CN111662436A - Dark blue luminous polymer and preparation method thereof - Google Patents
Dark blue luminous polymer and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 7
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052710 silicon Inorganic materials 0.000 claims abstract 2
- 239000010703 silicon Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920002098 polyfluorene Polymers 0.000 description 7
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001194 electroluminescence spectrum Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
The invention belongs to the field of organic light-emitting display, and particularly relates to a deep blue light-emitting polymer and a preparation method thereof. The invention discloses a deep blue luminescent polymer which has a structure shown in a formula (I). The invention also provides a preparation method of the deep blue luminescent polymer, which comprises the following steps: step 1: under the protection of nitrogen, carrying out Suzuki coupling reaction on 2, 7-dibromo-9, 9-dioctyl fluorene, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctyl fluorene and 2, 7-dibromo-2 ', 3', 6', 7' -tetraoctyl-spiro silicon bifluorene to obtain a polymer shown in a formula (II); step 2: and (3) carrying out Suzuki coupling reaction on the polymer shown in the formula (II) and N- (4-biphenyl) -N- (4-bromophenyl) - (9, 9-dimethylfluorenyl) amine to obtain the polymer shown in the formula (I). The invention solves the technical problem that the existing luminescent polymer has low blue light saturation.
Description
Technical Field
The invention belongs to the field of organic light-emitting display, and particularly relates to a deep blue light-emitting polymer and a preparation method thereof.
Background
Since the first preparation of organic electroluminescent blue-light emitting diode (OLED) with a polyvinyl phenylene structure by 1990 Friend R.H. et al, the research on the hot tide of organic flat panel display materials and devices is initiated in the fields of material science and information technology. The blue light material has the lowest maturity, the fluorene polymer is taken as the main material to emit pure positive blue light at present, however, the poor spectral stability of the polyfluorene material is the most fatal weakness of the polyfluorene material, the emission wavelength of the polyfluorene blue light material can be red shifted and a green light emission band appears, so that the originally saturated deep blue light becomes green light or even yellow light, the chromatographic purity of the polyfluorene blue light material is seriously weakened, the application of the polyfluorene blue light material as the blue light polymer material is influenced, and the fluorescence quantum efficiency and the electroluminescent efficiency of the polyfluorene blue light material are also greatly reduced. Therefore, the low blue light saturation of the existing light-emitting polymers is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The invention aims to provide a deep blue luminescent polymer.
The invention also aims to provide a preparation method of the deep blue luminescent polymer.
The purpose of the invention is realized by the following scheme:
the invention provides a deep blue luminescent polymer, which has a structural formula shown as a formula (I):
wherein n is 300-.
The invention also provides a preparation method of the deep blue luminescent polymer, which comprises the following steps:
step 1: under the protection of nitrogen, carrying out Suz uki coupling reaction on 2, 7-dibromo-9, 9-dioctyl fluorene, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctyl fluorene and 2, 7-dibromo-2 ', 3', 6', 7' -tetraoctyl-spirosilabifluorene to obtain a polymer shown as a formula (II);
wherein n is 300-;
step 2: and (3) carrying out Suzuki coupling reaction on the polymer shown in the formula (II) and N- (4-biphenyl) -N- (4-bromophenyl) - (9, 9-dimethylfluorenyl) amine to obtain the polymer shown in the formula (I).
Preferably, the molar ratio of the 2, 7-dibromo-9, 9-dioctylfluorene, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene and 2, 7-dibromo-2 ', 3', 6', 7' -tetraoctyl-spirosilabifluorene in step 1 is 4:5: 1.
Preferably, in step 2, the molar ratio of the polymer shown in the formula (II) to the N- (4-biphenyl) -N- (4-bromophenyl) - (9, 9-dimethylfluorenyl) amine is 1: 2.
Preferably, the time of the Suzuki coupling reaction in the step 1 is 12 h.
Preferably, the temperature of the Suzuki coupling reaction in step 1 is 100 ℃.
Preferably, the time of the Suzuki coupling reaction in the step 2 is 12-36 h.
Preferably, the time of the Suzuki coupling reaction in the step 2 is 36 h.
Preferably, the temperature of the Suzuki coupling reaction in step 2 is 120 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
after the benzidine unit is introduced into the deep blue luminescent polymer prepared by the invention, the electroluminescence spectrum has obvious blue shift and narrowing, which shows that the color purity of the polymer prepared by the embodiment of the invention is obviously improved. And the device prepared from the dark blue luminescent polymer has the color coordinate blue shifted to the dark blue region of CIE (y is less than 0.1), which shows that the polymer prepared by the invention can emit dark blue light.
Drawings
FIG. 1 is an electroluminescence spectrum of deep blue light-emitting polymers obtained in examples 1 to 3 of the present invention and comparative example 1;
wherein the reference numerals
PFOSiT-36 for A, PFOSSiT-24 for B, PFOSSiT-12 for C, D: a polymer represented by the formula (II).
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Step 1: under nitrogen protection, 2, 7-dibromo-9, 9-dioctylfluorene (131.6mg, 0.24mmol), 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene (192.8mg, 0.3mmol), 2, 7-dibromo-2 ', 3', 6', 7' -tetraoctyl-spirosilabifluorene (57.24mg, 0.06mmol), palladium acetate (2mg), tricyclohexylphosphine (3mg), tetraethylhydroxylamine (1ml) and toluene (10ml) were added to a 50ml two-necked flask, and heated and stirred at 100 ℃ for 12 hours under dark conditions, and then 2ml of an aqueous solution of tetrabutylhydroxylamine was added and reacted for 12 hours to obtain a polymer represented by the formula (II) (435.6mg, 78%) having the chemical reaction equation:
step 2: to a 250ml three-necked flask, N- (4-biphenyl) -N- (4-bromophenyl) - (9, 9-dimethylfluorenyl) amine (185.8mg, 0.36mmol) and 100ml of toluene were added and then 2ml of an aqueous tetrabutylhydroxylamine solution was added to a polymer represented by the formula (II) (125.6mg, 0.18mmol), reacted at 120 ℃ for 36 hours, allowed to stand and cooled, and capped with phenylboronic acid (25mg, 0.2mmol) to obtain a reaction solution.
And step 3: and dropwise adding the reaction solution into 200ml of methanol for precipitation, filtering, drying, and extracting filter residues in a Soxhlet extractor with methanol, acetone and n-hexane sequentially for 12 hours. The solid is dissolved in toluene again, silica gel column chromatography of 200-300 mesh and 300-400 mesh is adopted by taking the toluene as eluent, and the toluene solution of the polymer is precipitated in 200ml of methanol again after concentration. Filtration and drying in vacuo gave polymer PFOSIT-36(356.03mg, 82% yield) according to the chemical reaction equation:
example 2
This example differs from example 1 in that the reaction time in step 2 is 24 hours, and the final polymer PFOSIT-24(287.23mg, 80% yield) is obtained.
Example 3
The difference between this example and example 1 is: the reaction time in step 2 was 12 hours, and the polymer PFOSIT-12(156.57mg, yield 84%) was finally obtained.
Comparative example 1
Under the protection of nitrogen, 2, 7-dibromo-9, 9-dioctylfluorene (131.6mg, 0.24mmol), 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene (192.8mg, 0.3mmol), 2, 7-dibromo-2 ', 3', 6', 7' -tetraoctyl-spirosilabifluorene (57.24mg, 0.06mmol), palladium acetate (2mg), tricyclohexylphosphine (3mg), tetraethylhydroxylamine (1ml) and toluene (10ml) were added to a 50ml two-necked flask, and heated and stirred at 100 ℃ for 12 hours under a dark condition, and then 2ml of an aqueous solution of tetrabutylhydroxylamine was added to react for 12 hours to obtain a polymer (435.6mg, 78%) represented by the formula (II),
in summary, fig. 1 shows the electroluminescence spectra of the deep blue light emitting polymers prepared in examples 1-3 of the present invention and comparative example 1, and it can be seen from fig. 1 that the polymer shown in formula (II) in comparative example 1 has 460nm main peak and 434nm and 488nm shoulder peak, and the electroluminescence spectra of the pfosi prepared in examples 1-3 after introducing benzidine unit into the polymer main chain show obvious blue shift and narrowing, indicating that the color purity of the polymer prepared in the examples of the present invention is significantly improved.
Electroluminescent devices were prepared using the polymers shown in PFOSIT-36, PFOSIT-24, PFOSIT-12 in examples 1 to 3 of the present invention and formula (II) in comparative example 1, respectively, as the light-emitting layer, and their electroluminescent properties were measured (device structure: ITO/PEDOT: PSS (30nm)/Polymer (80nm)/CsF (1.0nm)/Al (100 nm)).
Table 1 Performance of Polymer light emitting device represented by PFOSIT-36, PFOSIT-24, PFOSIT-12 and formula (II)
As can be seen from table 1, after the benzidine unit is introduced, the current efficiency performance of the light emitting device is significantly improved and the spectrum is more blue. The blue shift of the spectrum can be attributed to that benzidine disturbs effective conjugation of the polyfluorene main chain, the color coordinates of the device based on the polymer shown in the formula (II) are (0.18, 0.13), and after the benzidine is introduced, the color coordinates of PFOSIT series devices are blue-shifted to a deep blue light region of CIE (y <0.1), which shows that the polymer prepared by the invention can emit deep blue light.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A deep blue light emitting polymer, characterized in that, its structural formula is shown in formula (I):
wherein n is 300-.
2. A preparation method of a deep blue luminescent polymer is characterized by comprising the following steps:
step 1: under the protection of nitrogen, carrying out Suzuki coupling reaction on 2, 7-dibromo-9, 9-dioctyl fluorene, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctyl fluorene and 2, 7-dibromo-2 ', 3', 6', 7' -tetraoctyl-spiro silicon bifluorene to obtain a polymer shown in a formula (II);
wherein n is 300-;
step 2: and (3) carrying out Suzuki coupling reaction on the polymer shown in the formula (II) and N- (4-biphenyl) -N- (4-bromophenyl) - (9, 9-dimethylfluorenyl) amine to obtain the polymer shown in the formula (I).
3. The method for preparing a deep blue light-emitting polymer according to claim 2, wherein the molar ratio of the 2, 7-dibromo-9, 9-dioctylfluorene, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene and 2, 7-dibromo-2 ', 3', 6', 7' -tetraoctyl-spirosilabifluorene in step 1 is 4:5: 1.
4. The method according to claim 2, wherein the molar ratio of the polymer represented by formula (II) to the N- (4-biphenyl) -N- (4-bromophenyl) - (9, 9-dimethylfluorenyl) amine in step 2 is 1: 2.
5. The method for preparing a deep blue light-emitting polymer according to claim 2, wherein the time of the Suzuki coupling reaction in step 1 is 12 hours.
6. The method for preparing a deep blue light-emitting polymer according to claim 2, wherein the temperature of the Suzuki coupling reaction in step 1 is 100 ℃.
7. The method for preparing a deep blue light-emitting polymer according to claim 2, wherein the time of the Suzuki coupling reaction in step 2 is 12-36 h.
8. The method for preparing a deep blue light-emitting polymer according to claim 7, wherein the time of the Suzuki coupling reaction in step 2 is 36 h.
9. The method for preparing a deep blue light-emitting polymer according to claim 2, wherein the temperature of the Suzuki coupling reaction in step 2 is 120 ℃.
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| CN101255336A (en) * | 2007-11-06 | 2008-09-03 | 华南理工大学 | Blue fluorene polymer with stable electroluminescent spectrum and its preparation method and application |
| WO2012034264A1 (en) * | 2010-09-13 | 2012-03-22 | 海洋王照明科技股份有限公司 | Fluorene containing organic semiconductor material, preparation method and use thereof |
| CN109776768A (en) * | 2018-12-31 | 2019-05-21 | 华南理工大学 | A kind of blue light conjugated polymer and the preparation method and application thereof based on triphenylamine and sulphur dibenzofuran unit |
-
2020
- 2020-06-15 CN CN202010544346.3A patent/CN111662436A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255336A (en) * | 2007-11-06 | 2008-09-03 | 华南理工大学 | Blue fluorene polymer with stable electroluminescent spectrum and its preparation method and application |
| WO2012034264A1 (en) * | 2010-09-13 | 2012-03-22 | 海洋王照明科技股份有限公司 | Fluorene containing organic semiconductor material, preparation method and use thereof |
| CN109776768A (en) * | 2018-12-31 | 2019-05-21 | 华南理工大学 | A kind of blue light conjugated polymer and the preparation method and application thereof based on triphenylamine and sulphur dibenzofuran unit |
Non-Patent Citations (2)
| Title |
|---|
| WANG-LIN YU ET AL.: ""Spiro-Functionalized Polyfluorene Derivativesas Blue Light-Emitting Materials"", 《ADV. MATER.》 * |
| XIUSHANG XU，ET AL.: ""Deep-blue emitting poly(2′,3′,6′,7′-tetraoctyl-2,7-spirosilabifluorene) simultaneously with good color purity and high external quantum efficiency"", 《ORGANIC ELECTRONICS》 * |
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