CN101161698B - Break-in conjugated branched polymer material and preparation method and uses thereof - Google Patents
Break-in conjugated branched polymer material and preparation method and uses thereof Download PDFInfo
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- 239000002861 polymer material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 7
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- -1 n-octyl Chemical group 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 9
- 229920000547 conjugated polymer Polymers 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000021615 conjugation Effects 0.000 claims description 4
- 125000003136 n-heptyl 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])* 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000006608 n-octyloxy group Chemical group 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 125000002704 decyl 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])* 0.000 claims 2
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- 239000000126 substance Substances 0.000 abstract description 2
- 229920000587 hyperbranched polymer Polymers 0.000 abstract 2
- 238000013086 organic photovoltaic Methods 0.000 abstract 2
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
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- 238000006243 chemical reaction Methods 0.000 description 24
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- 150000001412 amines Chemical class 0.000 description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 15
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 15
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- 238000001035 drying Methods 0.000 description 10
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Chemical group 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
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- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- HVQSEKGARNNWON-UHFFFAOYSA-N boric acid pyrene Chemical compound OB(O)O.c1cc2ccc3cccc4ccc(c1)c2c34 HVQSEKGARNNWON-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- 239000007818 Grignard reagent Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
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- HYGLETVERPVXOS-UHFFFAOYSA-N 1-bromopyrene Chemical compound C1=C2C(Br)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 HYGLETVERPVXOS-UHFFFAOYSA-N 0.000 description 1
- KAYXDWIILRESPY-UHFFFAOYSA-N 2-[7-(1,3,2-dioxaborinan-2-yl)-9,9-dioctylfluoren-2-yl]-1,3,2-dioxaborinane Chemical compound C1=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(B4OCCCO4)=CC=C3C2=CC=C1B1OCCCO1 KAYXDWIILRESPY-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- NJRNORJLPQYHHY-UHFFFAOYSA-N 2-bromo-9-phenylfluoren-9-ol Chemical compound C12=CC=CC=C2C2=CC=C(Br)C=C2C1(O)C1=CC=CC=C1 NJRNORJLPQYHHY-UHFFFAOYSA-N 0.000 description 1
- HIMHGSMPEUWUCL-UHFFFAOYSA-N 4-(2-bromo-9-phenylfluoren-9-yl)-N,N-bis[4-(2-bromo-9-phenylfluoren-9-yl)phenyl]aniline Chemical compound C1(=CC=CC=C1)C1(C2=CC=CC=C2C=2C=CC(=CC1=2)Br)C1=CC=C(C=C1)N(C1=CC=C(C=C1)C1(C2=CC=CC=C2C=2C=CC(=CC1=2)Br)C1=CC=CC=C1)C1=CC=C(C=C1)C1(C2=CC=CC=C2C=2C=CC(=CC1=2)Br)C1=CC=CC=C1 HIMHGSMPEUWUCL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- BBTDVOYRMGTHOB-UHFFFAOYSA-N C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34.[Br] Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34.[Br] BBTDVOYRMGTHOB-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
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- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
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- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
Abstract
The present invention relates to a conjugation-broken hyperbranched polymer material, a preparation method thereof, and a technology field of the organic photovoltaic material, and specifically to a conjugation-broken hyperbranched polymer material and a preparation method thereof. The material is used in organic active display, organic optical storage, organic photovoltaic cell, organic field effect tube, chemical and biology sensor, organic laser, etc. and the material is a polymeric material with 9, 9-diaryl fluorine as a branched monomer based on triphenylamine. The material has the advantage that synthesization is easy to be achieved, and a special non-planar structure is formed and pi-conjugate chain is broken, and the material has a high thermal stability and glass temperature. Conceivably, the series of materials will be photovoltaic functional materials with a commercialization future.
Description
Technical field
The invention belongs to the organic photoelectrical material technical field.Be specifically related to a kind of break-in conjugated branched polymer material and preparation method thereof, and relate to of the application of these materials in organic electroluminescent, organic optical storage, organic field-effect tube, organic solar batteries, nonlinear optical organic, chemistry and fields such as bio-sensing and organic laser.
Technical background
From Tang research group of Kodak [Tang, C.W. in 1987; Van Slyke, S.A.Appl.Phys.Lett.1987,51,913.] and nineteen ninety univ cambridge uk [Burroughes, J.H.; Bradley, D.D.C.; Brown, A.B.; Marks, R.N.; Mackay, K.; Friend, R.H.; Burn, P.L.; Holmes, A.B.Nature1990,347,539.] delivered respectively make film-type organic electroluminescence device (Organic Light-emitting Diodes) and polymer LED (PolymericLight-emitting Diodes) with organic and polymer fluorescent material since, organic flat pannel display becomes the demonstration product of the another generation marketization after liquid-crystal display.Meanwhile other organic electronics and photoelectronic industry include field such as electromechanical memory devices, organic field-effect tube, organic solar batteries, nonlinear optics, bio-sensing and laser and nonlinear optical material and are also just moving towards the marketization.Organic and the advantage plastic electronic product is that the material preparation cost is low, technology simple, has the snappiness and the plasticity-of commodity polymer.Therefore, develop the novel organic photoelectric information material of market potential and attracted the scientist of the different subjects of many domestic and international universities and the concern and the input of research institution and company with practicality.
Up to the present, a large amount of documents and patent report the carrier transport structure primitive is combined with luminescent material be implemented in the simple Devices current carrier and can balance inject and transmission, device shows good performance at aspect of performances such as luminous efficiency and brightness.Combination mainly comprises main chain conjugation mode, side chain conjugation mode, side chain interrupts mode and main chain interrupts mode.Wherein, main chain interrupts mode only seldom document and patent report, does not still have document and patent report based on half conjugated polymers that interrupts of two quaternary carbon atoms.Yet, have high thermostability and second-order transition temperature based on the structural unit of two quaternary carbon atoms.When utilizing two quaternary carbon atoms designs to interrupt half conjugated polymers can to guarantee the thermostability of material and spectrum stability, also can effectively realize the modulation of the HOMO energy level of material, thereby the balance that realizes device is injected by introducing the carrier transport structure unit.In addition, interrupt half conjugated polymers and can might realize electric bi-stable state character by electron tunneling.Therefore, the present invention designs and has developed a series of organic light emissions and electricity storage photoelectric materials that interrupt half conjugated polymers by two quaternary carbon atoms.In addition, enlarge such material in organic electronic, photoelectron or photoelectric material use range by having introduced to have to increase solubleness, the gathering of obstruct chromophoric group or increase stable structural chain.
Summary of the invention
Technical problem: the objective of the invention is to propose break-in conjugated branched polymer material and preparation method and application, should be based on the interrupting half conjugated polymers and can effectively introduce the carrier transport structure unit of two quaternary carbon atoms, and design effective synthetic route and realize that such interrupts the synthetic of half conjugated polymers.In addition, pointed out such material at organic electroluminescent, the application in organic electronic fields such as electromechanical memory devices and laser is arranged.
Technical scheme: break-in conjugated branched polymer material of the present invention be based on triphenylamine complexity 9, the 9-diaryl fluorene is the polymer materials of branched monomer, has following structure:
In the formula: R
1For hydrogen or have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom; W is carbon or nitrogen; E is a capping group, x, the y numeral between 1～100,
E is specially a kind of in the following array structure:
Ar is the conjugation group, and is identical or different when occurring, and is specially down a kind of in the array structure:
Wherein, the symbol in the formula has following implication:
-
*The band of position that is connected with branched monomer for Ar between the structural unit;
R
2Identical or different during appearance, and be not selected from hydrogen or normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or positive certain herbaceous plants with big flowers base or the n-octyloxy chain any one;
In interrupting the hyperbranched conjugated polymer material, R
1Be selected from hydrogen or normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or positive certain herbaceous plants with big flowers base or the n-octyloxy chain any one respectively.
In break-in conjugated branched polymer material, W is a carbon in compound-material I, has following structure:
The preparation method of break-in conjugated branched polymer material, specific as follows: 1. prepare based on 9 of the complexity of triphenylamine by step earlier, the 9-diaryl fluorene is a branched monomer, again by step 2. linked reaction prepare compound-material I; Wherein 1. step is example with the branched monomer by catalytic pair of boron trifluoride ethyl ether complex-gram prepared in reaction three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine:
Wherein 2. step is example to prepare compound-material I by the Suzuki linked reaction:
The Suzuki linked reaction is the carbon-carbon bond linked reaction that palladium catalysis boric acid and halogen take place; Catalyst consumption is 0.1 to 20mol%; Suitable solvent is low-pole or aprotic, polar organic solvent or its mixed solvent; Be reflected at 30 to 150 ℃ of temperature; Reaction times is 1 to 7 day.
Beneficial effect: characterized the high polymer material structure by ultimate analysis, infrared spectra (FTIR), nucleus magnetic resonance (NMR), chromaticness online (GCMS), ground substance assistant laser parsing time-of-fight mass spectrometry (MALDI-TOF-MS), gel chromatography (GPC), by the thermostability that thermogravimetric analysis and differential thermal analysis have been tested material, characterized their electrochemical properties by cyclic voltammetry.
The wherein thermogravimetric analysis of such material and differential thermal analysis test has shown good thermostability; The electrochemical properties that the cyclic voltammetry of carbazoles blue light material characterizes shows that oxidation potential reduces greatly, effectively the injectability in the hole of improving; And blue light material has kept high luminous efficiency.Therefore, such material can be used as the material of main part of stablizing blue light material and white light and phosphorescence efficiently.
Such molecular material also can be applied to organic electronic fields such as dynamo-electric storage medium.Compound-material I is applicable to organic light emitting diode device, electromechanical memory devices is arranged, organic solar batteries, organic laser diode component, organic field-effect tube etc.
On this basis, design preliminary device and estimated break-in conjugated branched polymer material electroluminescent behavior and electric bi-stable state character, prepared the blue-light device and the white light parts of break-in conjugated branched polymer material.Transparent anode is produced on on glass or the plastic, then the break-in conjugated branched polymer material after spin coating break-in conjugated branched polymer material on the conductive layer or doping, evaporation negative electrode at last.Experimental result shows: these break-in conjugated branched polymer materials can be used as stablizes blue light material and white light and phosphorescent light body material.
Major advantage of the present invention is:
1. synthesize and conveniently be easy to get;
2. the characteristics that special on-plane surface conformation and pi-conjugated chain interrupt;
3. high glass transition temperature and high thermal stability have been kept.
Description of drawings:
Fig. 1. contain the electric current-voltage-brightness curve of blue-light device of the copolymer material of three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine branching unit of 5%.
Fig. 2. contain the electroluminescent spectrum under the different current densities of blue-light device of copolymer material of three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine branching unit of 5%.
Fig. 3. contain 5% three (4-(the 2-bromo-9-phenyl fluorenes-9-yl) phenyl) copolymer materials of amine branching unit and the electric current-voltage-brightness curve of the white light parts of MEHPPV blend.
Fig. 4. contain the electroluminescent spectrum under the different current densities of three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) copolymer material of amine branching unit of 5% and the white light parts of MEHPPV blend.
Embodiment
In order to understand the content of patent of the present invention better, further specify technical scheme of the present invention below by concrete example, specifically comprise the preparation of synthetic, property testing and device.But these embodiments do not limit the present invention.
2-bromo-9-phenyl-fluorenes-9-alcohol
2-bromo-9-phenyl-9H-fluoren-9-ol
(4.48g is 29mmol) with magnesium Mg (0.58g, 24mmol) reaction generation Grignard reagent to get bromo-benzene, with be dissolved in 2-bromine Fluorenone (3.135g in the tetrahydrofuran (THF) (20mL), 12.1mmol) 60 ℃ of reactions 24 hours, generate a large amount of white precipitates, add saturated colour NHCl at last
4Ge Shi salt is converted into alcohol.After reaction finishes, extracted with diethyl ether, drying is revolved steaming, sherwood oil: methylene dichloride mixed solvent (3:2) silicagel column purifying obtains the slightly yellowish solid tertiary alcohol (3.70g, 90%).
GC-MS(EI-m/z)：334/336(M
+).
1H?NMR(400MHz，CDCl
3，ppm)：δ7.657-7.655(d，J＝7.2Hz，1H)，7.638-7.449(m，3H)，7.403-7.35(m，3H)，7.32-7.235(m，5H)，2.512(s，1H).
13CNMR(100MHz，CDCl
3，ppm)：δ152.631，150.293，142.58，138.854，138.7，132.422，129.599，129.104，128.604，128.463，127.743，125.543，125.105，122.316，121.74，120.423，83.698.
Three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine
tris(4-(2-bromo-9-phenyl-9H-fluoren-9-yl)phenyl)amine
Ought measure 2-bromo-9-phenyl-fluorenes-9-alcohol (3.41mmol, 7.22 * 10 by 3:1
-4M) and triphenylamine (12mmol) be dissolved in the methylene dichloride, under the condition of room temperature, drip the number boron trifluoride. etherate (10.4mmol, 9.02 * 10
-4M) reaction is 120 minutes, adds ethanol (50mL) and water (150mL) cancellation reaction, dichloromethane extraction, and drying is revolved steaming, and sherwood oil silicagel column purifying obtains white powder solid (productive rate is 90.1%) with tetrahydrofuran (THF) and sherwood oil recrystallization.
MALDI-TOF-MS(m/z)：[M
+]calcd.For1199.0，Found：1199.1.
1H?NMR(400MHz，CDCl
3，ppm)：δ7.71-7.691(d，J＝7.6Hz，3H)，7.604-7.584(d，J＝8.0Hz，3H)，7.502(s，3H)，7.47-7.445(d，J＝8.0Hz，3H)，7.366-7.319(m，6H)，7.284-7.247(d，J＝8.0Hz，3H)，7.223-7.14(m，15H)，6.997-6.975(d，J＝8.4Hz，6H)，6.891-6.869(d，J＝8.4Hz，6H).
13C?NMR(100MHz，CDCl
3，ppm)：δ153.55，151.346，146.195，145.409，139.363，139.328，139.15，130.885，129.571，129.037，128.573，128.331，128.22，127.824，127.06，126.441，123.906，121.702，121.528，120.398，65.298.
2,2 '-(9,9-two-octane fluorenes-2,7-two bases)-two ([1,3,2] dioxo bora hexanaphthene)
2，2′-(9，9-dioctylfluoren-2，7-diyl)bis(1，3，2-dioxaborinane)
Magnesium chips (2.1quiv.) and the adding of a little crystallization iodine are had in 250 milliliter of four neck flask of reflux exchanger and dropping funnel, and described flask has carried out heat drying also with vacuumizing logical nitrogen.At first, drip 2 in the tetrahydrofuran (THF) (10ml) that be dissolved in of 1ml as quickly as possible, 7-two bromo-9,9-octane fluorenes (1equiv.) solution, and mixture is heated dripping the position.After the reaction beginning, slowly drip rest solution, its rate of addition is as the criterion with the reaction mixture automatic boiling.Add tetrahydrofuran (THF) (about 1100ml) then, and mixture was refluxed 2 hours.Clarification Grignard reagent (Grignard) solution with its generation is cooled to room temperature subsequently, and slowly be added drop-wise in tetrahydrofuran (THF) (10ml) solution of new distillatory three different third boric acid esters (3.0equiv.) excessive in the 250ml four neck flasks under-78 ℃ the nitrogen atmosphere that produces by dry ice and acetone, its rate of addition is as the criterion at-78 ℃ with internal temperature.The reinforced afterreaction device that finishes is slowly got back to room temperature.Ice sulfuric acid with 5% (100g frozen water/3ml97% sulfuric acid) is added into hydrolysis in the white suspension.Suction strainer goes out undissolved inorganic sediment and washs, and with sodium chloride aqueous solution to the mother liquor extracting twice, with sal epsom organic phase is carried out drying, vacuum rotary steam removes solvent, and in warm hexane and acetone soln the thick product of twice acquisition of agitator treating, white powder (productive rate is 78%).
1H?NMR，δ(400，CD
3OD)：7.74(m，4H)，7.59(s，2H)，2.00(m，4H)，0.94-1.24(m，20H)0.80(t，J＝7.2Hz，6H)，0.52(m，4H).Anal.Calcd?forC
29H
44O
4B
2：C，72.83；H，9.27.Found：C，73.21；H，9.87。
The two boric acid continuation and 1 that obtain, the ammediol back flow reaction generates 2,2 '-(9,9-two-octane fluorenes-2,7-two bases)-two ([1,3,2] dioxy borine)
1H NMR (400, CDCl
3) δ 7.78 (d, J=7.7Hz, 2H), 7.72 (s, 2H), 7.71 (d, J=7.4Hz, 2H), 4.21 (t, J=5.4Hz, 8H), 2.12-1.94 (m, 8H), 1.32-1.00 (m, 20H), 0.81 (t, J=6.7Hz, 6H), 0.58 (br., 4H).
1-bromine pyrene
1-bromopyrene
Get pyrene (12.5mmol) and be dissolved in DMF (17.42ml), and with NBS (2.046g, 11.5mmol) be dissolved in DMF (21.78ml), under frozen water, drip hybrid reaction, added the back stirring at normal temperature 24 hours, the frozen water dilution, extracted with diethyl ether, drying is revolved steaming, and sherwood oil silicagel column purifying obtains white solid (productive rate is 84.6%).
GC-MS(EI-m/z)：280(M
+)。
Pyrene boric acid
pyren-1-yl-1-boronic?acid
At first, get bromine pyrene (2.53mmol) and put into 250mL two neck flasks, described flask has carried out heat drying and has vacuumized logical nitrogen airtight back three times, uses through strict anhydrous and oxygen-free device processing before high pure nitrogen uses.Then, reaction unit is put into-78 ℃ the low temperature that is produced by dry ice and acetone bathe, and get the fresh distillatory tetrahydrofuran (THF) (20mL) of anhydrous and oxygen-free.Subsequently with n-Butyl Lithium (2.373mL, 3.800mmol, 1.6Msolution in hexane) slowly be added in the two neck flasks, and under-78 ℃ low temperature, reacted about 1 hour, at last, 2-sec.-propyl boric acid ester (5.064mmol) is injected into reactor rapidly, and room temperature is slowly got back in reaction, and reaction is spent the night.Reaction finishes the back with the dilute hydrochloric acid hydrolysis of triplication 3 hours, frozen water cancellation reaction, sodium-chlor washing extracted with diethyl ether, drying, the dried solvent of vacuum rotary steam, obtains thick product.Recrystallization is purified in normal hexane/methylene dichloride mixed solvent, obtains white solid (80%).
With pyrene end capped three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine and 9,9-diaryl fluorene multipolymer
Get three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine (0.1443g, 0.12mmol), 2,2 '-(9,9-two-octane fluorenes-2,7-two bases)-two ([1,3,2] dioxo bora hexanaphthene) (0.78mmol) with 2,7-dibromo 9,9-dioctyl alkane fluorenes (0.3290g, 0.6mmol) mixed dissolution in the mixed solvent of toluene (24mL) and tetrahydrofuran (THF), add catalyst P d (PPh
3)
4(0.010g, 0.008mmol), lucifuge is led to nitrogen, adds K again
2CO
3(2M, 12mL), reaction is 72 hours under 75 ℃ condition, adds pyrene boric acid and catalyzer after the reaction and respectively reacts 12 hours, and is last, adds 1-bromine pyrene and catalyzer and reacts 12 hours again; Added hydrazine hydrate (85%) violent stirring 24 hours, and used the toluene extraction, drying is revolved steaming, by being added drop-wise in the methyl alcohol reprecipitation repeatedly, obtains white solid (0.5430g, productive rate are 83.2%) with the acetone drawer at last.
1H-NMR(400MHz，CDCl
3)：δ(ppm)7.78-7.85(broad)，7.63-7.70(broad)，7.52(broad)，7.37(broad)，7.11(broad)，6.95(broad)，2.12(broad)，1.56(broad)，1.08-1.25(broad)，0.81-0.83(broad)；
13C-NMR(100MHz，CDCl
3)：δ(ppm)152.04，140.74，140.26，129.153128.49，126.99，126.40，121.73，120.21，55.57，53.64，40.62，32.02，30.26，29.45，24.149，22.83，14.29.
Get three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine (0.0962g, 0.08mmol), 2,2 '-(9,9-two-octane fluorenes-2,7-two bases)-two ([1,3,2] dioxo bora hexanaphthene) (0.92mmol) with 2,7-dibromo 9,9-dioctyl alkane fluorenes (0.4387g, 0.8mmol) mixed dissolution in the mixed solvent of toluene (30mL) and tetrahydrofuran (THF), add catalyst P d (PPh
3)
4(0.010g, 0.008mmol), lucifuge is led to nitrogen, adds K again
2CO
3(2M, 15mL), reaction is 72 hours under 75 ℃ condition, adds pyrene boric acid and catalyzer after the reaction and respectively reacts 12 hours, and is last, adds 1-bromine pyrene and catalyzer and reacts 12 hours again; Added hydrazine hydrate (85%) violent stirring 24 hours, and used the toluene extraction, drying is revolved steaming, by being added drop-wise in the methyl alcohol reprecipitation repeatedly, obtains white solid (0.5947g, productive rate are 79.5%) with the acetone drawer at last.
1H-NMR(400MHz，CDCl
3)：δ(ppm)7.78-7.85(broad)，7.63-7.70(broad)，7.55(broad)，7.38(broad)，7.12(broad)，6.96(broad)，2.12(broad)，1.56(broad)，1.08-1.25(broad)，0.81-0.83(broad)；
13C-NMR(100MHz，CDCl
3)：δ(ppm)152.04，140.72，140.25，129.01，128.46，127.44，126.39，121.83，121.72，120.20，55.57，40.63，32.03，30.27，29.46，24.15，22.84，14.31.
Embodiment 3, with the end capped copolymer material that contains three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine branching unit of 15% of pyrene:
Get three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine (0.0361g, 0.03mmol), 2,2 '-(9,9-two-octane fluorenes-2,7-two bases)-two ([1,3,2] dioxo bora hexanaphthene) (0.645mmol) with 2,7-dibromo 9,9-dioctyl alkane fluorenes (0.3291g, 0.6mmol) mixed dissolution in the mixed solvent of toluene (20mL) and tetrahydrofuran (THF), add catalyst P d (PPh
3)
4(0.010g, 0.008mmol), lucifuge is led to nitrogen, adds K again
2CO
3(2M, 10mL), reaction is 72 hours under 75 ℃ condition, adds pyrene boric acid and catalyzer after the reaction and respectively reacts 12 hours, and is last, adds 1-bromine pyrene and catalyzer and reacts 12 hours again; Added hydrazine hydrate (85%) violent stirring 24 hours, and used the toluene extraction, drying is revolved steaming, by being added drop-wise in the methyl alcohol reprecipitation repeatedly, obtains white solid (0.4282g, productive rate are 80.0%) with the acetone drawer at last.
1H-NMR(400MHz，CDCl
3)：δ(ppm)7.78-7.85(broad)，7.63-7.70(broad)，7.55(broad)，7.38(broad)，7.12(broad)，6.96(broad)，2.12(broad)，1.56(broad)，1.08-1.25(broad)，0.81-0.83(broad)；
13C-NMR(100MHz，CDCl
3)：δ(ppm)152.04，140.73，140.26，129.01，128.528，127.44，126.39，121.83，121.73，120.20，55.58，40.64，32.04，30.28，29.46，24.16，22.84，14.31.
Product is made into the trichloromethane dilute solution of 1 μ M accurately, and removes oxygen by argon cleaning.Adopt Tianjin, island UV-3150 ultraviolet-visual spectrometer and RF-530XPC fluorescence spectrophotometer to carry out absorption spectrum and emission spectrometry, photoluminescence spectra is to measure under the maximum absorption wavelength of uv-absorbing.Solid film is by the preparation of solution spin-coating film technology, and thickness is 300nm.
Thermogravimetric analysis (TGA)) carry out on the DTG-60H of Tianjin, island company (Shimadzu) thermogravimetric analyzer, the heating sweep velocity is that 10 ℃/min and nitrogen flow rate are 20cm
3/ min.Differential scanning calorimetry (DSC) carries out on the DSC-60A of Tianjin, island company (Shimadzu) tester, sample at first is heated to the state of low ten degree of decomposed sample temperature with the speed of 10 ℃/min, then, the beginning temperature is got back in cooling under the liquid nitrogen condition, and the same second time is with the speed heat temperature raising scanning of 10 ℃/min.
Embodiment 6, to the end capped electrochemical gaging that contains the copolymer material of three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine branching unit of 15% of pyrene:
Electrochemistry cyclic voltammetric (CV) experiment is finished on an Eco Chemie B.V.AUTOLAB potentiostat voltammetric analyzer, adopts three-electrode system, comprises platinum carbon working electrode, Ag/Ag
+For reference electrode, platinum filament are counter electrode.Oxidising process adopts methylene dichloride as solvent, and reduction process adopts tetrahydrofuran (THF) as solvent, hexafluoro phosphorus TBuA (Bu
4N
+PF
6 -) as supporting electrolyte, concentration is 0.1M.All electrochemistry experiments all are to carry out under the normal temperature condition nitrogen atmosphere, voltage sweep speed 0.1V/s.Use ferrocene (FOC) as benchmark, can calculate the HOMO and the lumo energy of material by the beginning voltage of measuring oxidation and reduction process.
Embodiment 15, to the preparation and the sign of the electroluminescent device of the end capped copolymer material that contains three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine branching unit of 5% of pyrene:
The luminescent device preparation that is blue light material with the end capped copolymer material that contains three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine branching unit of 5% of pyrene: ITO/PEDOT:PSS (50nm)/HBPF1 (70nm)/Ba (4nm)/A1 (120nm), wherein ITO is that square resistance is the transparency electrode of 10-20 Ω/; PEDOT:PSS is a hole mobile material, and HBPF1 is that the copolymer material that contains three (4-(2-bromo-9-phenyl fluorenes-9-yl) phenyl) amine branching unit of 5% adopts the solution spin coating technique, and film thickness is 70nm; At last, evaporation A1 negative electrode again.
At first, indium tin metal oxide compound (ITO) glass substrate in pure water, acetone and 2-isopropanol bath towards sound 15 minutes.The toluene solution of copolymer material (10mg/mL) is spun on the ITO substrate, subsequently 10
-5Remove solvent under the normal temperature in the vacuum chamber of Torr.The polymeric film gauge control is about 80nm.At last, the A1 electrode that 400-nm is thick is 10
-7Adding mask plate by hot evaporation under the Torr pressure realizes.Measurement is being carried out on the device of big or small 0.15cm * 0.15cm, 0.2cm * 0.2cm and 0.4cm * 0.4cm. and current density-voltage curve (J-V) is carrying out on the device of 0.2cm * 0.2cm size. and electric switch and switching time carry out with Agilent 16440A SMU/ oscilloscope on the 4156A of Hewlett-Packard analyzing parameters of semiconductor instrument respectively.
Claims (4)
1. break-in conjugated branched polymer material, it is characterized in that this material be based on triphenylamine complexity 9, the 9-diaryl fluorene is the polymer materials of branched monomer, has following structure:
In the formula: R
1For hydrogen or have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom; W is a carbon; E is a capping group, x, the y numeral between 1～100,
E is specially a kind of in the following array structure:
Ar is the conjugation group, and is identical or different when occurring, and is specially down a kind of in the array structure:
Wherein, the symbol in the formula has following implication:
-
*For between the structural unit, the band of position that is connected with branched monomer of Ar;
R
2Be selected from hydrogen or normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or positive decyl or the n-octyloxy chain any one.
2. the hyperbranched conjugated polymer material that interrupts according to claim 1 is characterized in that the R among the described compound-material I
1Be selected from hydrogen or normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or the positive decyl any one respectively.
3. the application of a break-in conjugated branched polymer material as claimed in claim 1, it is characterized in that being applied to LED device, wherein the structure of LED device is transparent anode/hole injection layer/luminescent layer/electron injecting layer/negative electrode, wherein, adopt break-in conjugated branched polymer material as luminescent layer.
4. the application of a break-in conjugated branched polymer material as claimed in claim 1, it is characterized in that being applied to information recording device, wherein the structure of device is transparent anode/electric bi-stable layer/negative electrode, wherein break-in conjugated branched polymer material as the electric bi-stable layer by solution spin coating or spray ink Printing mode prepare, negative electrode prepares by vacuum coating technology.
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