CN110408007B - Preparation method of POSS hybrid conjugated polymer - Google Patents
Preparation method of POSS hybrid conjugated polymer Download PDFInfo
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- CN110408007B CN110408007B CN201910662067.4A CN201910662067A CN110408007B CN 110408007 B CN110408007 B CN 110408007B CN 201910662067 A CN201910662067 A CN 201910662067A CN 110408007 B CN110408007 B CN 110408007B
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- dioctyl
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 25
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 25
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-Br2Car Natural products C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 claims abstract description 21
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 claims abstract description 19
- CYKLQIOPIMZZBZ-UHFFFAOYSA-N 2,7-dibromo-9,9-dioctylfluorene Chemical compound C1=C(Br)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(Br)=CC=C3C2=C1 CYKLQIOPIMZZBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- WJOGFABTCIRSRB-UHFFFAOYSA-N OBO.C1=CC=C2CC3=CC=CC=C3C2=C1 Chemical compound OBO.C1=CC=C2CC3=CC=CC=C3C2=C1 WJOGFABTCIRSRB-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000000944 Soxhlet extraction Methods 0.000 claims description 5
- MWBJSOHMMAMFDQ-UHFFFAOYSA-N boric acid;9h-fluorene Chemical compound OB(O)O.C1=CC=C2CC3=CC=CC=C3C2=C1 MWBJSOHMMAMFDQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 2
- 239000012065 filter cake Substances 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- NLJDBTZLVTWXRG-UHFFFAOYSA-N tert-butylazanium;iodide Chemical compound [I-].CC(C)(C)[NH3+] NLJDBTZLVTWXRG-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 8
- 229920002098 polyfluorene Polymers 0.000 abstract description 8
- YRWMGOSKROWAIT-UHFFFAOYSA-N 2-(4-bromophenyl)-1h-benzimidazole Chemical compound C1=CC(Br)=CC=C1C1=NC2=CC=CC=C2N1 YRWMGOSKROWAIT-UHFFFAOYSA-N 0.000 abstract description 4
- XBHOUXSGHYZCNH-UHFFFAOYSA-N 2-phenyl-1,3-benzothiazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2S1 XBHOUXSGHYZCNH-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 229910052763 palladium Inorganic materials 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 238000005401 electroluminescence Methods 0.000 abstract description 3
- 238000005424 photoluminescence Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 18
- 239000007787 solid Substances 0.000 description 13
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- -1 bromopropyl phenyl Chemical group 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006862 quantum yield reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002503 iridium Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UUNGBOQAZQUJMZ-UHFFFAOYSA-N 3-bromopropyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CCCBr UUNGBOQAZQUJMZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/18—Definition of the polymer structure conjugated
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- 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
The invention relates to a preparation method of a POSS hybrid conjugated polymer. The preparation method comprises the steps of preparing an iridium complex from 2- (4-bromophenyl) -benzimidazole and 2-phenylbenzothiazole, preparing 3, 6-dibromocarbazole phenyl POSS from trisilanol phenyl POSS, and carrying out Suzuki polycondensation on the iridium complex, the 3, 6-dibromocarbazole phenyl POSS, 2, 7-dibromo-9, 9-dioctyl fluorene and 9, 9-dioctyl-2, 7-dipicolinic acid boronate fluorene under the action of a palladium tetratriphenylphosphine catalyst to obtain the POSS hybrid conjugated polymer. The polyfluorene host unit, the iridium complex object unit and the nano POSS are bonded and combined to obtain the high-efficiency and stable luminescent conjugated polymer hybrid material which can be used in the fields of photoluminescence, electroluminescence, information storage, sensors and the like.
Description
Technical Field
The invention relates to the technical field of luminescence, in particular to a POSS hybrid conjugated polymer and a preparation method thereof.
Background
Phosphorescent metal complexes have relatively long phosphorescence lifetime and are easy to cause concentration quenching and triplet-triplet annihilation, so that the phosphorescent metal complexes are usually bonded to a polymer host material as a guest to achieve the purposes of inhibiting exciton quenching and improving device efficiency. The polyfluorene material has a wide energy band structure, high fluorescence quantum yield and carrier mobility and deep blue spectral characteristics, is an ideal blue light main body material of a conjugated polymer, and can introduce a phosphorescent metal complex into a side chain or a main chain of the conjugated polymer to obtain the conjugated main chain polymer phosphorescent material.
The conjugated polymer luminescent materials such as polyfluorene and the like have poor luminescent stability and environmental stability, and meanwhile, the molecules are parallel to each other due to pi-pi interaction between the molecules and a rigid plane structure, so that the face-to-face tightly stacked aggregate is easy to form, the solubility is poor, the processing and film-forming properties are influenced, and meanwhile, the blue shift of an electron absorption spectrum is caused by the aggregation, the peak shape is widened, the aggregation even causes fluorescence quenching, so that the development of the luminescent materials in the field of electronic devices is influenced to a certain extent. The defects can be better overcome by introducing polyhedral oligomeric silsesquioxane (POSS) with a nano-size cage shape into conjugated polymers such as polyfluorene and the like, so that the performance of the polymer is improved. POSS can generally be incorporated into polymers as the core of dendrimeric/hyperbranched polymers (chem. mater.,2006,18:3780), as well as the side groups (Macromolecules,2005,38:7453,24) or the ends (adv. funct. mater.,2003,13:25) or blocks (polym.,2014,55:6696) of the polymer chains.
The invention discovers that POSS is vertically grafted to a conjugated main chain containing an iridium complex/polyfluorene to obtain a POSS hybrid conjugated polymer material taking the iridium complex as an object and the polyfluorene as a main body, and the POSS hybrid conjugated polymer material has excellent luminous performance and stability, has good solubility and film forming property, and can be used in the fields of electroluminescence, photoluminescence, electrical storage information, chemistry, biosensors and the like.
Disclosure of Invention
The invention aims to provide a POSS hybrid conjugated polymer material which can be used in the fields of electroluminescence, photoluminescence, electric storage information, chemistry, biosensors and the like.
The invention also aims to provide a preparation method of the POSS hybrid conjugated polymer. The preparation method comprises the steps of preparing an iridium complex from 2- (4-bromophenyl) -benzimidazole and 2-phenylbenzothiazole, preparing 3, 6-dibromocarbazole phenyl POSS from trisilanol phenyl POSS, and carrying out Suzuki polycondensation on the iridium complex, the 3, 6-dibromocarbazole phenyl POSS, the 2, 7-dibromo-9, 9-dioctyl fluorene and the 9, 9-dioctyl-2, 7-dipicolinyl boronate fluorene under the action of a tetratriphenylphosphine palladium catalyst to obtain the POSS hybrid conjugated polymer.
The technical scheme adopted for realizing the purpose of the invention is as follows:
(1) preparation of iridium complexes
The preparation method comprises the steps of heating and refluxing iridium trichloride and 2- (4-bromophenyl) -benzimidazole in a mixed solvent of ethylene glycol monoethyl ether and water to prepare a chlorine-bridged iridium dimer, and then heating and refluxing the chlorine-bridged iridium dimer and 2-phenyl benzothiazole in a solvent of ethylene glycol monoethyl ether under the action of anhydrous sodium carbonate to react to prepare the iridium complex.
The structural formula of the iridium complex is as follows:
the structural formula of the 3, 6-dibromo carbazole phenyl POSS is as follows:
(2) preparation of 3, 6-dibromo carbazole phenyl POSS
Under the action of triethylamine, trisilanol phenyl POSS reacts with bromopropyl trichlorosilane to obtain bromopropyl phenyl POSS, and then reacts with 3, 6-dibromocarbazole under the alkaline condition to prepare the 3, 6-dibromocarbazole phenyl POSS.
(3) Preparation of POSS hybrid conjugated polymer
Under the protection of nitrogen, dissolving an iridium complex, 3, 6-dibromocarbazole phenyl POSS, 2, 7-dibromo-9, 9-dioctyl fluorene and 9, 9-dioctyl-2, 7-dipicolinic acid ester fluorene according to molar ratio in a toluene solvent and a 2M potassium carbonate aqueous solution, adding a proper amount of tetratriphenylphosphine palladium catalyst and tetra-n-butyl ammonium iodide phase transfer agent, magnetic stirring reflux polymerization reaction is carried out for 48 hours at 110 ℃ under nitrogen, then phenyl boric acid and bromobenzene are sequentially used as end capping agents for end capping reaction for 8 hours respectively, and cooling to room temperature, precipitating with methanol, filtering to collect a solid, sequentially carrying out soxhlet extraction with methanol and acetone to remove small molecules and oligomers, collecting a polymer solution subjected to soxhlet extraction with chloroform, concentrating to a proper concentration, precipitating with methanol, collecting a finally obtained flocculent solid, and carrying out vacuum drying for 12 hours to obtain the POSS hybrid conjugated polymer.
The ratio of the total mole number of the iridium complex, 3, 6-dibromo carbazole phenyl POSS and 2, 7-dibromo-9, 9-dioctyl fluorene to the mole number of 9, 9-dioctyl-2, 7-dipicolinic acid ester fluorene is 1: 1.
The molar ratio of the iridium complex to 9, 9-dioctyl-2, 7-dipinacolol borate fluorene is 0.1-10: 100.
The molar ratio of the 3, 6-dibromocarbazole phenyl POSS to the 9, 9-dioctyl-2, 7-dipinacolol borate fluorene is 0.1-6: 100.
The toluene solvent and the aqueous potassium carbonate solution need to be sufficiently deoxygenated beforehand.
The invention has the following advantages:
1. according to the invention, polyfluorene is taken as a host and an iridium complex is taken as an object, POSS is introduced into the host and the object, and the isolation and dilution effects of a cage-shaped polyhedral structure of POSS are utilized to inhibit the aggregation of luminescent groups, so that the fluorescence of the polyfluorene of the host is effectively transferred to the phosphorescence of the iridium complex of the object, and the luminescent property of the material is improved.
2. The nanometer POSS group is hung and connected to the rigid main chain, so that the reduction of the solubility of the polymer caused by the stacking of the rigid main chain can be effectively avoided, the obtained polymer material has excellent solubility and film-forming property, and the performance of an OLED device can be effectively improved.
3. The POSS nano-material and the organic/inorganic hybrid characteristics can be fully exerted, so that the thermal stability and the luminescent color stability of the luminescent material are improved.
Drawings
FIG. 1 is the fluorescence emission spectra of the iridium complex (curve a) and POSS hybrid conjugated polymer (curve b) solid powders of example 1 under 365nm wavelength excitation.
FIG. 2 is an infrared spectrum of a POSS hybrid conjugated polymer of example 1.
FIG. 3 is the fluorescence emission spectra of the POSS hybrid conjugated polymer of example 2 with a solid powder of POSS free polymer (curve a) at 365nm wavelength excitation.
Figure 4 is an atomic force microscope image of a POSS hybrid conjugated polymer thin film of example 2.
FIG. 5 is an atomic force microscope image of a control film without POSS polymer.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention in any way.
In FIG. 3, curve a shows the fluorescence emission spectrum of the POSS-free polymer of example 2; curve b represents the fluorescence emission spectrum of the POSS hybrid conjugated polymer of example 2.
Example 1
1. Preparation of iridium complexes
Under argon protection, 0.35g of IrCl was added to a round bottom flask3·3H2O, 0.63g of 2- (4-bromophenyl) -benzimidazole, 30mL of ethylene glycol monoethyl ether and 10mL of distilled water, refluxing at 120 ℃ for 24 hours, cooling to room temperature, extracting with saturated brine and ethyl acetate, removing the organic phase, and drying in vacuum to obtain the 2- (4-bromophenyl) -benzimidazole chlorine bridged dimer.
Under the protection of argon, 0.3g of 2- (4-bromophenyl) -benzimidazole chlorine bridged dimer, 0.1g of 2-phenylbenzothiazole and 30mg of anhydrous sodium carbonate are added into a round-bottom flask, the round-bottom flask is vacuumized, nitrogen is introduced, 50mL of ethylene glycol monoethyl ether is injected by a syringe, reflux reaction is carried out for 12 hours at 120 ℃ under argon, the round-bottom flask is cooled to room temperature, reaction liquid is extracted by saturated saline and ethyl acetate, a yellow solid is obtained by spin-drying a solvent, column chromatography purification is carried out by taking dichloromethane as an eluent, and the iridium complex is obtained by spin-drying the solvent. The yield was 50%.
1H NMR(400MHz,HDMSO)δ8.21–8.07(m,2H),7.67(d,J=8.0Hz,3H),7.58(d,J=8.3Hz, 3H),7.15(t,J=7.5Hz,3H),7.07(d,J=8.1Hz,3H),6.72(s,2H),6.67(s,3H),5.98–5.88(m,3H), 3.43(d,J=6.9Hz,2H)。
The fluorescence emission spectrum of the prepared iridium complex solid powder under 365nm wavelength excitation is shown as a curve a in figure 1, the emission peaks are positioned at 546nm and 585nm, and yellow light is emitted.
2. Preparation of 3, 6-dibromo carbazole phenyl POSS
0.38g of bromopropyltrichlorosilane was weighed into a round-bottomed flask, evacuated and purged with nitrogen. 30mL of tetrahydrofuran and 20mL of triethylamine are added, 0.93g of trisilanol phenyl POSS is diluted by 10mL of tetrahydrofuran and then slowly added into a flask dropwise, the mixture is stirred at room temperature for reaction, white turbidity is generated, and after the reaction is carried out for 4 hours, the mixture is extracted by saturated saline to obtain white solid bromopropylphenyl POSS, wherein the yield is 86%.
Adding 0.325g of 3, 6-dibromocarbazole and 5mL of dimethyl sulfoxide into a round-bottom flask, dropwise adding 5mL of 10% NaOH solution after dissolving, stirring for 20min at normal temperature, slowly dropwise adding 10mL of dimethyl sulfoxide solution dissolved with 0.863g of bromopropylphenyl POSS, and heating to 40 ℃ for reaction for 5 hours. After the reaction is finished, adjusting the pH value to be neutral by using dilute hydrochloric acid, filtering, and recrystallizing by using ethanol to obtain white flocculent solid. The yield was 78%.
1H NMR(400MHz,CDCl3)δ8.03(s,7H),7.81–7.71(m,14H),7.52–7.32(m,14H), 3.60–3.48(m,2H),2.97(s,2H),2.90(d,J=0.5Hz,2H),2.06–1.91(m,2H),1.64(s,2H),1.06–0.94 (m,2H)。
3. Preparation of POSS hybrid conjugated polymer
Under the protection of nitrogen, 0.01mmol of iridium complex, 0.01mmol of 3, 6-dibromocarbazole phenyl POSS, 0.98mmol of 2, 7-dibromo-9, 9-dioctyl fluorene and 1mmol of 9, 9-dioctyl-2, 7-dipicolinic acid borate fluorene are dissolved in 10mL of toluene and 4mL of 2M potassium carbonate aqueous solution which are fully deoxidized in advance, 20mg of tetratriphenylphosphine palladium catalyst and 30mg of tetra-n-butyl ammonium iodide phase transfer agent are added, after the magnetic stirring reflux polymerization reaction is carried out for 48 hours under nitrogen at 110 ℃, 0.2g of phenylboronic acid and 0.2mL of bromobenzene are sequentially used as end capping reagents for carrying out end capping reaction for 8 hours respectively, the mixture is cooled to room temperature, methanol is used for precipitation, the solid is collected by filtration, small molecules and oligomers are removed by sequential methanol and acetone, the polymer solution of chloroform extraction is collected, methanol is used for precipitation after being concentrated to proper concentration, the finally obtained flocculent solid is collected, vacuum drying for 12 hours to obtain POSS hybrid conjugated polymer solid powder with the yield of 60 percent and the number average molecular weight of 1.2 multiplied by 104The molecular weight distribution PDI was 1.7.
The infrared spectrum of the POSS hybrid conjugated polymer solid powder prepared in the example is shown in the attached figure 2.
The fluorescence emission spectrum of the POSS hybrid conjugated polymer solid powder under 365nm wavelength excitation is shown as curve b in figure 1, and blue light and yellow light bipolar emission are shown.
The polymeric material has the following structural formula:
example 2
Preparation of iridium complex and preparation of 3, 6-dibromocarbazole phenyl POSS are the same as in example 1.
The experimental procedure for the preparation of POSS hybrid conjugated polymers was as in example 1, wherein the iridium complexes, 3, 6-dibromocarbazolylphenyl POSS, 2, 7-dibromo-9, 9-dioctylfluorene and 9, 9-dioctyl2, 7-dipinacoloborate fluorene molar charge are shown in table 1.
TABLE 1
FIG. 3 shows the fluorescence emission spectra of the POSS hybrid conjugated polymer prepared in this example (curve b) and the control sample without POSS polymer (curve a) under 365nm wavelength excitation, and it can be seen that the polymer containing POSS has stronger fluorescence in the yellow part, indicating that the introduction of POSS makes the host blue fluorescence more shifted to the guest yellow. By measuring the fluorescence quantum yield of the polymer powder, the fluorescence quantum yield of the polymer of the example is 13.86%, while the fluorescence quantum yield of the polymer without POSS is 10.43%, which shows that the introduction of POSS can improve the luminescence property of the polymer.
The thermal stability analysis of the POSS hybrid conjugated polymer material prepared in the embodiment shows that the temperature corresponding to the polymer is 302 ℃ when the weight loss is 5%, which shows that the prepared POSS hybrid conjugated polymer material has excellent thermal stability.
FIGS. 4 and 5 show that the POSS-containing conjugated polymer film (FIG. 4) has a smoother surface and reduced surface roughness with an RMS deviation of 3.03nm, while the POSS-free polymer film (FIG. 5) has an RMS deviation of 5.30nm, indicating that the introduction of POSS is effective in improving the solubility and film-forming properties of the polymer.
Claims (3)
1. A preparation method of POSS hybrid conjugated polymer is characterized in that under the protection of nitrogen, iridium complex, 3, 6-dibromocarbazole phenyl POSS, 2, 7-dibromo-9, 9-dioctyl fluorene and 9, 9-dioctyl-2, 7-dipivalol borate fluorene are dissolved in a toluene solvent and a 2M potassium carbonate aqueous solution according to molar ratio, a proper amount of tetrakis (triphenylphosphine) palladium and tert-butyl ammonium iodide are added, stirring reflux reaction is carried out at 110 ℃ under nitrogen atmosphere for 48 hours, then end-capping reaction is carried out by phenylboronic acid and bromobenzene for 8 hours respectively, cooling to room temperature, precipitating with methanol, filtering, sequentially carrying out soxhlet extraction on a filter cake with methanol and acetone to remove small molecules and oligomers, then carrying out soxhlet extraction with chloroform, concentrating the soxhlet extraction solution to a proper concentration, precipitating with methanol, filtering, and carrying out vacuum drying to obtain the POSS hybrid conjugated polymer;
the structural formula of the iridium complex is as follows:
the structural formula of the 3, 6-dibromo carbazole phenyl POSS is as follows:
the ratio of the total mole number of the iridium complex, 3, 6-dibromo carbazole phenyl POSS and 2, 7-dibromo-9, 9-dioctyl fluorene to the mole number of 9, 9-dioctyl-2, 7-dipicolinic acid ester fluorene is 1: 1;
the molar ratio of the 3, 6-dibromocarbazole phenyl POSS to the 9, 9-dioctyl-2, 7-dipinacolol borate fluorene is 0.1-6: 100.
2. The preparation method of the POSS hybrid conjugated polymer as claimed in claim 1, wherein the molar ratio of the iridium complex to 9, 9-dioctyl-2, 7-dipinacolone boronate fluorene is 0.1-10: 100.
3. The method of claim 1, wherein the toluene solvent and the aqueous potassium carbonate solution are pre-deoxygenated.
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