CN103450878A - Bipolar copolymer luminescent material, preparation method, and applications thereof - Google Patents
Bipolar copolymer luminescent material, preparation method, and applications thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 229920001577 copolymer Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000005401 electroluminescence Methods 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 40
- 238000005859 coupling reaction Methods 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
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- 238000000638 solvent extraction Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- DADZIMNFQANSAN-UHFFFAOYSA-N C(C1=CC=CC=C1)CC(C)=O.[Ar] Chemical compound C(C1=CC=CC=C1)CC(C)=O.[Ar] DADZIMNFQANSAN-UHFFFAOYSA-N 0.000 claims description 4
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 4
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 claims description 4
- YXPUNWKYPJPPFC-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.P YXPUNWKYPJPPFC-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 16
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 abstract description 5
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 230000005525 hole transport Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- 229950000688 phenothiazine Drugs 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- 150000003851 azoles Chemical class 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- OVZSYYOOTBORKV-UHFFFAOYSA-N anthracene 1H-pyrrole Chemical group C=1C=CNC=1.C1=CC=CC2=CC3=CC=CC=C3C=C21 OVZSYYOOTBORKV-UHFFFAOYSA-N 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002390 heteroarenes Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P ORPNDFMZTDVBGA-UHFFFAOYSA-N 0.000 description 1
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 1
- VSLDDSJTIWMSPL-UHFFFAOYSA-N 4h-trioxine Chemical compound C1OOOC=C1 VSLDDSJTIWMSPL-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(C)C=Cc(cc1)cc2c1N(*)c(ccc(C=Cc1nc(cc3c(-c4ccccc4)c(C4(C)C)c4nc3c3)c3c(-c3ccccc3)c1)c1)c1S2 Chemical compound CC(C)(C)C=Cc(cc1)cc2c1N(*)c(ccc(C=Cc1nc(cc3c(-c4ccccc4)c(C4(C)C)c4nc3c3)c3c(-c3ccccc3)c1)c1)c1S2 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention belongs to the field of organic semiconductor materials, and discloses a bipolar copolymer luminescent material, a preparation method, and applications thereof. The bipolar copolymer luminescent material has a structure formula, which is represented in the description, wherein R represents alkyl group with a carbon number between 1 and 20, and n is an integer between 10 and 50. The structure of the bipolar copolymer luminescent material provided by the invention has a phenothiazine unit, which has a hole transport performance, and an anthrazole unit, which has an electron transport performance, and the phenothiazine unit and the anthrazole unit are coupled and polymerized through Heck; furthermore, anthrazole contains two nitrogen atoms, and is an excellent electro transport unit; phenothiazine is aromatic heterocyclic compounds containing electron-rich nitrogen and sulphur atoms, and has a very good hole transport ability; N is modified through alkyl groups to improve the solubility and film-forming ability of the copolymer; phenothiazine groups are induced into the main chain of the anthrazole polymer to achieve the goal of charge balance of electroluminescent devices, and thus the problem of low efficiency of organic electroluminescence is solved.
Description
Technical field
The present invention relates to the organic semiconductor material field, relate in particular to a kind of bipolarity co-polymer luminescent material, its preparation method and application.
Background technology
From people's reported first such as the C.W.Tang of Kodak in 1987, by evaporation coating method, prepare with Alq
3since bi-layer devices structure for luminescent material, organic electroluminescent has just obtained people's very big concern.Organic electroluminescent can be divided into the fluorescence and phosphorescence electroluminescent.According to spin quantum statistical theory, the formation probability ratio of singlet state exciton and triplet exciton is 1:3, the singlet state exciton only account for " electron-hole pair " 25%.Therefore, the fluorescence that comes from the radiative transition of singlet state exciton just only accounts for 25% of total input energy, and the electroluminescent of phosphor material just can utilize the energy of whole excitons, thereby has larger superiority.Mostly adopt the Subjective and Objective structure in present electrophosphorescence device, soon the phosphorescent emissions material in main substance, to avoid burying in oblivion of triplet state-triplet state, improves phosphorescent emissions efficiency with certain doped in concentrations profiled.
Recently, about the polymer body material with bipolarity carrier transport, report is also arranged; As, (the J.Phys.Chem.B.2005 such as Wu, 109,14000.) reported a series of take gather fluorenes as main chain, the polymer body material that side chain contains carbazole and oxadiazole group, a kind of title complex of osmium of take is guest materials, the maximum external quantum efficiency 8.37% of the electroluminescent device of preparation, high-high brightness 16720cd/m
2.
Yet, the synthetic relatively complexity of the polymer body material with bipolarity transmission performance of having reported at present, preparation condition is harsher; The luminous efficiency of the electroluminescent device simultaneously, prepared with this material is lower.
Summary of the invention
One of problem to be solved by this invention is the bipolarity co-polymer luminescent material that provides a kind of preparation technology simply and can improve the organic electroluminescence device luminous efficiency.
Technical scheme of the present invention is as follows:
A kind of bipolarity co-polymer luminescent material, is characterized in that, it has following general structure:
In formula, R is C
1～C
20alkyl, the integer that n is 10-50.
Two of problem to be solved by this invention is to provide the preparation method of above-mentioned bipolarity co-polymer luminescent material, comprises the steps:
In oxygen-free environment, by general structure, be
compd A and general structure be
the compd B ratio that is 1: 1～1.2 according to mol ratio add in the reactor containing the organic solvent of catalyzer and carry out the Heck coupling reaction, this coupling reaction carries out under 70～130 ° of C, and after coupling reaction 24～96h, be cooled to room temperature, stop coupling reaction, make the bipolarity co-polymer luminescent material with following general structure:
Wherein, R is C
1～C
20alkyl, the integer that n is 10-50.
The preparation method of described bipolarity co-polymer luminescent material, preferably, the Heck coupling reaction also comprises the purification step to the bipolarity co-polymer luminescent material after finishing:
The Heck coupling reaction adds the methyl alcohol precipitating after finishing in reactor, after filtering by apparatus,Soxhlet's subsequently, then uses successively methyl alcohol and normal hexane extracting; Then take chloroform as solvent extraction to colourless, collect chloroformic solution and also be spin-dried for, obtain powder, and then will obtain powder and after 50 ° of dry 24h of C, obtain the bipolarity co-polymer luminescent material of purifying under vacuum.
In the preparation method of above-mentioned bipolarity co-polymer luminescent material, described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, and the mol ratio of described catalyzer and compd A is 1:20 ~ 1:100; Perhaps
The mixture that described catalyzer is organic palladium and organophosphorus ligand, the mol ratio of organic palladium and organophosphorus ligand is 1:4～8, and the mol ratio of described organic palladium and compd A is 1:20 ~ 1: 100; Described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Described organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl.
Above-mentioned organic solvent is at least one in toluene, DMF and tetrahydrofuran (THF).
The preparation method of described bipolarity co-polymer luminescent material, preferably, the temperature of reaction of described Heck coupling reaction is 90～120 ° of C, the reaction times is 48～72h.
Above-mentioned bipolarity co-polymer luminescent material, can be widely used in the luminescent layer of organic electroluminescence device, as the material of main part of luminescent layer.
Bipolarity co-polymer luminescent material provided by the invention, the thiodiphenylamine unit that this material structure has the hole transport performance passes through the Heck coupling polymerization with the anthracene azoles unit with electronic transmission performance, and the anthracene azoles contains two nitrogen, it is a good electric transmission unit, and have rigidity and planarity preferably, thermal stability is good; Thiodiphenylamine is the class nitrogen that contains electron rich and the heteroaromatic compound of sulphur atom, there is good cavity transmission ability, pass through alkyl modified on N, thereby improve solubility property and the film forming properties of multipolymer, introduce phenothiazinyl on anthracene azoles based polyalcohol main chain, realize the carrier balance of electroluminescent device, thereby solve the organic electroluminescence device low efficiency problem.
Bipolarity co-polymer luminescent material preparation method provided by the invention, adopted better simply synthetic route, thereby reduce technical process, and starting material are cheap and easy to get, makes manufacturing cost reduce; And the polymeric material novel structure made, solubility property is good, and film forming properties is good, applicable to organic electroluminescence device.
The accompanying drawing explanation
Fig. 1 is bipolarity co-polymer luminescent material preparation technology schema of the present invention;
Fig. 2 is the organic electroluminescence device structural representation that embodiment 6 makes;
The electroluminescent spectrum figure that Fig. 3 is the organic electroluminescence device that makes of embodiment 6.
Embodiment
Bipolarity co-polymer luminescent material provided by the invention, belong to electron-transporting type bipolarity co-polymer luminescent material, and it has following general structure:
In formula, R is C
1～C
20alkyl, the integer that n is 10-50.
Bipolarity co-polymer luminescent material provided by the invention, the thiodiphenylamine unit that this material structure has the hole transport performance passes through the Heck coupling polymerization with the anthracene azoles unit with electronic transmission performance, and the anthracene azoles contains two nitrogen, it is a good electric transmission unit, and have rigidity and planarity preferably, thermal stability is good; Thiodiphenylamine is the class nitrogen that contains electron rich and the heteroaromatic compound of sulphur atom, there is good cavity transmission ability, pass through alkyl modified on N, thereby improve solubility property and the film forming properties of multipolymer, introduce phenothiazinyl on anthracene azoles based polyalcohol main chain, realize the carrier balance of electroluminescent device, thereby solve the organic electroluminescence device low efficiency problem.
In view of this, above-mentioned bipolarity co-polymer luminescent material can also be widely used in the luminescent layer of organic electroluminescence device, as the luminescent layer material of main part.
The present invention also provides the preparation technology of above-mentioned bipolarity co-polymer luminescent material, as shown in Figure 1, comprises the steps:
S1, the compd A that following general structure is provided respectively and compd B:
Wherein, in compd A, R is C
1～C
20alkyl;
S2, under oxygen-free environment (at least one gas in nitrogen, argon gas forms), the ratio that is 1:1～1.2 according to mol ratio by compd A and B be added into the organic solvent that contains catalyzer reactor (as, flask or two-mouth bottle) in, carry out Heck coupling reaction 24～96h under 70～130 ° of C, be cooled to subsequently room temperature, stop coupling reaction, obtain the reaction solution that contains the bipolarity co-polymer luminescent material, this bipolarity co-polymer luminescent material has following general structure:
In formula, the integer that n is 10-50;
After S3, reaction finish, in flask, add the methyl alcohol precipitating, by using successively methyl alcohol and normal hexane extracting after the apparatus,Soxhlet's filtering reacting liquid; Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain powder, powder after 50 ° of dry 24h of C, is obtained to the bipolarity co-polymer luminescent material of purifying under vacuum.
In the preparation method of above-mentioned bipolarity co-polymer luminescent material, in step S2:
Described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, and the mol ratio of described catalyzer and compd A is 1:20 ~ 1:100; Perhaps
The mixture that described catalyzer is organic palladium and organophosphorus ligand, the mol ratio of organic palladium and organophosphorus ligand is 1:4～8, and the mol ratio of described organic palladium and compd A is 1:20 ~ 1: 100; Described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Described organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl;
Above-mentioned organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
Preferably, in step S2, the temperature of reaction of Heck coupling reaction is 90～120 ° of C, and the reaction times is 48～72h.
Bipolarity co-polymer luminescent material preparation method provided by the invention, adopted better simply synthetic route, thereby reduce technical process, and starting material are cheap and easy to get, makes manufacturing cost reduce; And the polymeric material novel structure made, solubility property is good, and film forming properties is good, applicable to organic electroluminescence device.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
In following embodiment 1 ~ 5, the monomer of compd A is bought and is obtained from the market, and the disclosed method of the monomer reference literature of compd B (J.AM.CHEM.SOC.9VOL.125, NO.44,2003) is synthetic to be obtained.
Embodiment 1
The bipolarity multipolymer material of main part of the present embodiment, poly-{ N-n-octyl-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } (P1) (wherein, R is the octane base, and n=34), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under argon shield, by N-n-octyl-3,7-divinyl thiodiphenylamine (73mg, 0.2mmol), 2,7-bis-is bromo-4,9-diphenylanthrancene azoles (98mg, 0.2mmol) add in the flask that fills the 10ml toluene solvant and fully dissolve, vacuumize deoxygenation and be filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol); Flask is heated to 100 ℃ and carries out Heck coupling reaction 60h.Subsequently, stop coupling reaction after cooling, to dripping in 50ml methyl alcohol and carry out sedimentation in flask; Use successively methyl alcohol and normal hexane extracting 24h after filtering by apparatus,Soxhlet's.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, after the collection powder, under vacuum, after 50 ℃ of dry 24h, is gathered { N-n-octyl-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } product, productive rate 85%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=22.6kDa, M
w/ M
n=2.2.
Embodiment 2:
The bipolarity multipolymer material of main part of the present embodiment, poly-{ N-methyl-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } (P2) (wherein, R is methyl, and n=10), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and the protection of argon gas gas mixture; by N-methyl-3; 7-divinyl thiodiphenylamine (80mg; 0.3mmol), 2; 7-bis-bromo-4; 9-diphenylanthrancene azoles (147mg; 0.3mmol) and the 15mL tetrahydrofuran (THF) add in the two-mouth bottle of 50mL specification; after passing into the about 20min of gas mixture air-discharging of nitrogen and argon gas after fully dissolving; then by tetra-triphenylphosphine palladium (4mg; 0.003mmol) add wherein, then, after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 70 ℃ and carry out Heck coupling reaction 96h.Subsequently, stop coupling reaction after cooling, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, after the collection powder, is gathered { N-methyl-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } product after 50 ℃ of dry 24h under vacuum.Productive rate is 65%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=10.1kDa, M
w/ M
n=2.4.
Embodiment 3:
The bipolarity multipolymer material of main part of the present embodiment, poly-{ N-NSC 62789 base-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } (P3) (wherein, R is the NSC 62789 base, and n=50), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by N-NSC 62789 base-3,7-divinyl thiodiphenylamine (159mg, 0.3mmol), 2,7-bis-bromo-4,9-diphenylanthrancene azoles (162mg, 0.33mmol), palladium (3.5mg, 0.015mmol) and three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) joins the N that fills 12mL, in the flask of dinethylformamide, fully dissolve, subsequently toward after leading to the about 30min of nitrogen purge gas in flask; Flask is heated to 130 ℃ and carries out Heck coupling reaction 24h.Subsequently, stop coupling reaction after cooling, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collecting after powder under vacuum 50 ℃ of dry 24h, be poly-{ N-NSC 62789 base-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } product, productive rate 80%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=43.6kDa, M
w/ M
n=2.0.
Embodiment 4:
The bipolarity multipolymer material of main part of the present embodiment, poly-{ N-normal butane base-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } (P4) (wherein, R is the normal butane base, and n=44), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by N-normal butane base-3,7-divinyl thiodiphenylamine (92mg, 0.3mmol), 2,7-bis-bromo-4,9-diphenylanthrancene azoles (176mg, 0.36mmol), three or two argon benzyl acetone two palladiums (9mg, 0.009mmol) and 2-dicyclohexyl phosphines-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) join in the flask of the DMF that fills 12mL and fully dissolve, subsequently toward after leading to the about 30min of nitrogen purge gas in flask; Flask is heated to 120 ℃ and carries out Heck coupling reaction 36h.Subsequently, stop coupling reaction after cooling, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collecting after powder under vacuum 50 ℃ of dry 24h, be poly-{ N-normal butane base-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } product, productive rate is 72%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=28.1kDa, M
w/ M
n=2.1.
Embodiment 5:
The bipolarity multipolymer material of main part of the present embodiment, poly-{ N-dodecyl-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } (P5) (wherein, R is dodecyl, and n=21), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and the protection of argon gas gas mixture; by N-dodecyl-3; 7-divinyl thiodiphenylamine (126mg; 0.3mmol), 2; 6-bis-iodo-3; 7-phenylbenzene benzo [1; 2-b:4; 5-b '] two furans (147mg, 0.3mmol) and 15mL toluene adds in the two-mouth bottle of 50mL specification, after passing into the about 20min of gas mixture air-discharging of nitrogen and argon gas after fully dissolving; then by tetra-triphenylphosphine palladium (8mg; 0.006mmol) add wherein, then, after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 90 ℃ and carry out Heck coupling reaction 48h.Subsequently, stop coupling reaction after cooling, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, after the collection powder, is gathered { N-dodecyl-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } product after 50 ℃ of dry 24h under vacuum.Productive rate is 82%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=16.8kDa, M
w/ M
n=2.3.
The present embodiment is organic electroluminescence device, the bipolarity multipolymer material of main part that the material of main part of its luminescent layer adopts embodiment 1 to make, gather { N-n-octyl-3,7-divinyl thiodiphenylamine-co-2,7-bis-bases-4,9-diphenylanthrancene azoles } (P1), guest materials adopts (methyl ethyl diketone) two (the 2-methyldiphenyl is [F, H] quinoxalines also) to close iridium (Ir (MDQ)
2(acac)), guest materials is doped in material of main part according to the ratio of 10% mass percent, and manifestation is P 1:Ir (MDQ)
2(acac).
As shown in Figure 2, organic electroluminescence device comprises the ITO conductive glass that stacks gradually (being called for short ITO) 1, hole injection layer 2(PEDOE:PSS), luminescent layer 3(P1:Ir (MDQ)
2(acac)), hole blocking layer 4(2,9-dimethyl-4,7-phenylbenzene-1, the 10-phenanthroline, BCP), electron transfer layer 5(tri--oxine aluminium, Alq
3), cathode layer (comprising lithium fluoride layer 6 and aluminium lamination 7).
The concrete grammar that electroluminescent device is made is:
Spin coating PEDOT:PSS successively on conductive glass (ITO) substrate through cleaning, spin coating P1:Ir (MDQ)
2(acac), evaporation BCP and Alq
3, then evaporation lithium fluoride and aluminium obtains organic electroluminescence device as cathode layer, the structure of this device and thickness are: ITO(150nm)/PEDOT:PSS (30nm)/P1:Ir (MDQ)
2(acac) (20nm)/BCP (30nm)/Alq
3(30nm)/LiF (1.5nm)/Al (150nm)
The electroluminescent spectrum figure that Fig. 3 is the organic electroluminescence device that makes of embodiment 6; Wherein, electric current-the brightness-voltage characteristic of device is to be completed by the Keithley source measuring system with the correction silicon photoelectric diode (Keithley 2400Sourcemeter, Keithley 2000Cuirrentmeter), electroluminescent spectrum is by the French JY SPEX CCD3000 of company spectrometer measurement, and all measurements all complete in atmosphere at room temperature.Result shows, the maximum lumen efficiency of device is 17.2cd/A, and high-high brightness is 63610cd/m
2, the emission maximum peak value of this material is positioned at 610nm.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. a bipolarity co-polymer luminescent material, is characterized in that, it has following general structure:
In formula, R is C
1～C
20alkyl, the integer that n is 10-50.
2. the preparation method of a bipolarity co-polymer luminescent material, is characterized in that, comprises the steps:
In oxygen-free environment, by general structure, be
compd A and general structure be
the compd B ratio that is 1:1～1.2 according to mol ratio add in the reactor containing the organic solvent of catalyzer and carry out the Heck coupling reaction, this coupling reaction carries out under 70～130 ° of C, and after coupling reaction 24～96h, be cooled to room temperature, stop coupling reaction, make the bipolarity co-polymer luminescent material with following general structure:
Wherein, R is C
1～C
20alkyl, the integer that n is 10-50.
3. the preparation method of bipolarity co-polymer luminescent material according to claim 2, is characterized in that, the Heck coupling reaction also comprises the purification step to the bipolarity co-polymer luminescent material after finishing:
The Heck coupling reaction adds the methyl alcohol precipitating after finishing in reactor, after filtering by apparatus,Soxhlet's subsequently, then uses successively methyl alcohol and normal hexane extracting; Then take chloroform as solvent extraction to colourless, collect chloroformic solution and also be spin-dried for, obtain powder, and then will obtain powder and after 50 ° of dry 24h of C, obtain the bipolarity co-polymer luminescent material of purifying under vacuum.
4. according to the preparation method of the described bipolarity co-polymer luminescent material of claim 2 or 3, it is characterized in that, described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; The mol ratio of described catalyzer and compd A is 1:20 ~ 1:100.
5. according to the preparation method of the described bipolarity co-polymer luminescent material of claim 2 or 3, it is characterized in that, the mixture that described catalyzer is organic palladium and organophosphorus ligand, and the mol ratio of organic palladium and organophosphorus ligand is 1:4～8; The mol ratio of described organic palladium and compd A is 1:20 ~ 1:100.
6. the preparation method of bipolarity co-polymer luminescent material according to claim 5, is characterized in that, described organic palladium is palladium or three or two argon benzyl acetone two palladiums.
7. the preparation method of bipolarity co-polymer luminescent material according to claim 5, is characterized in that, described organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl.
8. according to the preparation method of the described bipolarity co-polymer luminescent material of claim 2 or 3, it is characterized in that, described organic solvent is at least one in toluene, DMF and tetrahydrofuran (THF).
9. according to the preparation method of the described bipolarity co-polymer luminescent material of claim 2 or 3, it is characterized in that, the temperature of reaction of described Heck coupling reaction is 90～120 ° of C, and the reaction times is 48～72h.
10. the described bipolarity co-polymer luminescent material of claim 1 is as the application of the luminescent layer material of main part of organic electroluminescence device.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107964091A (en) * | 2017-11-22 | 2018-04-27 | 北京大学深圳研究生院 | A kind of multifunctional bipolar conducting polymer and preparation method and application |
| CN108003329A (en) * | 2017-11-22 | 2018-05-08 | 北京大学深圳研究生院 | A kind of multifunctional bipolar conducting polymer and preparation method and application |
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2012
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107964091A (en) * | 2017-11-22 | 2018-04-27 | 北京大学深圳研究生院 | A kind of multifunctional bipolar conducting polymer and preparation method and application |
| CN108003329A (en) * | 2017-11-22 | 2018-05-08 | 北京大学深圳研究生院 | A kind of multifunctional bipolar conducting polymer and preparation method and application |
| CN107964091B (en) * | 2017-11-22 | 2020-05-19 | 北京大学深圳研究生院 | Multifunctional bipolar conductive polymer and preparation method and application thereof |
| CN108003329B (en) * | 2017-11-22 | 2020-05-19 | 北京大学深圳研究生院 | Multifunctional bipolar conductive polymer and preparation method and application thereof |
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