methanol solution again, and filtering is dry, obtains yellowish green toner Last shaped polymer.GPC：Mn=11KDa, PDI=1.53.
Shown in chemical equation such as formula (7)：
Embodiment 7
The preparation of polymer P 3
Under nitrogen protection, M1 (212.6mg, 0.3mmol), M5 (78.1mg, mmol) are dissolved in 10ml toluene, then Add sodium tert-butoxide (96mg, 1mmol), three (dibenzalacetone) two palladium (8 mg), tri-butyl phosphine (6mg)；It is heated to 100 DEG C reaction 48 hours；Reaction stops, and after cooling, by reaction solution precipitating in methanol (200ml), filtering, after drying, crude product is first Extracted afterwards with methanol, acetone, n-hexane, dissolve polymer with toluene, using toluene as eluent, post layer is carried out with neutral alumina Analysis purification；The toluene solution of concentrated polymer, precipitating is in methanol solution again, and filtering is dry, obtains yellow powder polymerization Thing.GPC：Mn=8.2KDa, PDI=1.32.
Chemical equation is shown below：
Embodiment 8
The preparation of polymer LED
Take well in advance square resistance be 10 Ω tin indium oxide (ITO) glass, successively with acetone, detergent, go from Sub- water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes；The polyethoxy for having polystyrolsulfon acid is mixed in spin coating on ITO Thiophene (PEDOT:PSS=1:6, w/w) film, thickness 40nm； PEDOT:PSS films dry 8 in vacuum drying oven at 80 DEG C small When；Polyvinylcarbazole (PVK) chlorobenzene solution (1wt.%) is then spin-coated on PEDOT:The surface of PSS films, thickness are 20nm, as hole transmission layer；The xylene solution (1wt.%) of polymer P 2 is spin-coated on the surface of PVK films again, thickness is 80 nm, as luminescent layer；The thick metal Al layers of one layer of 1.5nm thick CsF and 120nm, device is finally deposited successively on luminescent layer Part structure：ITO/PEDOT:PSS/PVK/ polymer/CsF/Al.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (9)

1. a kind of main chain contains S, the D-A type polymer of S- dioxo-dibenzothiophenes, it is characterised in that its chemical structural formula such as formula (1) shown in：
In formula, the molar fraction of x unit components, meet：0<x≤0.5；N is repeat unit, n=10~1000；R1For hydrogen atom, The alkyl of carbon number 1~30 or the cycloalkyl of carbon number 1~30；Ar1For nitrogenous aromatic heterocycle, Ar2For carbon number 6~60 aromatic hydrocarbyl or the aromatic heterocycle of carbon number 3~60.
2. main chain according to claim 1 contains S, the D-A type polymer of S- dioxo-dibenzothiophenes, it is characterised in that institute State nitrogenous aromatic heterocycle Ar1One or more of derivative selected from following chemical structural formula or following chemical structural formula：
Wherein, * is represented and S, S- dioxo-dibenzothiophene are connected, and * * are represented and Ar2It is connected；R2For hydrogen atom, carbon number 1~ 30 alkyl or the cycloalkyl of carbon number 1~30；R3For the alkyl or cycloalkyl of carbon number 1~30, carbon number 6~30 Alkyl or alkoxy substituted phenyl.
3. main chain according to claim 1 contains S, the D-A type polymer of S- dioxo-dibenzothiophenes, it is characterised in that institute State Ar2One or more of derivative selected from following chemical structural formula or following chemical structural formula：
Wherein, * is represented and S, S- dioxo-dibenzothiophene are connected, R4For the alkyl or cycloalkyl of carbon number 1~30, carbon atom The alkyl or alkoxy substituted phenyl of number 6~30.
4. the main chain described in any one of claims 1 to 3 contains S, the preparation side of the D-A type polymer of S- dioxo-dibenzothiophenes Method, it is characterised in that comprise the following steps：The S that 2,8- positions are substituted, S- dioxo-dibenzothiophene and nitrogenous heteroaromatic Base Ar1C-N couplings are carried out by copper catalysis or palladium chtalyst, obtain D-A type polymer reaction monomer；D-A type polymer reaction Monomer and Ar2Reacted by Suzuki, described main chain is prepared in Buchwald-Hartwig reactions or Ullmann reactions Containing S, the D-A type polymer of S- dioxo-dibenzothiophenes.
5. main chain according to claim 4 contains S, the preparation method of the D-A type polymer of S- dioxo-dibenzothiophenes, its It is characterised by, the temperature of the Suzuki reactions is 60~90 DEG C, and the time is 12~48 hours；Described Buchwald- The temperature of Hartwig and Ullmann reactions is 80-120 DEG C, and the time is 12-48 hours.
6. main chain according to claim 4 contains S, the preparation method of the D-A type polymer of S- dioxo-dibenzothiophenes, its It is characterised by, the Suzuki catalysts are tetrakis triphenylphosphine palladium or palladium；Described Buchwald-Hartwig Catalysts are palladium or three (dibenzalacetone) two palladium；The catalyst of described Ullmann reactions is copper or iodate It is cuprous.
7. the main chain described in any one of claims 1 to 3 contains S, the D-A type polymer of S- dioxo-dibenzothiophenes is poly- in preparation Application in polymer LEDs luminescent layer or flat-panel monitor.
8. application according to claim 7, it is characterised in that described main chain contains S, the D-A of S- dioxo-dibenzothiophenes Type polymer, which prepares the step of polymer LED luminescent layer, to be included：The main chain is contained into S, S- dioxo-dibenzothiophenes D-A type polymer dissolved with organic solvent, by spin coating, inkjet printing or printing film forming, obtain the polymer light-emitting two The luminescent layer of pole pipe.
9. application according to claim 8, it is characterised in that the organic solvent includes dimethylbenzene, chlorobenzene or methyl four Hydrogen furans.
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CN110776620A (en) * 2018-07-31 2020-02-11 华南理工大学 D-pi-A polymer containing S, S-dioxo-dibenzothiophene derivative unit and preparation method and application thereof
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