CN1876753A - An fluorene analogue electroluminescent material and its synthesis method thereof - Google Patents
An fluorene analogue electroluminescent material and its synthesis method thereof Download PDFInfo
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- CN1876753A CN1876753A CN 200610028367 CN200610028367A CN1876753A CN 1876753 A CN1876753 A CN 1876753A CN 200610028367 CN200610028367 CN 200610028367 CN 200610028367 A CN200610028367 A CN 200610028367A CN 1876753 A CN1876753 A CN 1876753A
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Abstract
The invention relates the fluorenes electroluminescent material and preparing method. The method comprises the following steps: using 9 site-doubly-bound butt-joint fluorenes as mother body, connecting fragments with the two ends of fluorenes, using groups with specific function to cap, and getting oligomer. The said material can be used to prepare organic electroluminescence device of excellent property, photo-voltaic cell, information storage, thin film transistor, and other organic photoconducting devices.
Description
Technical field
The invention belongs to organic information functional material technical field, be specifically related to a kind of fluorene analogue electroluminescent material and synthetic method thereof.
Background content
The organic/polymer electroluminescent device is one of focus forward position of current scientific research, the indicating meter made from it has high image quality, screen size can arbitrarily be adjusted, energy consumption is low, light weight and approaching, adopt the flexible macromolecule substrate collapsible, advantage such as tooling cost is low, thus represented the development trend of following technique of display.In display of organic electroluminescence, realize that the big area full color shows that stable red, green and blue three primary colours must be arranged.But have only red at present and greenly just have necessary luminous efficiency of business development and life-span, the high stable, high-level efficiency of realizing the material blue emission at present or a difficult problem.The common material that is used to prepare organic electroluminescent LED has benzene, fluorenes, carbazole, to phenylacetylene support, thiophene and their derivative etc.Poly-fluorenes is a kind of compound with rigid plane biphenyl modular construction, can go up limited several reflecting points by ring, and particularly the carbon on No. 9 positions obtains a series of derivatives.
Poly-fluorenes is to be obtained by human iron trichloride oxidative coupling fluorenes such as Fukuda the earliest, the polymkeric substance that obtains is because molecular weight is low, branching is more serious, and because residual iron ion strong absorption exciton, finally cause the polymer materials can't be luminous and do not have a practical value.Through constantly improving, on the polymer manufacture of fluorenes, obtained significant progress afterwards.The wherein ground-breaking work of tool is that people such as Suzuki finish.The poly-fluorenes molecular weight height that they obtain, the degree of branching is little, and molecular weight distribution is narrow.Wherein the poly-fluorenes photodiode of green light can be 22cm/W in peak efficient, under the situation of driving voltage less than 6V, and the luminous continuously 10000cd/m that surpasses
2
Fluorenes and derivative thereof can become the research focus of luminescent material, and this mainly is the energy gap owing to the fluorenes broad, higher characteristics such as luminous efficiency.But the electron affinity of fluorenes is little, and the solvability of poly-fluorenes is limited.No. 9 position carbon atoms of fluorenes become carbonyl again than being easier to oxidation, this easily forms " trap " to the exciton that electronics, hole-recombination produced and certain " cancellation " effect is arranged, and can reduce the luminescent lifetime of device.In order to improve the comprehensive electroluminescent properties of fluorenes, mainly at present adopt preparation small molecules fluorenes fluorescent material, introduce on fluorenes that different side group post polymerization prepares fluorenes homopolymer, fluorenes monomer and other monomer copolymerizations and preparation is derived and next methods such as branch-shape polymer by fluorenes.Reaction commonly used has Suzuki reaction, Yamamoto reaction, Wittig reaction and Stille reaction etc. in material synthetic process, wherein uses morely with the Suzuki reaction again.Because it is shorter that the organic electroluminescent phenomenon is found the time, the luminous basic theory of relevant material is not still set up fully, and this makes and can run into many parameters in the research process of electroluminescent organic material.Macromolecular material is because structure has the characteristics of polymolecularity, from the purifying aspect of operability, the final product of experiment and aspect such as sign all have unpredictalbe mutability, this makes and occurs self-contradictory result sometimes unexpectedly by the repeated bad of result of study.And micromolecular electroluminescent organic material structure is clear and definite, and the performance and the orthogonality relation between the structure of material are more direct.Experiment also than being easier to control, can obtain the very high product of purity.In addition, such material has the irreplaceable advantage of high-molecular luminous material at aspects such as solvability and workabilitys, and the fluorenes micromolecular luminescent material of therefore synthetic various structures just becomes a kind of very important means.
Summary of the invention
The objective of the invention is to propose fluorenes micromolecular electroluminescent material and synthetic method thereof a kind of solvability and highly processable, that experiment condition is easy to control.
The fluorenes micromolecular electroluminescent material that the present invention proposes is that the two fluorenes with 9 two keys butt joints are parent, connects the repeated fragment of different lengths at two fluorenes two ends, and with than a kind of oligomer that obtains behind the sterically hindered end group end-blocking greatly.The general structure of this oligomer can be expressed as follows:
Wherein, linking group X can be a kind of of phenyl ring, naphthalene nucleus, anthracene nucleus and other aromatic ring compounds, also can not have, and R is a side group, is made up of fragment and end group two portions.
Among the above-mentioned side group R, fragment can constitute in the good unit of cavity transmission ability one or more by fluorenes and derivative thereof, thiophene, carbazole and to vinylbenzene etc., also Ke Yi You oxadiazole, thiazole, benzothiazole, benzo pyridine, quinoline, hydroxyquinoline and derivative thereof etc. constitute in the good monomer of electron transport ability one or more, also can be the combinations between the above-mentioned two class groups.Its repeating unit number is generally between 1-3.
Among the above-mentioned side group R, end group can be sterically hindered big group, comprises spiral fluorenes, anthracene, the hole is had the triphenylamine of better transmission performance and benzene analog derivative that other contain different functional groups etc.
For the solvability of improving such organic polymer material and the thermostability that improves material, also contain on the side group fragment and be useful on long-chain groups such as the deliquescent long chain alkane that improves material, alcoxyl hydrocarbon, siloxanes, the carbon atom number of this long chain alkyl group is generally between 10-20.
The synthetic method of the oligomer that the present invention proposes mainly contains two kinds: one: with the fluorenes is the center, the synthetic earlier oligomer that has fragment, end group, by Clich reaction or Wittig reaction, after forming butt joint on 9 of fluorenes in the middle of two oligomers, obtain target oligomer material then; Two: with above-mentioned Clich reaction or Wittig reaction, on 9 of fluorenes, form butt joint earlier, obtain fluorenes oligomer parent with active end.Four active ends by fluorenes carry out further Suzuki reaction or other linked reactions with side group then, just can obtain target compound.
General synthetic method is can schematic representation as follows:
Wherein R contains fluorenes or contains thiophene Yi Ji the fragment of the two block structures of the P-N of oxadiazole.
Above-mentioned oligomer has good electroluminescent properties, is a kind of more satisfactory electroluminescent organic material, can be widely used in the preparation of electroluminescent device.Also can be used for preparing other organic luminescent device, as photovoltaic cell, message memory, thin film transistor etc.
Embodiment
Below the present invention will be further described by some embodiment, but embodiment does not limit covering scope of the present invention:
Embodiment 1
Choose the small molecules derivative of 2-bromo-spiral fluorenes and other fluorenes, be composite catalyst, under 90 ℃ of temperature, carry out the Suzuki reaction, prepare a series of fragment, productive rate about 30% with toluene solvant with triphenyl phosphorus palladium (O) title complex/yellow soda ash.By with the reaction of the Glich under NBS bromination and the sodium tert-butoxide catalysis, just can arrive target compound I then.Concrete synthesis condition is:
1, in the 50mL two-neck bottle of magneton and nitrogen conduit is housed, add 2.6 grams 9,9-2 dodecane-2,7-dibromo fluorenes, anhydrous and oxygen-free is handled, and adds the tetrahydrofuran (THF) dissolving of 25mL anhydrous and oxygen-free with the dry syringe of crossing, and stirs.Adding dry ice-propanone bathes, after treating that temperature-stable arrives-78 ℃, in 30 minutes, slowly splash into the butyllithium 2.5mL of 1.6M, after-78 ℃ of following continuously stirring are reacted 1 hour, the syringe of crossing with drying once adds the trimethylchlorosilane of 0.6mL, remove acetone the dry ice bath, continuously stirring reaction at room temperature 1 hour.Adding go out reaction back of a large amount of shrends and obtain organic phase dry the separation with petroleum ether extraction, revolve to steam and obtain being flaxen liquid, is that eluent carries out column chromatography and just can obtain colourless transparent liquid with sherwood oil, and generally productive rate can reach more than 90%.
2, the single fluorenes product of protecting with above-mentioned 2.38 grams that obtain is dissolved in the tetrahydrofuran (THF) of 25mL; all the other operations are the same; after the triisopropyl boric acid ester that adds 1.3mL; continuously stirring reaction at room temperature obtained white emulsion liquid in 24 hours later on; after the hydrochloric acid quencher reaction with a large amount of 2.0M; after separating drying with an amount of extracted with diethyl ether, revolve to steam and obtain thick liquid after desolventizing.With volume ratio is that 2: 1 sherwood oil and ethyl acetate mixed solution are that eluent carries out column chromatography and just can obtain a certain amount of white solid.
3, with 1.9 grams 2,7-dibromo fluorenone and the single protection of 7.1 grams boration fluorenes join the stirring magneton are housed, and in the three-necked bottle of 250mL spherical condensation tube and nitrogen conduit, the anhydrous and oxygen-free operation is carried out in sealing.Add an amount of triphenyl phosphorus palladium catalyst in glove box, lucifuge is handled, and adds the aqueous sodium carbonate of the 2M of the toluene of 150mL and 25mL with syringe, and in 90 ℃ oil bath, the continuously stirring reaction is 48 hours under the nitrogen protection.With after the dichloromethane extraction separation drying, obtain the white three difluorene solids of two protections for the eluent column chromatography with the sherwood oil after having reacted.
4, above-mentioned 2.88 grams, three difluorenes that obtain are dissolved in the tetracol phenixin of 50mL, under bathing, cryosel splashes into the iodine chloride hexane solution 3mL of 1.0M, stirring reaction is after half hour, and pouring reactant into a large amount of mass concentrations is that 5% Sulfothiorine is colourless to reactant.After the dichloromethane extraction washing drying, can obtain three difluorenes of two iodos with methanol wash.
5, the 2-boric acid spiral fluorenes of iodo three difluorenes that obtain and 2.1 times of mol ratios is carried out the Suzuki linked reaction in toluene solution and just can obtain compound 9,9,9 ", 9 " 4 dodecanes-2,7 " two spiral fluorenes-three fluorenes.
6, with above-mentioned obtain 9,9,9 "; 9 "-4 dodecanes-2,7 " two spiral fluorenes-three fluorenes are in carbon tetrachloride solution, under 80 ℃, under the Benzoyl Peroxide of catalytic amount causes, the continuously stirring reaction is after 10 hours; use carbon tetrachloride extraction; carry out with sherwood oil behind saturated aqueous common salt and the anhydrous magnesium sulfate drying that column chromatography is later just can to obtain 9 ' 9 '-two purer bromo-9,9,9 ", 9 " 4 dodecanes-2,7 -two spiral fluorenes-three difluorene.
7, with above-mentioned 9 ' 9 '-two bromo-9,9,9 ", 9 " 4 dodecanes-2,7 " two spiral fluorenes-three difluorenes are in anhydrous tetrahydro furan, and with the anhydrous tertiary butanol sodium tetrahydrofuran solution of exsiccant needle tubing adding catalytic amount, the room temperature continuously stirring was reacted 12 hours.Solution colour becomes scarlet by light red, add a large amount of shrends reaction of going out, dichloromethane extraction just can obtain crude product behind saturated aqueous common salt and the anhydrous magnesium sulfate drying, the said products is carried out column chromatography with normal hexane just can obtain pure target compound I.Its structural formula is as follows:
Compound I
Concrete synthesis step is:
Embodiment 2
Choosing the small molecules derivative of 2-bromo-spiral fluorenes and other fluorenes, is that catalyzer, temperature are carried out the Suzuki reaction under 90 ℃ at triphenyl phosphorus palladium (O) title complex/yellow soda ash, just can obtain target compound II.Synthesis condition is:
1, reference example 1 just can obtain 9,9,9 ", 9 " 4 dodecanes-2,7 " two spiral fluorenes-three fluorenes.
2, with above-mentioned 9,9,9 "; 9 "-4 dodecanes-2,7 " two spiral fluorenes-three fluorenes add in a certain amount of pyridine, add the Tetrabutyl amonium bromide of catalytic amount; under the situation of logical oxygen; the reaction of room temperature continuously stirring obtained yellow suspension liquid body in 48 hours, revolve to steam to desolventize after the back washs the gained yellow powder with massive laundering, and recrystallization is done with dehydrated alcohol in dry back just can obtain 9 '-ketone-9; 9; 9 ", 9 " 4 dodecanes-2,7 " two spiral fluorenes-three fluorenes.
3, with 9.2 grams 2; 4-dicyano-1; 3 dimethyl benzenes; 6 gram NBS and 0.5 gram benzoyl peroxide are dissolved in 200 milliliters the carbon tetrachloride solution; under the situation of nitrogen protection; the continuously stirring back flow reaction is after 10 hours; with mass concentration is that 5% sodium thiosulfate solution stirs the back dichloromethane extraction; behind saturated aqueous common salt and the anhydrous magnesium sulfate drying; with volume ratio is that 3: 1 ethyl acetate petroleum ether mixing solutions is done the developping agent column chromatography and just can be obtained pure 2; 4-dicyano-1,3 xylylene bromide.
4, will provide for oneself 2, the triethyl-phosphite of 4-dicyano-1,3 xylylene bromide and twice as high molar ratio reflux stirring reaction 3 hours in chloroform, steam desolventize after, use the toluene recrystallization, in 110 ℃ of baking ovens, be put in the moisture eliminator gained crystal stand-by after dry 1 hour.
5, three difluorene one monomers and the step 4 gained phosphorus bromide with mol ratios such as strictnesses is solvent with the dimethyl formamide, in the there-necked flask that stirs magneton, dropping funnel and reflux condensing tube is housed, under high degree of agitation, a certain amount of freshly prepd sodium ethylate sodium solution is slowly splashed in the reaction solution, keep little boiling.Continued stirring reaction 1 hour after dropwising, obtain target compound II with the methanol wash post precipitation.
Compound I I
Embodiment 3
Choose the parent of Compound I and contain thiophene Yi Ji the two block structure fragments of the P-N of oxadiazole just can obtain target compound III.X wherein can be 1-3.Concrete synthesis condition can be according to embodiment 1 described carrying out.
Compound III
Embodiment 4
Choose Compound I I parent and contain thiophene Yi Ji the oxadiazole fragment just can obtain having the target compound IV of the two block structures of P-N.Concrete experiment condition can be with reference to embodiment 1 and 2 described carrying out.
Compound IV
Embodiment 5
The fragment of choosing the Compound I parent and containing fluorenes just can obtain having the target compound V of the two block structures of P-N.The characteristics of this polymer materials are: end group both can be to contain aromatic amine oligomer material, also can be the oligomer material that contains strong electron-withdrawing group group-trifluoromethyl, whole material obtains a big conjugation oligomer material by direct connection of two keys of No. 9 positions of fluorenes in the middle of three difluorenes.Concrete synthesis condition can be with reference to embodiment 1 and 2 described carrying out.
Wherein,
Compound V
Embodiment 6
Choose Compound I I parent and contain thiophene Yi Ji the oxadiazole fragment just can obtain having the target compound VI of the two block structures of P-N.The characteristics of this polymer materials are: end group both can be to contain aromatic amine oligomer material, also can be the oligomer material that contains strong electron-withdrawing group group-trifluoromethyl, the two keys of whole material by No. 9 positions of fluorenes in the middle of three difluorenes be connected with an anthryl group and obtain a big conjugation oligomer material.Concrete synthesis condition can be with reference to embodiment 1 and 2 described carrying out.
Wherein,
Compound VI
Embodiment 7
The fragment of choosing Compound I I parent and fluorenes just can obtain target compound VII.The characteristics of this polymer materials are: end group both can be to contain aromatic amine oligomer material, also can be the oligomer material that contains strong electron-withdrawing group group-trifluoromethyl, the two keys of whole material by No. 9 positions of fluorenes in the middle of three difluorenes be connected with an anthryl group and obtain a big conjugation oligomer material.Concrete synthesis condition can be with reference to embodiment 1 and 2 described carrying out.
Wherein,
Compound VI I
Embodiment 8
The fragment of choosing Compound I parent and fluorenes just can obtain target compound VIII.The characteristics of this polymer materials are: end group both can be to contain aromatic amine oligomer material, also can be the oligomer material that contains strong electron-withdrawing group group-trifluoromethyl, whole material obtains a big conjugation oligomer material by direct connection of two keys of No. 9 positions of fluorenes in the middle of three difluorenes.Concrete synthesis condition can be with reference to embodiment 1 and 2 described carrying out.
Wherein,
Compound VIII
Claims (12)
1, a kind of fluorene analogue electroluminescent material is characterized in that it being that two fluorenes with 9 two keys butt joints are parent, connects the repeated fragment of different lengths at two fluorenes two ends and with the oligomer that obtains behind the sterically hindered end group end-blocking greatly, its general structural formula is as follows:
Wherein, linking group X is a kind of of phenyl ring, naphthalene nucleus, anthracene nucleus and other aromatic ring compounds, does not perhaps have, and R is a side group, is made up of fragment and end group two portions.
2, fluorene analogue electroluminescent material according to claim 1, it is characterized in that described fragment constitutes by the unit fluorenes that the hole is had better transmittability and derivative thereof, thiophene, carbazole and to one or more groups in the vinylbenzene, perhaps, perhaps constitute by above-mentioned two class moiety combinations by in electron transport ability good Dan Yuan oxadiazole, thiazole, benzothiazole, benzo pyridine, quinoline, hydroxyquinoline and the derivative thereof one or more are constituted; Segmental repeating unit number is between 1-3.
3, fluorene analogue electroluminescent material according to claim 1 is characterized in that described end group is sterically hindered big group: spiral fluorenes, anthracene, the hole is had the triphenylamine of better transmission performance and the benzene analog derivative that other contain different functional groups.
4, fluorene analogue electroluminescent material according to claim 1 is characterized in that also containing on the described side group R and is useful on long chain alkane, alkoxyl group, the silica hydrocarbyl group that improves material dissolves, and the carbon atom number of this group is 10-20.
5, a kind of synthetic method of oligomer as claimed in claim 1, it is characterized in that: one, be the center with the fluorenes, the synthetic earlier oligomer that has fragment, end group, then by Clich reaction or Wittig reaction, on 9 of fluorenes in the middle of two oligomers, form butt joint, obtain target oligomer material; Perhaps two, earlier with Clich reaction or Wittig reaction, on 9 of fluorenes, form butt joint, obtain the fluorenes oligomer parent with active end group, four active ends by fluorenes carry out further Suzuki reaction or other linked reactions with side group then, obtain the target oligomer.
6, fluorene analogue electroluminescent material according to claim 1 is characterized in that structural formula is:
7, fluorene analogue electroluminescent material according to claim 1 is characterized in that structural formula is:
8, fluorene analogue electroluminescent material according to claim 1 is characterized in that structural formula is:
9, fluorene analogue electroluminescent material according to claim 1 is characterized in that structural formula is:
10, fluorene analogue electroluminescent material according to claim 1 is characterized in that structural formula is:
Wherein,
11, fluorene analogue electroluminescent material according to claim 1 is characterized in that structural formula is:
Wherein,
12, fluorene analogue electroluminescent material according to claim 1 is characterized in that structural formula is:
Wherein,
13, fluorene analogue electroluminescent material according to claim 1 is characterized in that structural formula is:
Wherein,
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232473A (en) * | 2013-04-22 | 2013-08-07 | 南京邮电大学 | Fluorenyl organic framework material, preparation and application method thereof |
| CN103304540A (en) * | 2012-03-09 | 2013-09-18 | 海洋王照明科技股份有限公司 | Phosphorescent host material and preparation method thereof, and organic electroluminescent device |
| CN105418679A (en) * | 2015-10-29 | 2016-03-23 | 南京邮电大学 | Triphenylphosphine oxide unit bridged bipolar host material and application thereof |
| US10907093B2 (en) | 2016-10-17 | 2021-02-02 | Samsung Display Co., Ltd. | Condensed cyclic compound and organic light-emitting device including the same |
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2006
- 2006-06-29 CN CN 200610028367 patent/CN1876753A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304540A (en) * | 2012-03-09 | 2013-09-18 | 海洋王照明科技股份有限公司 | Phosphorescent host material and preparation method thereof, and organic electroluminescent device |
| CN103304540B (en) * | 2012-03-09 | 2016-08-03 | 海洋王照明科技股份有限公司 | Phosphorescent light body material, its preparation method and electroluminescent device |
| CN103232473A (en) * | 2013-04-22 | 2013-08-07 | 南京邮电大学 | Fluorenyl organic framework material, preparation and application method thereof |
| CN105418679A (en) * | 2015-10-29 | 2016-03-23 | 南京邮电大学 | Triphenylphosphine oxide unit bridged bipolar host material and application thereof |
| US10907093B2 (en) | 2016-10-17 | 2021-02-02 | Samsung Display Co., Ltd. | Condensed cyclic compound and organic light-emitting device including the same |
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