CN1438254A - Polyalkyl-fluorene conjugated polymer and use - Google Patents
Polyalkyl-fluorene conjugated polymer and use Download PDFInfo
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- CN1438254A CN1438254A CN 03117424 CN03117424A CN1438254A CN 1438254 A CN1438254 A CN 1438254A CN 03117424 CN03117424 CN 03117424 CN 03117424 A CN03117424 A CN 03117424A CN 1438254 A CN1438254 A CN 1438254A
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Abstract
The invention refers to a polyalkyl fluorene conjugated polymer whose construction consists of 9,9' double substituted fluorene construction unit and diaryl substituted cubic acid or maleic amino one. The conjugated polymer is used as the luminescent material and can be applicable to make electroluminescent devices.
Description
One, technical field
The present invention relates to the poly alkyl fluorene conjugated polymer material, relate to the poly alkyl fluorene conjugated polymer material of the side's of containing acid groups or maleinamide group in more detail.
The invention still further relates to this poly alkyl fluorene conjugated polymer material in the application of preparation in the luminescent material, special is the application in luminescent layer and the electron transfer layer in preparation photodiode, the flat-panel monitor.
Two, background technology
Since first electroluminescent devices of report such as nineteen ninety Burroughes based on the phenylacetylene conjugated polymers, conjugated polymers is because its potential can be used for ultra-thin, flexible, big area, multicolor displaying, and on the technology of making electroluminescent device, have simple to operate, be easy to industrialized advantage, become the focus of present flat pannel display area research.The polymer luminescent material system mainly concentrates on following a few class: p-phenylene vinylene (PPV), Polythiophene (PTh), poly alkyl fluorene (PAF), polyparaphenylene (PPh) etc.Wherein poly alkyl fluorene has bigger energy gap, is typical case's representative of blue light polymkeric substance.Simultaneously, poly alkyl fluorene has good light and thermally stable, so be considered to have the base polymer electroluminescent material of development prospect.The conjugation group of introducing other on the main chain of poly alkyl fluorene forms the alternating copolymer of poly alkyl fluorene, because the structure difference of the group of introducing can realize the panchromatic demonstration of polymer electroluminescence, is significant.At present, poly alkyl fluorene has been realized high fluorescence efficiency as blue light material, hangs down and problems such as description of materials is few but the poly alkyl fluorene base polymer of other color still faces fluorescence efficiency.
In the making of polymer electroluminescent device, the problem of anode and hole transmission layer solves substantially.Present anode material (indium dioxide tin) and hole mobile material (polyvinyl carbazole, poly-(3, the 4-diethoxy) thiophene) can satisfy the flat-panel display device industrialization demands substantially.But electron transport material generally all is small molecule material and need forms electron transfer layer with the mode of high vacuum vapor deposition that technology makes difficulty and device cost increases.Inject balance in order to reach current carrier, need make cathode material with active metals such as calcium, barium, this makes the stability of device be affected, and also the manufacture craft and the device cost of device is had higher requirement.The researchist is making great efforts to seek to improve the method for photopolymer photodiode always, and material is one of the most basic factor.Thereby numerous research group and the demonstration companies in the world endeavours to develop new conjugated polymer luminescent material always.
Three, summary of the invention
The object of the present invention is to provide a kind of new poly alkyl fluorene conjugated polymer material, in more detail the multipolymer of the side's of containing acid groups or maleinamide unit structure unit and fluorene structural units.
The invention still further relates to above-mentioned poly alkyl fluorene conjugated polymers in the application of preparation in the luminescent material, special is the application in luminescent layer and the electron transfer layer in preparation photodiode, the flat-panel monitor.
Conjugated polymers of the present invention has the structure of following general formula (I) expression:
Wherein A is two substituted fluorene structural units, and B is square acid or the maleinamide structural unit that diaryl replaces.Conjugated polymers structural unit A of the present invention is the represented group of following general formula (II):
Wherein R1 and R2 are independently selected from straight chain C 1-20 alkyl or alkoxyl group, branching C1-20 alkyl or alkoxyl group under each situation.Preferentially be selected from C4-8 alkyl or alkoxyl group, branching C4-8 alkyl or alkoxyl group, especially preferentially be selected from C6-8 alkyl or alkoxyl group.Override is selected from hexyl, octyl group and iso-octyl.
Conjugated polymers of the present invention, wherein structural unit B is selected from following general formula (III) or the represented group of general formula (IV):
Wherein R3 and R4 are independently selected from hydrogen, straight chain C 1-20 alkyl or alkoxyl group, branching C1-20 alkyl or alkoxyl group under each situation.Preferentially be selected from hydrogen, C4-8 alkyl or alkoxyl group, branching C4-8 alkyl or alkoxyl group.
Wherein R5 is independently selected from straight chain C 1-20 alkyl, branching C1-20 alkyl under each situation.Preferentially be selected from C4-12 alkyl or alkoxyl group, branching C4-12 alkyl or alkoxyl group.
The present invention discloses the poly alkyl fluorene conjugated polymers as luminescent material, advantage with high-quantum efficiency, permanent stability, electron-transporting, while side's acid groups or the unitary introducing of maleinamide unit structure can be regulated the glow color of poly alkyl fluorene, are applicable to the making electroluminescent device.
The poly alkyl fluorene conjugated polymers that the present invention relates to adopts the Suzuki coupling manner synthetic, be described below in conjunction with embodiment, but these embodiment does not limit the present invention.
Four, embodiment
The monomeric preparation of A
Embodiment 13,4-two (4-bromophenyl)-3-cyclobutene-1, the preparation of 2-diketone
Press Polymer Bulletin, 1999,42,183-190 disclosed method preparation 3,4-two (4-bromophenyl)-3-cyclobutene-1,2-diketone.In 100 milliliters three-necked bottle, adding side's acid 3.04 grams (26.6 mmole), thionyl chloride 6.42 gram (54.0 mmole) and N, dinethylformamide (DMF) (catalytic amount).About reacting by heating miscellany to 65 ℃, reacted about 2 hours.The cooling reaction solution adds 20 milliliters of bromobenzenes and aluminum trichloride (anhydrous) 8.5 grams (63.8 mmole), about 30 hours of room temperature reaction then in miscellany.Miscellany is poured in 20 ml waters, used ethyl acetate extraction, the extraction liquid anhydrous magnesium sulfate drying, the evaporated under reduced pressure solvent gets crude product.Ethyl alcohol recrystallization get pure product (fusing point: 172 ℃, productive rate: 46%).
Embodiment 2 N-dodecyls-3,4-two (4-bromophenyl) pyrroles-2, the preparation of 5-diketone
Press Polymer Bulletin, 2001,46, the 29-35 disclosed method prepares N-dodecyl-3,4-two (4-bromophenyl) pyrroles-2,5-diketone.
With 3,4-two (4-bromophenyl)-3-cyclobutene-1,2-diketone 3.92 grams (10 mmole); metachloroperbenzoic acid 4.68 gram (19 mmoles; 70%) methylene dichloride (10 milliliters) stirring at room under nitrogen protection adds sodium bisulfite 1.0 grams after about 14 hours, continues to stir 1 hour.Get crude product with silicagel column (methylene dichloride is made eluent) elimination m-chlorobenzoic acid, get the green-yellow crystal at ethyl alcohol recrystallization.
With above-mentioned crystal 2 .27 gram (5.6 mmole), about 1 hour of toluene (20 milliliters) solution stirring of positive amino dodecane 1.1 grams (5.9 mmole), triethylamine and 20 milliliters of toluene of adding catalytic amount continued stir about 14 hours.Remove toluene under reduced pressure, by the N-dodecyl-3 that column chromatography is separated purely, 4-two (4-bromophenyl) pyrroles-2,5-diketone.
Embodiment 3 N-n-octyls-3,4-two (4-bromophenyl) pyrroles-2, the preparation of 5-diketone
Synthetic method is with reference to embodiment 2.
Embodiment 4 N-normal-butyls-3,4-two (4-bromophenyl) pyrroles-2, the preparation of 5-diketone
Synthetic method is with reference to embodiment 2.
Embodiment 52,7-hypoboric acid trimethyl-9, the preparation of 9 '-dihexyl fluorenes
Press Chemical Communication, 1999,1837-1838 disclosed method preparation 2,7-two bromo-9,9 '-dihexyl fluorenes.
In the presence of tetrabutylammonium chloride, with 2,7-dibromo fluorenes 10 grams (30.86 mmole), N-Hexyl Bromide 12.74 grams (77.2 mmole), 12 milliliters of 50% aqueous sodium hydroxide solutions and 50 millis are given birth to the methyl-sulphoxide miscellany and were reacted about 80 ℃ about 6 hours, react the back and got 2 by purifying and recrystallization, 7-two bromo-9,9-dihexyl fluorenes.2,7-two bromo-9,9-dihexyl fluorenes 16.3 grams (33 mmole), processing makes Grignard reagent through magnesium in anhydrous tetrahydro furan, in this Grignard reagent, drip the tetrahydrofuran solution of bormethyl acid esters, at room temperature reacted again about 48 hours after about 2 hours in reaction about-78 ℃, in this mixed liquid, pour into to contain in the 5% vitriolic trash ice and continued stir about 24 hours.The miscellany extracted with diethyl ether gets solid with the extraction liquid evaporate to dryness, in n-hexane/acetone (4: 1) recrystallization get pure 2,7-hypoboric acid base-9,9-dihexyl fluorenes.With 9,9-dihexyl-2,7-fluorenes hypoboric acid 6.3 grams (15 mmole) and 1, ammediol 2.0 gram (33 mmole) back flow reaction can make 2 in about 10 hours, 7-hypoboric acid trimethyl-9,9 '-dihexyl fluorenes.
The preparation of B conjugated polymers
Embodiment 6 poly-{ (9,9-dihexyl fluorenes)-[3,4-two (4-bromophenyl)-3-cyclobutene-1,2-diketone] } preparations (PFCD)
Under argon shield, take by weighing 2,7-hypoboric acid trimethyl-9,9 '-dihexyl fluorenes 0.502g (1 mole), 3,4-two (4-bromophenyl)-3-cyclobutene-1,2-diketone 0.392g (1 mole), triphenyl phosphorus palladium 12mg (0.01 mole), toluene 2.5ml, DMF2.5ml, K
2CO
3Aqueous solution 5ml (2M) places the 100ml three-necked bottle.Reaction is about 48 hours about mixture heating up to 90 ℃, after having reacted mixture is cooled to room temperature, be poured onto in the mixture (volume ratio 10: 1) of 200ml first alcohol and water, get fibrous solid, suction filtration, repeatedly wash this solid with the first alcohol and water, the gained solid gets the yellow-green colour solid with acetone repetitive scrubbing in withdrawal device, and vacuum-drying makes polymer P FCD.
Embodiment 7 poly-{ (9,9-dihexyl fluorenes)-[N-dodecyl-3,4-two (4-bromophenyl) pyrroles-2,5-diketone] } preparations (PFPD12)
Under argon shield, take by weighing 2,7-hypoboric acid trimethyl-9,9 '-dihexyl fluorenes 0.502g (1 mole), 3N-dodecyl-3,4-two (4-bromophenyl) pyrroles-2,5-diketone 0.575g (1 mole), triphenyl phosphorus palladium 12mg (0.01 mole), toluene 5ml,, K
2CO
3Aqueous solution 5ml (2M) places the 100ml three-necked bottle.Reaction is about 48 hours about mixture heating up to 90 ℃, after having reacted mixture is cooled to room temperature, be poured onto in the mixture (volume ratio 10: 1) of 200ml first alcohol and water, get fibrous solid, suction filtration, repeatedly wash this solid with the first alcohol and water, the gained solid gets the glassy yellow solid with acetone repetitive scrubbing in withdrawal device, and vacuum-drying makes polymer P FPD12.
Embodiment 8 poly-{ (9,9-dihexyl fluorenes)-[N-n-octyl-3,4-two (4-bromophenyl) pyrroles-2,5-diketone] } preparations (PFPD8)
Synthetic method is with reference to embodiment 7.
Embodiment 9 polymer polies { (9,9-dihexyl fluorenes)-[N-normal-butyl-3,4-two (4-bromophenyl) pyrroles-2,5-diketone] } preparation (PFPD4)
Synthetic method is with reference to embodiment 7
Following example is to the device and the performance specification of luminescent material made proposed by the invention, but the present invention will be not limited to listed example.
The preparation of embodiment 10 polymer electroluminescent devices
Ito glass is handled with oxygen-plasma after ultrasonic cleaning, and the square resistance of ito glass is 20 Ω/, and the hole injection layer polymkeric substance is PEDOT, and luminescent layer adopts PFPD8, and electron transfer layer is Alq
3. cathode electrode Mg/Ag (10: 1), hole transmission layer and luminescent layer all adopt the mode of spin coating to make.Apply positive bias between ITO and metal electrode, send gold-tinted (560nm), brightness is 300cd/m
2, playing bright voltage is 9.5V.
ITO noted earlier refers to indium tin oxide-coated glass, and PEDOT refers to gather (3, the 4-diethoxy) basic thiophene.
Claims (10)
1, a kind of poly alkyl fluorene conjugated polymers is characterized in that having the structure of following general formula (I) expression:
Wherein A is 9,9 ' dibasic fluorene structural units, and B is square acid or the maleinamide structural unit that diaryl replaces.
2, conjugated polymers as claimed in claim 1 is characterized in that structural unit A is the group of following general formula (II) expression:
R wherein
1And R
2Under each situation, be independently selected from straight chain C 1-20 alkyl or alkoxyl group, branching C1-20 alkyl or alkoxyl group.
3, poly alkyl fluorene conjugated polymers as claimed in claim 2 is characterized in that R
1And R
2Under each situation, be independently selected from straight chain C 4-8 alkyl or alkoxyl group, branching C4-8 alkyl or alkoxyl group.
4, poly alkyl fluorene conjugated polymers as claimed in claim 3 is characterized in that R
1And R
2Under each situation, be independently selected from C6-8 alkyl or alkoxyl group.
5,, it is characterized in that said alkyl is selected from hexyl, octyl group and own octyl group as claim 2 or 3 or 4 described poly alkyl fluorene conjugated polymerss.
6, conjugated polymer material as claimed in claim 1 is characterized in that structural unit B is selected from following general formula (III), (IV) Biao Shi group:
Wherein R3 and R4 are independently selected from hydrogen, straight chain C 1-20 alkyl or alkoxyl group, branching C1-20 alkyl or alkoxyl group under each situation.
Wherein R5 is independently selected from straight chain C 1-20 alkyl, branching C1-20 alkyl under each situation.
7, poly alkyl fluorene conjugated polymers as claimed in claim 6 is characterized in that R
3And R
4Under each situation, be independently selected from hydrogen, straight chain C 4-8 alkyl or alkoxyl group, branching C4-8 alkyl or alkoxyl group.
8, as claim 6 or 7 described poly alkyl fluorene conjugated polymerss, it is characterized in that R
5Under each situation, be independently selected from straight chain C 4-12, alkyl or alkoxyl group, branching C4-12 alkyl or alkoxyl group.
9, as the application of the arbitrary poly alkyl fluorene conjugated polymers in the claim 1 to 8 in the preparation luminescent material.
10, as the arbitrary conjugated polymers in the claim 1 to 8 in preparation photodiode, flat-panel monitor luminescent layer and the application in the electron transfer layer.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305926C (en) * | 2005-03-17 | 2007-03-21 | 复旦大学 | Fluorene water soluble conjugate polymer containing polyethyene diamine side chain and its use |
| CN1325530C (en) * | 2004-08-26 | 2007-07-11 | 复旦大学 | Luminous polyurethane material and its synthesis method |
| CN100357390C (en) * | 2004-05-18 | 2007-12-26 | 统宝光电股份有限公司 | Luminescent materials and preparation method thereof and luminescent elements using same |
| CN100366657C (en) * | 2004-07-29 | 2008-02-06 | 复旦大学 | Buffering layer material for organic/high molecule luminous diode |
| CN100379836C (en) * | 2006-04-10 | 2008-04-09 | 武汉大学 | Process for preparing green light emitting materials polyalkyl fluorene |
| CN102382284A (en) * | 2011-06-28 | 2012-03-21 | 四川大学 | Poly-squaric acid conjugated polymer preparation method and application thereof |
| JP2021521304A (en) * | 2018-04-30 | 2021-08-26 | ハイドロ−ケベック | Squaric acid-based polymers, their manufacturing methods and their use |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422220C (en) * | 2005-09-08 | 2008-10-01 | 复旦大学 | Hindered amine end capped conjugated molecular material, and its preparing method and use |
| CN100489006C (en) * | 2007-06-21 | 2009-05-20 | 中国科学院长春应用化学研究所 | Method for preparing poly (9,9 dialkyl fluorene) |
-
2003
- 2003-03-10 CN CN 03117424 patent/CN1216921C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357390C (en) * | 2004-05-18 | 2007-12-26 | 统宝光电股份有限公司 | Luminescent materials and preparation method thereof and luminescent elements using same |
| CN100366657C (en) * | 2004-07-29 | 2008-02-06 | 复旦大学 | Buffering layer material for organic/high molecule luminous diode |
| CN1325530C (en) * | 2004-08-26 | 2007-07-11 | 复旦大学 | Luminous polyurethane material and its synthesis method |
| CN1305926C (en) * | 2005-03-17 | 2007-03-21 | 复旦大学 | Fluorene water soluble conjugate polymer containing polyethyene diamine side chain and its use |
| CN100379836C (en) * | 2006-04-10 | 2008-04-09 | 武汉大学 | Process for preparing green light emitting materials polyalkyl fluorene |
| CN102382284A (en) * | 2011-06-28 | 2012-03-21 | 四川大学 | Poly-squaric acid conjugated polymer preparation method and application thereof |
| JP2021521304A (en) * | 2018-04-30 | 2021-08-26 | ハイドロ−ケベック | Squaric acid-based polymers, their manufacturing methods and their use |
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