CN106866939A - The preparation of the diaryl fluorene polymer light sulfate ferroelectric functional material of one class new 9,9 and photoelectric device application - Google Patents
The preparation of the diaryl fluorene polymer light sulfate ferroelectric functional material of one class new 9,9 and photoelectric device application Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 9
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims description 7
- -1 diaryl fluorene Chemical compound 0.000 title claims description 6
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 230000021615 conjugation Effects 0.000 claims abstract description 9
- 238000010276 construction Methods 0.000 claims abstract description 7
- 239000008204 material by function Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 150000003254 radicals Chemical class 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229920002098 polyfluorene Polymers 0.000 claims description 6
- 239000007868 Raney catalyst Substances 0.000 claims description 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- FYEFHYMUEWRCRF-UHFFFAOYSA-N 2,7-dibromofluoren-1-one Chemical compound BrC1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 FYEFHYMUEWRCRF-UHFFFAOYSA-N 0.000 claims description 4
- 238000003747 Grignard reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 229940045872 sodium percarbonate Drugs 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- YOXUOHDHFCBGHY-UHFFFAOYSA-N 1-bromofluoren-9-one Chemical class C12=CC=CC=C2C(=O)C2=C1C=CC=C2Br YOXUOHDHFCBGHY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006462 rearrangement reaction Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 2
- 150000003851 azoles Chemical class 0.000 claims 1
- 150000004768 bromobenzenes Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002220 fluorenes Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RXACYPFGPNTUNV-UHFFFAOYSA-N 9,9-dioctylfluorene Chemical class C1=CC=C2C(CCCCCCCC)(CCCCCCCC)C3=CC=CC=C3C2=C1 RXACYPFGPNTUNV-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
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- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
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- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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Abstract
It is 49,9 Diarylfluorene polymer light sulfate ferroelectric functional materials with conjugation substituted radical the invention discloses a kind of construction unit, this invention belongs to organic photoelectrical material and field of information display.Specially reset using Bayer Wei Lige and prepare 4 containing conjugated structure substituted radical 9,9 Diarylfluorene monomers, then it is polymerized by Yamamoto and obtains polymer, and by this type materials application in organic photoelectric subdomains such as polymer LED (PLED), polymer thin film transistors (OFET).Such polymeric material has preparation process is simple, and cost of material is low, solvable liquefaction large area processing, is with a wide range of applications in the flexible electronic such as printed electronic field.
Description
Technical field
The invention belongs to organic photoelectrical material technical field, and in particular to a kind of construction unit is 4 and replaces containing conjugation
The preparation and its application of 9, the 9- Diarylfluorene polymer light sulfate ferroelectric functional materials of group, the compound have excellent photoelectricity
Performance, can be applied to the organic photoelectrics such as polymer LED (PLED), organic laser, OTFT (OFET)
Subdomains.
Technical background
Information technology is one of core realm of whole modern science and technology, and information display technology is important ring therein
Section.From Tang research groups of Kodak in 1987 and nineteen ninety univ cambridge uk's all one's life laboratory Friend and
Since Heeger has invented small molecule and polymer electroluminescence diode (OLED/PLED) respectively, it has been prepared into because it has
Originally relatively low, material category is abundant, the optional degree of structure is high, performance is adjustable, preparation process is simple, low cost are manufactured and bio-compatible
The advantages of property and device miniaturization, ultrathin flexible, become the study hotspot of people.At present, polymer organic semiconductor has been
It is widely applied to the organic photoelectrics such as polymer LED, organic laser, polymer solar battery, thin film transistor (TFT)
Subdomains.
Wherein, moved with its carrier higher with the polyfluorene class organic semiconductor that poly- 9,9- dioctyl fluorenes (PFO) are representative
Shifting rate, metastable deep blue emission, the advantages of fluorescence efficiency is high, have in Organic Light Emitting Diode and field of thin film transistors
It is widely applied.However, with poly- 9,9- dioctyl fluorenes class material for the Organic Light Emitting Diode of luminescent layer is being used for a long time
In, the transmitting of green glow band can be presented between 510nm~580nm, this defect has had a strong impact on the stability of photoluminescence and device of device
Part service life.For the problem of green glow band, there are two kinds of views in the world at present, one kind is aggregation of multiple, i.e. main polymer chain
The aggregation derivative spectomstry red shift of alkyl chain and produce green glow band, another saying is that No. 9 position alkyl chains of fluorenes are oxidized to form fluorenes
Ketone, produces the transmitting of green glow band.For problem above, we are reset and grignard reaction by Bayer-Wei Lige, with relative moderate
2,7- dibromo fluorenones are raw material, and design has synthesized 9 fluorenes class monomers replaced by diaryl, wherein to increase its dissolubility, suppression
The aggregation of polymer processed, we targetedly introduce alkyl chain at 4, and introduce conjugation substituted radical in the end of alkyl chain,
It is the inoxidizability of group that this molecule can effectively improve the 9 of fluorenes, while improving the solubility property of polymer.Experiment card
Bright, such polyfluorene based semiconductor material maintains heat endurance and glass transition temperature higher higher, at the same have compared with
Carrier mobility and excellent photoelectric properties high, its good dissolubility be able to can be carried out by molten liquefied mode
Processing, is that a class has potential polymer organic photoelectric functional material.
The content of the invention
It is an object of the invention to design a kind of performance of synthesis, polymer light sulfate ferroelectric functional material with low cost, this kind is gathered
Compound photoelectric functional material can be processed by solution, have the advantages that prepared by large area, in organic electroluminescent, organic
The optoelectronic areas such as thin film transistor (TFT), organic laser are widely used.
Technical scheme is as follows：The polymeric material of designed synthesis of the invention, 4 of its construction unit are to be tied with conjugation
The substituted radical of structure unit, 9 is aryl substituent group, and this structure can effectively improve the oxidation resistance of polymer,
The introducing of No. 4 position oxyalkyl chains simultaneously can improve the solubility property of polymer, and skeleton symbol is as follows：
Wherein, R is, with 4~8 alkyl chains or oxyalkyl chain of carbon atom, to be preferably as follows three kinds of structures：
Ar is benzene, carbazole, diphenylamines equiconjugate substituted radical, is preferably as follows three kinds of structures：
Present invention also offers a kind of 49,9- Diarylfluorene polymer lights to be conjugated substituted radical of construction unit
The preparation method of sulfate ferroelectric functional material, is reset by Bayer-Wei Lige and grignard reaction synthesis obtains be polymerized monomer used, Ran Houtong
Cross Yamamoto polymerizations and obtain polymer, here with R as hexyl, Ar is for as a example by carbazole substituted radical, its specific reaction is included such as
Lower step：
(1) preparation of polymerized monomer, response path is as follows：
Step 1：Lactone is prepared by the bromo- 9-Fluorenones of 2,7- bis- by Bayer-Wei Lige rearrangement reactions, specific reaction condition is
2,7- dibromo fluorenones room temperature reaction 72h under conditions of trifluoroacetic acid and SODIUM PERCARBONATE is obtained.
Step 2：2,7- dibromo glycol, specially 2,7- dibromos lactone and 4~6 times of bromines of equivalent are obtained by grignard reaction
The RMgBr reaction of benzene, solvent is toluene, the lower 85 DEG C of reactions 24h of nitrogen protection.
Step 3：The 1- of No. 4 alkyl substitutions of position alcohol radical, specially 2,7- dibromos glycol and 1.5 times of equivalents it is bromo- oneself
Base carbazole reacts 24h prepared with acetone as solvent under room temperature, alkalescence condition.
Step 4：Principal monomer is obtained by friedel-craft reaction, specially upper step product is dissolved in anhydrous methylene chloride, borontrifluoride
2h is reacted under boron-ether catalytic condition to be obtained.
(2) preparation of polymer, specific reactive mode is as follows：
Take the bipyridyl and Raney nickel Ni (COD) of equivalent2In full of N2Two mouthfuls of flasks in, it is then molten in 75 DEG C of DMF
20min is activated in liquid, the monomer solution that addition afterwards is dissolved with toluene flows back 3 days under the conditions of 85 DEG C, then dry with 0.1ml
Dry bromobenzene end-blocking, is finally extracted with THF and hydrazine hydrate and gone out, and last handling process removes the Raney nickel of residual, Ran Houxuan with THF suction filtrations
Steaming is settled with absolute methanol, is finally extracted 3 days with absolute methanol, and vacuum drying afterwards obtains powdery product.
Tested by the thermogravimetric analysis to such polymeric material and differential thermal analysis, it was demonstrated that such polymer light Electricity Functional material
Material shows good heat endurance, and the electrochemical properties that cyclic voltammetry is characterized show that oxidation potential does not substantially change,
Maintain the good electroluminescent ability of 9,9- diaryl fluorenes.
The present invention is on the basis of material preparation, there is provided have 9, the 9- Diarylfluorenes for being conjugated substituted radical with 4
Polymer is the device preparation method of luminescent layer, and the structure of wherein device is：ITO/PEDOT：PSS/EML/TPBi/LiF/Al,
Luminescent layer is prepared by solution spin coating, test result indicate that such polymer shows efficient blue emission performance, Ke Yizuo
The display fields such as the polymer organic LED of Blue-light emitting host material application for efficient stable.
Brief description of the drawings
Fig. 1 be such poly-fluorene material that the specific embodiment of the invention one is provided be dissolved in toluene it is measured to absorbing and
Emission spectrum；
Fig. 2 is such poly-fluorene material of the offer of the specific embodiment of the invention one as the knot of the organic luminescent device of EML
Structure schematic diagram；
Fig. 3 is such poly-fluorene material of the offer of the specific embodiment of the invention one as the electroluminescent light of emitting layer material
Spectrogram；
Specific embodiment
Specific embodiment one：
(1) preparation of polymerized monomer, response path is as follows：
Step 1：Take 2,7- dibromo fluorenones 2.8g (8.28mmol) to be dissolved in the dry dichloromethane of 30ml, be subsequently adding
25ml trifluoroacetic acids.Under condition of ice bath, every addition SODIUM PERCARBONATE Na in 15min2CO41g, totally 5 times.Room temperature is returned to afterwards
Stirring 72h, sodium acid carbonate NaHCO is used after reaction completely4Remove remaining trifluoroacetic acid, and use stone after being extracted with dichloromethane
Oily ether：Dichloromethane (5: 1) silicagel column is purified, and obtains light yellow powder solid (yield 85%)
Step 2：Bromobenzene 12ml and magnesium chips (1.76g, 72.4mmol) are taken first, with an iodine initiation reaction, then ice bath
Lower addition tetrahydrofuran and under nitrogen protection reaction 2h are complete to magnesium chips reaction.Then weigh 2,7- dibromos lactone (4.24g,
12mmol) it is dissolved in 60ml dry toluenes, and the grignard reagent that will be prepared is added, and after reacting 8h at 85 DEG C, uses saturation
NH4Cl aqueous solution extraction is gone out reaction, then with dichloromethane extraction, with petroleum ether: dichloromethane=1: 1 silicagel column is obtained after purification
White solid (yield 90%)
Step 3：Weigh 2,7- dibromos glycol (1.5g, 3mmol), Anhydrous potassium carbonate (1g, 7.2mmol), the bromo- hexyl clicks of 1-
Azoles (1.49g, 4.5mmol) is simultaneously dissolved in 30ml acetone, and 12h is then reacted at room temperature, is then extracted with dichloromethane, is done
With petroleum ether after dry revolving: dichloromethane=8: 1 silicagel column is purified, transparent solid (yield 80%) is obtained
Step 4：Product prepared by step 3 is dissolved in anhydrous methylene chloride, 0.2ml or so boron trifluoride second is subsequently adding
Ether, reacts 3h at room temperature, is subsequently adding 5ml water extraction and goes out and reacts and extracted with dichloromethane, dries revolving and simultaneously uses petroleum ether: dichloro
Methane: 6: 1 purifying, obtain white solid, yield (87%)
(2) preparation (being polymerized by Yamamoto) of polymer：
Take the bipyridyl and Raney nickel Ni (COD) of equivalent2In full of N2Two mouthfuls of flasks in, it is then molten in 75 DEG C of DMF
20min is activated in liquid, the monomer solution that addition afterwards is dissolved with toluene flows back 3 days under the conditions of 85 DEG C, then dry with 0.1ml
Dry bromobenzene end-blocking, is finally extracted with THF and hydrazine hydrate and gone out, and last handling process removes the Raney nickel of residual, Ran Houxuan with THF suction filtrations
Steaming is settled with absolute methanol, is finally extracted 3 days with absolute methanol, and vacuum drying afterwards obtains thread product.
The specific embodiment of other types of fluorene-based polymers of the present invention is identical with above-mentioned specific embodiment one,
1- bromos-hexyl the carbazole of step 3 kind is only revised as the substituted radical of corresponding type monomers.
Specific embodiment two：
The preparation of polymer organic LED is comprised the following steps：
Step 1：Ito glass is cleaned by ultrasonic 30min respectively through deionized water, absolute ethyl alcohol, acetone, then in an oven
Dried under the conditions of 120 DEG C, process 10min in ultraviolet lamp box afterwards.
Step 2：By sol evenning machine by PEDOT：PSS is spin-coated on the ito glass piece handled well with the speed of 3000r/min
On, time 60s, and the 10min that annealed at 120 DEG C.
Step 3：The toluene solution (concentration 10mg/ml) of polymer is passed through into sol evenning machine in glove box with 1000r/min
Spin coating 40s, and the 20min that annealed under the conditions of 80 DEG C in the glove box.
Step 4：Using the method for vacuum evaporation respectively by TPBI (20nm), LiF (0.8nm), Al (100nm) evaporations poly-
On compound film.
Claims (6)
1. 4 of a kind of its construction unit have 9, the 9- Diarylfluorene polymer of conjugation substituted radical, it is characterised in that its
4 ends of alkoxy chain of construction unit are conjugation substituted radical, and the polyfluorene class luminescent material has below formula structure：
Wherein, R is with 4~8 alkyl chains or oxyalkyl chain of carbon atom；Ar is benzene, carbazole, the substitution of diphenylamines equiconjugate
Group.
2. polyfluorene type photonic functional material according to claim 1, it is characterised in that R is the one kind in following structure：
3. polyfluorene type photonic functional material according to claim 1, it is characterised in that the terminal substituent group Ar of alkoxy chain R
It is the one kind in following structure：
4. a kind of construction unit as claimed in claim 1 is 49,9- diaryl fluorene Type of Collective containing conjugation substituted radical
The preparation method of object light sulfate ferroelectric functional material monomer, it is characterised in that the monomer of this kind of polymer is by Bayer-Wei Lige and lattice
Family name is synthesized, and by taking the carbazole structure that 4 is hexyl connection as an example, specific response path is as follows：
Step 1：Lactone is prepared by the bromo- 9-Fluorenones of 2,7- bis- by Bayer-Wei Lige rearrangement reactions, specific reaction condition is 2,7-
Dibromo fluorenone room temperature reaction 72h under conditions of trifluoroacetic acid and SODIUM PERCARBONATE is obtained；
Step 2：2,7- dibromo glycol is obtained by grignard reaction, specially 2,7- dibromos lactone and 4~6 times of bromobenzenes of equivalent
RMgBr reacts, and solvent is toluene, the lower 85 DEG C of reactions 24h of nitrogen protection；
Step 3：The bromo- hexyl clicks of 1- of No. 4 alkyl substitutions of position alcohol radical, specially 2,7- dibromos glycol and 1.5 times of equivalents
Azoles, with acetone as solvent, reacts 24h prepared under room temperature, alkalescence condition；
Step 4：Principal polymeric monomer is obtained by friedel-craft reaction, specially upper step product is dissolved in anhydrous methylene chloride, in trifluoro
Reaction 2h is obtained under changing boron-ether catalytic condition.
5. a kind of 49,9- Diarylfluorene polymer light sulfate ferroelectric functional materials with conjugation substituted radical as described in right 1
Preparation method, it is characterised in that this kind of polyfluorene type photonic functional material is polymerized by Yamamoto by monomer and obtained, it is specific anti-
Answer condition as follows：Take the bipyridyl and Raney nickel Ni (COD) of equivalent2In full of N2Two mouthfuls of flasks in, then in 75 DEG C
20min is activated in DMF solution, the monomer solution that addition afterwards is dissolved with toluene flows back 3 days under the conditions of 85 DEG C, Ran Houyong
0.1ml dries bromobenzene end-blocking, is finally extracted with THF and hydrazine hydrate and gone out, and the nickel that last handling process THF suction filtrations remove residual is catalyzed
Agent, then revolving absolute methanol sedimentation is finally extracted 3 days with absolute methanol, and vacuum drying afterwards obtains powdery product.
6. a kind of 4 as described in right 19,9- Diarylfluorene polymer light sulfate ferroelectric functional materials with conjugation substituted radical
Application, it is characterised in that such polymeric material can be applied to organic light emitting diode device as luminescent layer (EML), its
The structure of middle Organic Light Emitting Diode is：ITO/PEDOT：PSS/EML/TPBi/LiF/Al.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698653A (en) * | 2019-10-22 | 2020-01-17 | 苏州朗和电子科技有限公司 | Side group branched blue-light polymer material, preparation method and application of luminescent device |
| CN115417975A (en) * | 2022-09-19 | 2022-12-02 | 南京工业大学 | Fluorenyl polymer film with spherical crystal structure and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167800A (en) * | 2011-05-10 | 2011-08-31 | 南京邮电大学 | 9-hydroxyl-9'-aromatic conjugate substituted fluorene-containing polymer material and preparation and application methods thereof |
| CN105175690A (en) * | 2015-09-29 | 2015-12-23 | 南京邮电大学 | Preparation method for poly(4-alkoxy-9,9-diphenyl fluorene) beta phase |
-
2017
- 2017-04-10 CN CN201710242326.9A patent/CN106866939A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167800A (en) * | 2011-05-10 | 2011-08-31 | 南京邮电大学 | 9-hydroxyl-9'-aromatic conjugate substituted fluorene-containing polymer material and preparation and application methods thereof |
| CN105175690A (en) * | 2015-09-29 | 2015-12-23 | 南京邮电大学 | Preparation method for poly(4-alkoxy-9,9-diphenyl fluorene) beta phase |
Non-Patent Citations (3)
| Title |
|---|
| GONZALO DEL POZO等: ""Fluorene-Based Rib Waveguides with Optimized Geometry for Long-Term Amplified Spontaneous Emission Stability"", 《JOURNAL OF POLYMER SCIENCE》 * |
| JIN-YI LIN等: ""A Rational Molecular Design of β‑ Phase Polydiarylfluorenes:Synthesis, Morphology, and Organic Lasers"", 《MACROMOLECULES》 * |
| 林进义: ""超分子方法调控芴基聚合物聚集行为及其光电性能研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698653A (en) * | 2019-10-22 | 2020-01-17 | 苏州朗和电子科技有限公司 | Side group branched blue-light polymer material, preparation method and application of luminescent device |
| CN115417975A (en) * | 2022-09-19 | 2022-12-02 | 南京工业大学 | Fluorenyl polymer film with spherical crystal structure and preparation method and application thereof |
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