CN103012163B - Double-fluoranthene organic semiconductor material as well as preparation method and application thereof - Google Patents
Double-fluoranthene organic semiconductor material as well as preparation method and application thereof Download PDFInfo
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- 0 **c(cc1)ccc1N(c(cc1)ccc1Br)c(cc1)ccc1Br Chemical compound **c(cc1)ccc1N(c(cc1)ccc1Br)c(cc1)ccc1Br 0.000 description 4
- QQGHPFDLUNMBGJ-UHFFFAOYSA-N O=C1C(c2ccccc2)=C(c2cccc3c2c2ccc3)C2=C1c1ccccc1 Chemical compound O=C1C(c2ccccc2)=C(c2cccc3c2c2ccc3)C2=C1c1ccccc1 QQGHPFDLUNMBGJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
A double-fluoranthene organic semiconductor material has a structural formula described in the specification, wherein R is C1-C20 linear chain alkyl, C1-C20 branch chain alkyl or C1-C20 alkoxyl. The double-fluoranthene organic semiconductor material emits pure blue lights, the double-fluoranthene organic semiconductor material can be easily dissolved in common organic solvents such as tetrahydrofuran, dichloromethane, methylbenzene and chloroform as an electron donating alkyl or alkoxyl flexible group is introduced into the structure, and solubility and film-forming property of the double-fluoranthene organic semiconductor material are improved; meanwhile, a fluoranthene group is a rigid group, so that the double-fluoranthene organic semiconductor material also has excellent thermal stability; and the fluoranthene group can cause the double-fluoranthene organic semiconductor material to have higher hole mobility. The invention also provides a preparation method of the double-fluoranthene organic semiconductor material and an application of the double-fluoranthene organic semiconductor material in an organic electroluminescence device.
Description
[technical field]
The present invention relates to photoelectric field, particularly relate to a kind of two fluoranthene organic semiconductor material and its preparation method and application.
[background technology]
In recent years, Organic Light Emitting Diode (OLED) achieves larger development.In three primary colours, ruddiness and green diode are all close to the requirement of practical application, but the greater band gap of blue light material, therefore there is larger carrier injection energy barrier in lower highest occupied molecular orbital (HOMO) energy level; Meanwhile, the emitted energy of blue light material is high, unstable, easy be there is energy trasfer and causes transmitting look impure, therefore develops relatively slow.But existing blue emitting material thermostability is not high, thus limits the application of blue emitting material.
[summary of the invention]
Based on this, be necessary the two fluoranthene organic semiconductor material providing a kind of thermostability higher.
In addition, there is a need to the preparation method that a kind of pair of fluoranthene organic semiconductor material is provided.
In addition, there is a need to provide the two application of fluoranthene organic semiconductor material in organic electroluminescence device.
A kind of two fluoranthene organic semiconductor material, has following structural formula:
Wherein, R is C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group.
A preparation method for pair fluoranthene organic semiconductor material, comprises the steps:
Step one, the compd A providing following structural formula to represent and compd B:
Wherein, R is C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group,
Step 2, compd A is added tetrahydrofuran (THF) and the formation of methanol mixed solvent in form solution, sodium hydroxide forming reactions mixed solution is added in described solution, the mol ratio of sodium hydroxide and compd A is 2: 1 ~ 3: 1, and described reaction mixture is at room temperature purified after stirring reaction and obtained Compound C:
Wherein, R is C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group;
Step 3, under atmosphere of inert gases, described compd B and Compound C are added in organic solvent are mixed to form reaction solution in molar ratio at 2: 0.7 ~ 2: 1, purifies after described reaction solution reacts at 160 DEG C ~ 170 DEG C and obtain two fluoranthene organic semiconductor material I:
Wherein, R is C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group.
In a preferred embodiment, in step 2, described reaction mixture at room temperature stirring reaction 1 hour, add extraction into ethyl acetate afterwards and retain organic phase, extract by water, bromine successively and retain organic phase, dry afterwards, except obtaining described Compound C after desolventizing.
In a preferred embodiment, in step 3, described organic solvent is p-Xylol or o-Xylol.
In a preferred embodiment, described in step 3, purification step is as follows: after described reaction solution is cooled to room temperature, add ethanol, filtering-depositing, and uses washing with alcohol to precipitate, and after dry, pillar layer separation obtains described pair of fluoranthene organic semiconductor material.
In a preferred embodiment, the preparation process of described compd A comprises the steps:
First, provide the Compound D that following structural formula represents,
Wherein, R is C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group;
Secondly, under atmosphere of inert gases, add in solvent at 1: 3 ~ 1: 3.2 in molar ratio by described Compound D and trimethylsilyl acetylene, purifying after back flow reaction under the effect of catalyzer obtains described compd A, wherein, described catalyzer is organic palladium and cuprous iodide co-catalyst.
In a preferred embodiment, the mol ratio of described organic palladium and described cuprous iodide is 2: 1 ~ 2.2: 1, the mol ratio of described organic palladium and Compound D is 0.05 ~ 0.1: 1, described organic palladium is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride or two (tricyclohexyl phosphine) palladium chloride.
In a preferred embodiment, described solvent is triethylamine.
In a preferred embodiment, described purification step is as follows: also filtered by the mixture ether obtained after described Compound D and trimethylsilyl acetylene back flow reaction and remove precipitation retaining liquid, remove the solvent in described liquid, then with normal hexane as eluent silica gel column chromatography be separated obtain described compd A.
A kind of organic electroluminescence device, comprises luminescent layer, and the material of luminescent layer is two fluoranthene organic semiconductor material.
This pair of fluoranthene organic semiconductor material launches ethereal blue light, owing to introducing supplied for electronic alkyl or alkoxyl group flexible group in the structure, this material has good solubility, material is readily dissolved in the conventional organic solvent such as tetrahydrofuran (THF), methylene dichloride, toluene, chloroform, improves solvability and the film-forming properties of two fluoranthene organic semiconductor material; Fluoranthene group is rigid radical simultaneously, makes material have excellent thermostability simultaneously; Fluoranthene group also makes material have higher hole mobility.
[accompanying drawing explanation]
Fig. 1 is the spectrogram of two fluoranthene organic semiconductor material prepared by embodiment one;
Fig. 2 is the structural representation of the organic electroluminescence device of an embodiment.
[embodiment]
Below in conjunction with the drawings and specific embodiments, two fluoranthene organic semiconductor material and its preparation method and application is illustrated further.
Two fluoranthene organic semiconductor material of one embodiment, have following structural formula:
Wherein, R is C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group.
Above-mentioned pair of fluoranthene organic semiconductor material launches ethereal blue light, owing to introducing supplied for electronic alkyl or alkoxyl group flexible group in the structure, this material has good solubility, material is readily dissolved in the conventional organic solvent such as tetrahydrofuran (THF), methylene dichloride, toluene, chloroform, improves solvability and the film-forming properties of two fluoranthene organic semiconductor material; Fluoranthene group is rigidity substituting group simultaneously, make material have excellent thermostability simultaneously, characterized the performance of this pair of fluoranthene organic semiconductor material by differential thermal analysis scanning, result shows that this material has excellent thermostability, and 5% thermal weight loss temperature of material is greater than 510 DEG C; And fluoranthene group makes material have higher hole mobility.
The preparation method of two fluoranthene organic semiconductor material of one embodiment, comprises the steps:
Step S1, the compd A providing following structural formula to represent and compd B (7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone):
Wherein, R is C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group,
Wherein, the preparation process of compd A comprises the steps:
First, provide the Compound D that following structural formula represents,
Wherein, R is C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group.
Secondly, under atmosphere of inert gases, add in solvent at 1: 3 ~ 1: 3.2 in molar ratio by Compound D and trimethylsilyl acetylene, after adding catalyzer, purify after reaction at a reflux temperature and obtains compd A, catalyzer is organic palladium and cuprous iodide co-catalyst.
In present embodiment, the mol ratio of organic palladium and cuprous iodide is 2: 1 ~ 2.2: 1.The mol ratio of organic palladium and Compound D is 0.05 ~ 0.1: 1, is preferably 0.06: 0.1.Organic palladium is tetrakis triphenylphosphine palladium (Pd (PPh
3)
4), two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2cl
2), [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride (Pd (dppf) Cl
2) or two (tricyclohexyl phosphine) palladium chloride (PdCl
2(PCy
3)
2).
Preferably, solvent is triethylamine.
In present embodiment, during purification, the mixture that Compound D and trimethylsilyl acetylene back flow reaction obtained after 48 hours is added ether and filter remove precipitation retaining liquid, removing liquid in solvent, then with normal hexane as eluent silica gel column chromatography separation obtain compd A.
Step S2, compd A is added tetrahydrofuran (THF) and the formation of methanol mixed solvent in form solution, sodium hydroxide forming reactions mixed solution is added in solution, the mol ratio of sodium hydroxide and compd A is 2: 1 ~ 3: 1, and at room temperature purifying after stirring reaction obtains Compound C:
Wherein, R is C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group.
In present embodiment, the volume ratio of tetrahydrofuran (THF) and methyl alcohol is 1: 1 ~ 4: 1.The aqueous sodium hydroxide solution forming reactions mixed solution that concentration is 5mol/L is added in solution.Reaction mixture at room temperature stirring reaction 1 hour.During purification, in reaction mixture, add extraction into ethyl acetate and retain organic phase, extracting to remove NaOH by water, bromine successively, use anhydrous sodium sulfate drying organic phase afterwards, obtain Compound C except after desolventizing.
Step S3, under atmosphere of inert gases, compd B and Compound C added in organic solvent be mixed to form reaction solution at 2: 0.7 ~ 2: 1 in molar ratio, reacting at 160 ~ 170 DEG C purified after 24 hours obtains two fluoranthene organic semiconductor material I:
Wherein, R is C
1~ C
20straight chained alkyl, C
1~ C
20branched-chain alkyl or C
1~ C
20alkoxyl group.
In present embodiment, organic solvent is p-Xylol or o-Xylol.Purify two fluoranthene organic semiconductor material time, reaction solution is cooled to room temperature, adds ethanol, filtering-depositing, and use washing with alcohol, pillar layer separation after dry.
Be appreciated that in above steps, the reaction times is all not limited to the time of pointing out in each step, as long as make to react completely in each step.
Two fluoranthene organic semiconductor material prepared by aforesaid method launch colour purity blue light, owing to introducing supplied for electronic flexible group in the structure, this material has good solubility, and material is readily dissolved in the conventional organic solvent such as tetrahydrofuran (THF), methylene dichloride, toluene, chloroform; Improve solvability and the film-forming properties of two fluoranthene organic semiconductor material; Fluoranthene group is rigidity substituting group simultaneously, makes material have excellent thermostability simultaneously; Fluoranthene group also makes material have higher hole mobility.
Be specific embodiment below.
Embodiment 1
The present embodiment prepares 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-methyl triphenylamine (D2PFMTPA)
Comprise the following steps:
Step S11, preparation 4,4 '-trimethylsilyl acetylene-4 "-methyl triphenylamine (compd A).
Be connected with in the there-necked flask of nitrogen to one, add catalyst P d (PPh
3)
2cl
2(630mg, 0.9mmol), CuI (45mg, 0.45mmol), 4,4 '-bromo-4 "-methyl triphenylamine (6.23g; 15mmol), trimethylsilyl acetylene (4.42g, 45mmol); using 60mL triethylamine as solvent, vacuumizes logical nitrogen three times, oil bath reflux 48h; reaction solution washed with diethylether also filters, and revolves and desolventizes, and is separated using normal hexane as eluent silica gel column chromatography; obtain light yellow solid (5.28g, productive rate 78%).
Reaction formula is as follows:
4,4 '-trimethylsilyl acetylene-4 " the proton nmr spectra test result of-methyl triphenylamine is as follows:
1H NMR(400MHz，CD
2Cl
2)δ(ppm)：7.34(d，6H)，6.98(d，6H)，2.12(s，3H)，0.19(s，18H)。
4,4 '-trimethylsilyl acetylene-4 " the mass spectrometric measurement result of-methyl triphenylamine is as follows:
MS：m/z 451。
Step S12, preparation 4,4 '-ethynyl-4 "-methyl triphenylamine.
At compd A (5.28g, add in 60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent 11.7mmol), drip the NaOH aqueous solution that 10mL concentration is 5M, reaction mixture, at stirring at room temperature 1h, then adds extraction into ethyl acetate and retains organic phase, extracts to remove NaOH successively by water, bromine, use anhydrous sodium sulfate drying organic phase afterwards, except desolventizing, obtain 4,4 '-ethynyl-4 "-methyl triphenylamine.
Reaction formula is as follows:
Step S13, preparation 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-methyl triphenylamine (D2PFMTPA).
To prepared by step S12 4,4 '-ethynyl-4 " add compd B (7; 9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g; 30mmol) in-methyl triphenylamine (11.7mmol); logical argon gas; add organic solvent o-Xylol 100mL; 170 DEG C (oil baths) heat 24h, after question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, pillar layer separation, obtain product D 2PFMTPA (12.28g, productive rate 85%).
Reaction formula is as follows:
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the proton nmr spectra test result of-methyl triphenylamine (D2PFMTPA) is as follows:
1H NMR(CD
2Cl
2，400MHz)：7.78-7.68(m，8H)，7.61-7.52(m，6H)，7.48-7.18(m，22H)，7.12-6.95(m，7H)，7.14(d，2H)，6.74(d，1H)，2.32(s，3H)。
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the mass spectrometric measurement result of-methyl triphenylamine (D2PFMTPA) is as follows: MS:m/z 963.
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the thermal weight loss temperature Td of-methyl triphenylamine (D2PFMTPA) 5% is 512 DEG C.
Embodiment 2
The present embodiment prepares 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-octyl triphenylamine (D2PFOTPA)
Comprise the following steps:
Step S21, preparation 4,4 '-trimethylsilyl acetylene-4 "-octyl triphenylamine (compd A).
Be connected with in the there-necked flask of argon gas to one, add catalyst P d (PPh
3)
2cl
2(630mg, 0.9mmol), CuI (45mg, 0.45mmol), 4,4 '-bromo-4 "-octyl triphenylamine (7.7g; 15mmol), trimethylsilyl acetylene (4.42g, 45mmol); using 60mL triethylamine as solvent, vacuumizes logical nitrogen three times, oil bath reflux 48h; washed with diethylether also filters, and revolves and desolventizes, and is separated using normal hexane as eluent silica gel column chromatography; obtain light yellow solid (6.42g, productive rate 78%).
Reaction formula is as follows:
4,4 '-trimethylsilyl acetylene-4 " the proton nmr spectra test result of-octyl triphenylamine is as follows:
1H NMR(400MHz，CD
2Cl
2)δ(ppm)：7.34(d，6H)，6.98(d，6H)，2.12(s，2H)，1.21-1.72(m，15H)，0.19(s，18H)。
4,4 '-trimethylsilyl acetylene-4 " the mass spectrometric measurement result of-octyl triphenylamine is as follows:
MS：m/z 549。
Step S22, preparation 4,4 '-ethynyl-4 "-octyl triphenylamine.
At compd A (6.42g, add in 45mL tetrahydrofuran (THF) and 45mL methanol mixed solvent 11.7mmol), drip the NaOH aqueous solution that 10mL concentration is 5M, reaction mixture, at stirring at room temperature 1h, then adds extraction into ethyl acetate and retains organic phase, extracts to remove NaOH successively by water, bromine, use anhydrous sodium sulfate drying organic phase afterwards, except desolventizing, obtain 4,4 '-ethynyl-4 "-octyl triphenylamine.
Reaction formula is as follows:
Step S23, preparation 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-octyl triphenylamine (D2PFOTPA).
To prepared by step S22 4,4 '-ethynyl-4 " add compd B (7; 9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g; 30mmol) in-octyl triphenylamine 11.7mmol; logical argon gas; add organic solvent o-Xylol 100mL; 170 DEG C (oil baths) heat 24h, after question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, pillar layer separation, obtain product D 2PFOTPA (12.73g, productive rate 80%).
Reaction formula is as follows:
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the proton nmr spectra test result of-octyl triphenylamine (D2PFOTPA) is as follows:
1H NMR(CD
2Cl
2，400MHz)：7.78-7.68(m，8H)，7.61-7.52(m，6H)，7.48-7.18(m，22H)，7.12-6.95(m，7H)，7.14(d，2H)，6.74(d，1H)，2.32(s，2H)，1.21-1.72(m，15H)。
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the mass spectrometric measurement result of-octyl triphenylamine (D2PFOTPA) is as follows: MS:m/z 1061.
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the thermal weight loss temperature Td of-octyl triphenylamine (D2PFOTPA) 5% is 519 DEG C.
Refer to Fig. 1, Fig. 1 is 4 of embodiment 2 preparation, 4 '-(7,10-phenylbenzene fluoranthene base)-4 " the fluorescence emission spectra figure of-octyl triphenylamine (D2PFOTPA); the maximum glow peak of emmission spectrum is at 442nm, and spectrum is narrower, visible 4; 4 '-(7,10-phenylbenzene fluoranthene base)-4 "-octyl triphenylamine can be used as the field that blue light emitting material is widely used in organic electroluminescence device.
Embodiment 3
The present embodiment prepares 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-octyloxy triphenylamine (D2PFOOTPA))
Comprise the following steps:
Step S31, preparation 4,4 '-trimethylsilyl acetylene-4 "-octyloxy triphenylamine (compd A).
Be connected with in the there-necked flask of nitrogen to one, add catalyst P d (PPh
3)
2cl
2(630mg, 0.9mmol), CuI (45mg, 0.45mmol), 4,4 '-bromo-4 "-octyloxy triphenylamine (7.94g; 15mmol), trimethylsilyl acetylene (4.42g, 45mmol); using 60mL triethylamine as solvent, vacuumizes logical nitrogen three times, oil bath reflux 48h; washed with diethylether also filters, and revolves and desolventizes, and is separated using normal hexane as eluent silica gel column chromatography; obtain light yellow solid (6.78g, productive rate 80%).
Reaction formula is as follows:
4,4 '-trimethylsilyl acetylene-4 " the proton nmr spectra test result of-octyloxy triphenylamine is as follows:
1H NMR(400MHz，CD
2Cl
2)δ(ppm)：7.34(d，6H)，6.98(d，6H)，4.12(t，2H)，1.21-1.79(m，15H)，0.19(s，18H)。
4,4 '-trimethylsilyl acetylene-4 " the mass spectrometric measurement result of-octyloxy triphenylamine is as follows:
MS：m/z 565。
Step S32, preparation 4,4 '-ethynyl-4 "-octyloxy triphenylamine.
At compd A (6.78g, add in 70mL tetrahydrofuran (THF) and 20mL methanol mixed solvent 12mmol), drip the NaOH aqueous solution that 10mL concentration is 5M, reaction mixture, at stirring at room temperature 1h, then adds extraction into ethyl acetate and retains organic phase, extracts to remove NaOH successively by water, bromine, use anhydrous sodium sulfate drying organic phase afterwards, except desolventizing, obtain 4,4 '-ethynyl-4 "-octyloxy triphenylamine.
Reaction formula is as follows:
Step S33, preparation 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-octyloxy triphenylamine (D2PFOOTPA).
To prepared by step S32 4, 4 '-ethynyl-4 " add compd B (7 in-octyloxy triphenylamine (12mmol), 9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g, 30mmol), logical argon gas, add organic solvent o-Xylol 100mL, 170 DEG C (oil baths) heat 24h, after question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, pillar layer separation, obtain product 4, 4 '-(7, 10-phenylbenzene fluoranthene base)-4 "-octyloxy triphenylamine (D2PFOOTPA) (13.74g, productive rate 85%).
Reaction formula is as follows:
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the proton nmr spectra test result of-octyloxy triphenylamine (D2PFOOTPA) is as follows:
1H NMR(CD
2Cl
2，400MHz)：7.78-7.68(m，8H)，7.61-7.52(m，6H)，7.48-7.18(m，22H)，7.12-6.95(m，7H)，7.14(d，2H)，6.74(d，1H)，4.02(t，2H)，1.22-1.85(m，15H)。
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the mass spectrometric measurement result of-octyloxy triphenylamine (D2PFOOTPA) is as follows:
MS：m/z 1077。
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the thermal weight loss temperature Td of-octyloxy triphenylamine (D2PFOOTPA) 5% is 521 DEG C.
Embodiment 4
The present embodiment prepares 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-eicosane oxygen base triphenylamine (D2PFTOTPA)
Comprise the following steps:
Step S41, preparation 4,4 '-trimethylsilyl acetylene-4 "-eicosane oxygen base triphenylamine (compd A).
Be connected with in the there-necked flask of nitrogen to one, add catalyst P d (PPh3) 4 (1038mg, 0.9mmol), CuI (45mg, 0.45mmol), 4,4 '-bromo-4 "-eicosane oxygen base triphenylamine (10.49g; 15mmol), trimethylsilyl acetylene (4.42g, 45mmol); using 60mL triethylamine as solvent; vacuumize logical nitrogen three times, oil bath reflux 48h, washed with diethylether also filters; revolve and desolventize; be separated using normal hexane as eluent silica gel column chromatography, obtain light yellow solid (8.8g, productive rate 80%)
Reaction formula is as follows:
4,4 '-trimethylsilyl acetylene-4 " the proton nmr spectra test result of-eicosane oxygen base triphenylamine is as follows:
1H NMR(400MHz，CD
2Cl
2)δ(ppm)：7.34(d，6H)，6.98(d，6H)，4.12(t，2H)，1.21-1.78(m，39H)，0.19(s，18H)。
4,4 '-trimethylsilyl acetylene-4 " the mass spectrometric measurement result of-eicosane oxygen base triphenylamine is as follows:
MS：m/z 733。
Step S42, preparation 4,4 '-ethynyl-4 "-eicosane oxygen base triphenylamine.
At compd A (8.8g, add in 60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent 12mmol), drip the NaOH aqueous solution that 10mL concentration is 5M, reaction mixture, at stirring at room temperature 1h, then adds extraction into ethyl acetate and retains organic phase, extracts to remove NaOH successively by water, bromine, use anhydrous sodium sulfate drying organic phase afterwards, except desolventizing, obtain 4,4 '-ethynyl-4 "-eicosane oxygen base triphenylamine.
Reaction formula is as follows:
Step S43, preparation 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-eicosane oxygen base triphenylamine (D2PFTOTPA).
To prepared by step S42 4,4 '-ethynyl-4 " add compd B (7; 9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g; 30mmol) in-eicosane oxygen base triphenylamine (12mmol); logical argon gas, add organic solvent o-Xylol 100mL, 170 DEG C (oil baths) heat 24h; after question response mixed solution is cooled to room temperature; add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, pillar layer separation, obtains product 4, and 4 '-(7,10-phenylbenzene fluoranthene base)-4 "-eicosane oxygen base triphenylamine (15.89g, productive rate 85%).
Reaction formula is as follows:
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the proton nmr spectra test result of-eicosane oxygen base triphenylamine (D2PFTOTPA) is as follows:
1H NMR(CD
2Cl
2，400MHz)：7.78-7.68(m，8H)，7.61-7.52(m，6H)，7.48-7.18(m，22H)，7.12-6.95(m，7H)，7.14(d，2H)，6.74(d，1H)，4.12(t，2H)，1.21-1.78(m，39H)。
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the mass spectrometric measurement result of-eicosane oxygen base triphenylamine (D2PFTOTPA) is as follows: MS:m/z 1246.
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the thermal weight loss temperature Td of-eicosane oxygen base triphenylamine (D2PFTOTPA) 5% is 527 DEG C.
Embodiment 5
The present embodiment prepares 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-tertiary butyl triphenylamine (D2PFBTPA)
Comprise the following steps:
Step S51, preparation 4,4 '-trimethylsilyl acetylene-4 "-methyl triphenylamine (compd A).
Be connected with in the there-necked flask of nitrogen to one, add catalyst P d (PPh
3)
2cl
2(630mg, 0.9mmol), CuI (45mg, 0.45mmol), 4,4 '-bromo-4 "-tertiary butyl triphenylamine (6.89g; 15mmol), trimethylsilyl acetylene (4.42g, 45mmol); using 60mL triethylamine as solvent, vacuumizes logical nitrogen three times, oil bath reflux 48h; reaction solution washed with diethylether also filters, and revolves and desolventizes, and is separated using normal hexane as eluent silica gel column chromatography; obtain light yellow solid (5.98g, productive rate 81%).
Reaction formula is as follows:
4,4 '-trimethylsilyl acetylene-4 " the proton nmr spectra test result of-tertiary butyl triphenylamine is as follows:
1H NMR(400MHz，CD
2Cl
2)δ(ppm)：7.34(d，6H)，6.98(d，6H)，1.32-1.78(s，9H)，0.19(s，18H)。
4,4 '-trimethylsilyl acetylene-4 " the mass spectrometric measurement result of-tertiary butyl triphenylamine is as follows:
MS：m/z 493。
Step S52, preparation 4,4 '-ethynyl-4 "-tertiary butyl triphenylamine.
At compd A (5.98g, add in 72mL tetrahydrofuran (THF) and 18mL methanol mixed solvent 12mmol), drip the NaOH aqueous solution that 10mL concentration is 5M, reaction mixture, at stirring at room temperature 1h, then adds extraction into ethyl acetate and retains organic phase, extracts to remove NaOH successively by water, bromine, use anhydrous sodium sulfate drying organic phase afterwards, except desolventizing, obtain 4,4 '-ethynyl-4 "-tertiary butyl triphenylamine.
Reaction formula is as follows:
Step S53, preparation 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-tertiary butyl triphenylamine (D2PFBTPA).
To prepared by step S52 4,4 '-ethynyl-4 " add compd B (7; 9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g; 30mmol) in-methyl triphenylamine (12mmol); logical argon gas; add organic solvent o-Xylol 100mL; 160 DEG C (oil baths) heat 24h, after question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, pillar layer separation, obtain product D 2PFBTPA (12.28g, productive rate 87%).
Reaction formula is as follows:
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the proton nmr spectra test result of-tertiary butyl triphenylamine (D2PFBTPA) is as follows:
1H NMR(CD
2Cl
2，400MHz)：7.76-7.68(m，8H)，7.62-7.52(m，6H)，7.48-7.19(m，22H)，7.12-6.97(m，7H)，7.15(d，2H)，6.76(d，1H)，1.32-1.86(s，9H)。
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the mass spectrometric measurement result of-methyl triphenylamine (D2PFBTPA) is as follows: MS:m/z 1005.
4,4 '-(7,10-phenylbenzene fluoranthene base)-4 " the thermal weight loss temperature T of-methyl triphenylamine (D2PFBTPA) 5%
dit is 514 DEG C.
Embodiment 6
Refer to Fig. 2, a kind of organic electroluminescence device 100 comprises the anode 20, hole transmission layer 30, luminescent layer 40, hole blocking layer 50, electron transfer layer 60, negative electrode 70 and the protective layer 80 that stack gradually.Wherein, the material of luminescent layer 40 is D2PFOTPA prepared by embodiment 2, and thickness is 30nm.
Anode 20 comprises substrate 21 and is formed at the tin indium oxide (ITO) 24 of described substrate 21 near described hole transmission layer 30 side.
When preparing above-mentioned electroluminescent organic material, by ito glass spin coating photoresist material, exposure, development, chloroazotic acid etching, be etched into required pattern and size makes anode 20; Then anode purge 20, uses each ultrasonic cleaning 10 ~ 15min such as pure water, acetone, ethanol successively; Clean up and carry out oxygen plasma treatment to it afterwards, the oxygen plasma treatment time is 5 ~ 15min, and power is 10 ~ 50W, improves the surperficial work content of anode 20 with this.Then anode 20 is put into organic vacuum cavity; evaporation hole transmission layer 30, luminescent layer 40, hole blocking layer 50, electron transfer layer 60 successively; then metallic cavity is moved into; continue evaporation negative electrode 70 and protective layer 80; finally obtain required high efficiency blue electroluminescent device; device trigger voltage is 5.4V, and maximum lumen efficiency is 12.7lm/W, and high-high brightness is 42000cd/m
2.
Wherein, hole transmission layer 30 is that p-adulterates hole transmission layer, material is 4,4 ', 4 "-three (3-aminomethyl phenyl aniline) triphenylamine (m-MTDATA): tetrafluoro para benzoquinone bismethane (F4-TCNQ), thickness is 40nm.The material of luminescent layer 40 is D2PFOTPA prepared by embodiment 2, and thickness is 30nm.The material of hole blocking layer 50 is 4,7-phenylbenzene-1,10-phenanthroline (Bphen), and thickness is 10nm.Electron transfer layer 60 is n-doping electron transfer layer, and material is 4,7-phenylbenzene-1,10-phenanthroline (Bphen): caesium (Cs), and thickness is 40nm.The material of negative electrode 70 is magnesium silver alloys, and wherein the mass ratio of magnesium (Mg) and silver (Ag) is 10: 1, the thickness 150nm of negative electrode 70.The material of protective layer 80 is Ag, and thickness is 10nm.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (1)
1. a preparation method for two fluoranthene organic semiconductor material, is characterized in that, comprise the steps:
Step S41, prepare compd A 4,4 '-trimethylsilyl acetylene-4 "-eicosane oxygen base triphenylamine:
Be connected with in the there-necked flask of nitrogen to one, add catalyst P d (PPh
3)
40.9mmol, CuI 0.45mmol, 4,4 '-bromo-4 "-eicosane oxygen base triphenylamine 15mmol; trimethylsilyl acetylene 45mmol, using 60mL triethylamine as solvent, vacuumizes logical nitrogen three times; oil bath reflux 48h; washed with diethylether also filters, and revolves and desolventizes, be separated; obtain light yellow solid 8.8g using normal hexane as eluent silica gel column chromatography
Reaction formula is as follows:
Step S42, preparation 4,4 '-ethynyl-4 "-eicosane oxygen base triphenylamine:
60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent is added in 12mmol compd A, drip the NaOH aqueous solution that 10mL concentration is 5M, reaction mixture is at stirring at room temperature 1h, then add extraction into ethyl acetate and retain organic phase, extracting to remove NaOH by water, bromine successively, use anhydrous sodium sulfate drying organic phase afterwards, except desolventizing, obtain 4,4 '-ethynyl-4 "-eicosane oxygen base triphenylamine
Reaction formula is as follows:
Step S43, preparation 4,4 '-(7,10-phenylbenzene fluoranthene base)-4 "-eicosane oxygen base triphenylamine D2PFTOTPA:
To prepared by step S42 4,4 '-ethynyl-4 " add 7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone 30mmol in-eicosane oxygen base triphenylamine 12mmol; logical argon gas, adds organic solvent o-Xylol 100mL, 170 DEG C of oil baths heating 24h; after question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing; washing with alcohol, vacuum-drying, pillar layer separation; obtain product 4; 4 '-(7,10-phenylbenzene fluoranthene base)-4 "-eicosane oxygen base triphenylamine 15.89g
Reaction formula is as follows:
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