CN107973900A - A kind of poly- anthracene compound and its preparation method and application - Google Patents
A kind of poly- anthracene compound and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to Organic Light Emitting Diode field, specifically discloses a kind of poly- anthracene compound and its preparation method and application, its structure is as shown in formula I, R1~R4Long-chain for identical either different C1~C20 is connected in a manner of alkyl or alkoxy with aryl.Then grignard reagent is made in 9,10 dibromoanthracenes and reactive magnesium by not isoplastic 9,10 dibromoanthracene of elder generation's anamorphic zone of the invention, finally carry out free radical polycondensation under the high temperature conditions and synthesize poly- 9,10 anthracene.The present invention has synthesized the oligomer of anthracene, the narrow only blue light-emitting of spectrum using the method for free radical coupling.Party's law system is clean, easy to operate, is not easy to bring impurity, synthetic yield is higher.The poly- anthracene compound can be applied in polymer LED.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of poly- anthracene and its synthetic method and in polymer light-emitting two
Application in pole pipe.
Background technology
Organic electroluminescent phenomenon can trace back to 1963, and Pope seminars and Visco seminars are found in micron thickness
Anthracene single crystal apply and be observed that blue emission not less than the DC voltage of 400V.Until 1987, Kodak
Doctor Deng Qingyun et al. has invented sandwich type organic bilayer film electroluminescent device, using 8-hydroxyquinoline aluminium as luminous
Layer material, in the case where being driven less than 10V voltages, device luminosity reaches 1000cd/m2, external quantum efficiency brings up to 1%, efficiency
For 1.51m/W, so as to evoke the research boom of electroluminescent organic material and device.Burroughes exists equal to nineteen ninety
Delivered on Nature publications and film be made using the method that solution is processed on high molecular material poly-phenylene vinylene (ppv) (PPV),
Electro optical phenomenon is found at lower voltages, opens the research and development of macromolecule FPD.It is currently based on sandwich device architecture
Organic Light Emitting Diode OLED industrialization, for mobile phone, flat panel TV, photon emitting system etc..
Anthracene is the OLED material of a major class excellent performance, and is used for electroluminescent material earliest.The derivative of anthracene is
Through being widely used in OLED material of main parts, wherein have to anthracene have triplet state fusion (triplet fusion) uniqueness
Can, common singlet emitter efficiency can be allowd to break through 25% when being used as Host.Poly- anthracene is a kind of excellent gathers
Compound luminescent material, but the homopolymer of anthracene is (can not to refer to Macrom with Suzuki or Yamamoto reactions come what is synthesized
olecular Chemistry And Physics 2006,207,1107.)
Have been reported that before this and (refer to Journal Of Applied Polymer Science with ferric trichloride oxidation polymerization
2013,127,4524), it may be possible to which by Oxidation Doping or oxidized, color is deeper, and post processing is cumbersome, and purification is compared
Difficulty, the fluorescence of product is colorful, and spectrum is very wide.
The content of the invention
It is an object of the present invention to providing a kind of poly- anthracene compound, these polymer are most of because side chain is long-chain
Substituted radical and dissolve in various solvents, be adapted to spin coating or printing-filming, so as in electroluminescent, photovoltaic cell and pass
Sense field is applied.
The second object of the present invention is the synthetic method for proposing that 2,3,6,7 are alkyl-substituted poly- anthracene.
A kind of poly- anthracene compound, its structure are as follows：
R1~R4Long-chain for identical either different C1~C20 is connected in a manner of alkyl or alkoxy with aryl.n
The concrete numerical value of n is not particularly limited in=1,2, the 3...... present invention.
The poly- anthracene compound, its structure for it is following any one：
The preparation method of the poly- anthracene compound, not isoplastic 9, the 10- dibromoanthracenes of first anamorphic zone, then by 9,10- bis-
Grignard reagent is made with reactive magnesium in bromine anthracene, finally carries out free radical polycondensation under the high temperature conditions and synthesizes poly- 9,10- anthracenes.
The specific preparation method of the poly- anthracene compound is as follows：
The magnesium of not isoplastic 9, the 10- dibromoanthracenes of band and activation is added in polymerization pipe, argon gas is changed and injects tetrahydrochysene afterwards several times
Furans, ultrasound disappears to magnesium at 50 DEG C~70 DEG C, injects toluene or trimethylbenzene, and tetrahydrofuran is removed in heating, and micro- back flow reaction 1~
3 days, add water quenching to go out, organic layer is separated, rotate solvent, cross silicagel column, washed with methanol, that is, obtain purpose product.
The poly- anthracene compound is applied in polymer LED.
Compared with prior art, the present invention has the advantages that：
(1) present invention has synthesized the oligomer of anthracene, the narrow only blue light-emitting of spectrum using the method for free radical coupling.Party's body of laws
System is clean, easy to operate, is not easy to bring impurity, synthetic yield is higher.
(2) Inventive polymers are most of because side chain dissolves in various solvents for the substituted radical of long-chain, are adapted to rotation
Painting or printing-filming, so as to be applied in electroluminescent, photovoltaic cell and sensory field.
Brief description of the drawings
Fig. 1 is 9,10- dibromoanthracenes1H-NMR spectrum.
Fig. 2 is 2- normal-butyl anthracenes1H-NMR spectrum.
Fig. 3 is 2- normal-butyl -9,10- dibromoanthracenes1H-NMR spectrum.
Fig. 4 is 2- normal-butyl -9,10- dibromoanthracenes13C-NMR spectrograms.
Fig. 5 is 2- tert-butyl group anthraquinones1H-NMR spectrum.
Fig. 6 is 2- tert-butyl anthracenes1H-NMR spectrum.
Fig. 7 is the 2- tert-butyl group -9,10- dibromoanthracenes1H-NMR spectrum.
Fig. 8 is the 2- tert-butyl group -9,10- dibromoanthracenes13C-NMR spectrograms.
Fig. 9 is 2,6- di-tert-butyl anthracenes1H-NMR spectrum.
Figure 10 is 2,6- di-t-butyl -9,10- dibromoanthracenes1H-NMR spectrum.
Figure 11 is 2,6- di-t-butyl -9,10- dibromoanthracenes13C-NMR spectrograms.
Figure 12 is tetra- octyl group anthraquinones of 2,3,6,7-1H-NMR spectrum.
Figure 13 is tetra- octyl group anthracenes of 2,3,6,7-1H-NMR spectrum.
Figure 14 is tetra- octyl group -9,10- dibromoanthracenes of 2,3,6,7-1H-NMR spectrum.
Embodiment
The synthesis to poly- anthracene is further described by the following examples.
Embodiment 1
The preparation of 9,10- dibromoanthracenes, synthetic route are as follows：
Add anthracene (10g, 56.1mmol) in the single-necked flask of 1000ml, chloroform 200ml, stirring and dissolving at room temperature,
Bromine (18g, 112.6mmol) and chloroform 100ml is added in the constant pressure funnel of 250ml, reaction unit is subjected to lucifuge, and by perseverance
Snorkel on pressure funnel is passed through in sodium hydroxide solution with pipe, when stirring 4 is small at room temperature.Sodium hydroxide solution is added to quench
Go out, organic layer is washed with salt after layering, adds anhydrous magnesium sulfate to dry, solvent is rotated after filtered on buchner funnel, uses vacuum pump
Drain, obtain yellow solid, with re crystallization from toluene, obtain yellow needles 16.7g, yield 88.6%.1H NMR(600MHz,
CDCl3)δ8.67–8.47(m,4H),7.69–7.58(m,4H).
In polymerization pipe add 9,10- dibromoanthracenes (0.25g, 0.744mmol), activation magnesium (0.0179g,
0.744mmol), argon gas is changed three times, injection tetrahydrofuran 2ml, ultrasound disappears to magnesium at 60 DEG C, injects toluene 25ml, heating removes
Fall tetrahydrofuran, micro- back flow reaction 2 days, adds water quenching to go out, organic layer is separated, and rotates solvent, crosses silicagel column, is washed with methanol
Three times, yellow powder 0.0426g, yield 32.1% are obtained.
Embodiment 2
The preparation of 2- normal-butyl -9,10- dibromoanthracenes, synthetic route are as follows：
The addition phthalic anhydride (11.11g, 75mmol) in three-necked flask, anhydrous Aluminum chloride (24g, 180mmol),
Chloroform 50ml, n-butylbenzene (10.07g, 75mmol) and chloroform 50ml are added in constant pressure funnel, is slowly added dropwise, 50 after dripping off
DEG C reaction 1 it is small when, then rise cooling, pour into the mixed solution of 48ml concentrated hydrochloric acids and 96g ice and be quenched, chlorination imitates extraction three
It is secondary, add anhydrous magnesium sulfate to dry, with solvent is rotated after filtered on buchner funnel, brown solid 21.09g is drained to obtain with vacuum pump,
Thick yield 99.6%.
2- (3- n-butylbenzenes formoxyl) benzoic acid (21.09g, 74.7mmol), the concentrated sulfuric acid are added in single-necked flask
126ml, 125 DEG C are reacted one hour, are poured into ice and are quenched, extracted with toluene, add anhydrous magnesium sulfate to dry, use filtered on buchner funnel
After rotate solvent, cross column, obtain yellow solid, add recrystallizing methanol to obtain yellow needles 2- normal-butyl -9,10- anthraquinones
8.21g, 90-92 DEG C of fusing point, yield 41.6%.1H NMR (600MHz, CDCl3) δ 8.33-8.28 (m, 2H), 8.22 (d, J=
7.9Hz, 1H), 8.11 (d, J=1.3Hz, 1H), 7.81-7.77 (m, 2H), 7.60 (dd, J=7.9,1.5Hz, 1H), 2.82-
2.77 (m, 2H), 1.69 (dt, J=13.1,7.6Hz, 2H), 1.40 (dq, J=14.8,7.5Hz, 2H), 0.96 (t, J=
7.4Hz,3H).
2- normal-butyl -9,10- anthraquinones (1.5g, 5.67mmol) are added in three-necked flask, add sodium borohydride
(0.6167g, 16.3mmol), changes argon gas three times, and 5.4g isopropanols are added dropwise, and back flow reaction is overnight, and ethanol 1.7g, reaction 5 is added dropwise
Hour, acetic acid 3g is added dropwise, reaction overnight, drops to after room temperature plus water quenching is gone out, extracted with dichloromethane, add anhydrous magnesium sulfate to dry,
Filtered on buchner funnel, is drained with vacuum pump to obtain yellow solid 1.45g, crossing column with petroleum ether obtains white solid after filtrate is rotated
0.84g, adds recrystallizing methanol to obtain white solid 2- normal-butyl anthracene 0.68g, 126-128 DEG C of fusing point, yield 51.2%.1H NMR
(600MHz, CDCl3) δ 8.36 (s, 1H), 8.32 (s, 1H), 7.97 (dd, J=6.6,3.0Hz, 2H), 7.92 (d, J=
8.7Hz, 1H), 7.74 (s, 1H), 7.45-7.40 (m, 2H), 7.32 (dd, J=8.7,1.4Hz, 1H), 2.82-2.77 (m,
2H), 1.72 (dq, J=13.0,7.6Hz, 2H), 1.46-1.38 (m, 2H), 0.96 (t, J=7.4Hz, 3H)
2- normal-butyls anthracene (1.61g, 6.87mmol) is added in the single-necked flask of 100ml, chloroform 30ml, is stirred at room temperature
Dissolving, bromine (2.2g, 13.77mmol) and chloroform 15ml are added in the constant pressure funnel of 100ml, reaction unit is kept away
Light, and the snorkel in constant pressure funnel is passed through in sodium hydroxide solution with pipe, when stirring 4 is small at room temperature.Add hydroxide
Sodium solution is quenched, and organic layer is washed with salt after layering, adds anhydrous magnesium sulfate to dry, solvent is rotated after filtered on buchner funnel,
Drained with vacuum pump, yellow needles 2- normal-butyl -9,10- dibromoanthracene 2.3g are obtained with ethyl alcohol recrystallization, 72-74 DEG C of fusing point,
Yield 85.4%.1H NMR(600MHz,CDCl3) δ 8.57-8.53 (m, 2H), 8.48 (d, J=9.0Hz, 1H), 8.31 (s,
1H), 7.63-7.56 (m, 2H), 7.48 (dd, J=9.0,1.2Hz, 1H), 2.90-2.85 (m, 2H), 1.79-1.71 (m, 2H),
1.48-1.40 (m, 2H), 0.98 (t, J=7.4Hz, 3H)13C NMR(151MHz,CDCl3)δ142.33,131.24,
131.13,130.56,129.99,129.54,128.22,128.14,127.28,126.97,125.92,123.32,122.60,
35.99,33.06,22.48,13.98.
In polymerization pipe add 2- normal-butyl -9,10- dibromoanthracenes (0.25g, 0.638mmol), activation magnesium (0.0153g,
0.638mmol), argon gas is changed three times, injection tetrahydrofuran 2ml, ultrasound disappears to magnesium at 60 DEG C, injects toluene 25ml, heating removes
Fall tetrahydrofuran, micro- back flow reaction 2 days, adds water quenching to go out, organic layer is separated, and rotates solvent, crosses silicagel column, is washed with methanol
Three times, yellow powder 0.0605g, yield 40.5% are obtained.
Embodiment 3
The preparation of 2- tert-butyl group -9,10- dibromoanthracenes, synthetic route are as follows：
Phthalic anhydride (11.11g, 75mmol) is weighed, anhydrous Aluminum chloride (24g, 180mmol), chloroform 50ml is in list
In mouth bottle, tert-butyl benzene (10.07g, 75mmol) and chloroform 50ml are added in constant pressure funnel, is slowly added dropwise, 50 DEG C after dripping off
React 1 it is small when, then rise cooling, pour into the mixed solution of 48ml concentrated hydrochloric acids and 96g ice and be quenched, chlorination imitate extraction three times,
Add anhydrous magnesium sulfate to dry, solvent rotated after filtered on buchner funnel, drain brown solid 21.68g, thick yield are more than
100%.
Addition 2- (3- tert-butyl-benzoyls) benzoic acid (4.35g, 15.4mmol) in single port bottle, concentrated sulfuric acid 25ml,
125 DEG C are reacted one hour, are poured into ice and are quenched, and toluene extraction, adds anhydrous magnesium sulfate to dry, with being rotated after filtered on buchner funnel
Solvent, column is crossed with silica gel, obtains yellow solid 1.74g, adds recrystallizing methanol to obtain yellow needles 2- tert-butyl group -9,10- anthraquinones
1.24g, 102-105 DEG C of fusing point, yield 30.5%.1H NMR(600MHz,CDCl3) δ 8.34 (d, J=2.0Hz, 1H), 8.33-
8.30 (m, 2H), 8.25 (d, J=8.2Hz, 1H), 7.83 (dd, J=8.2,2.1Hz, 1H), 7.81-7.77 (m, 2H), 1.43
(d, J=4.5Hz, 9H)
Addition 2- tert-butyl groups -9,10- anthraquinone (4.7g, 17.8mmol) in three-necked flask, sodium borohydride (1.9g,
50mmol), change argon gas three times, 17g isopropanols are added dropwise, back flow reaction is overnight, and ethanol 5.26g is added dropwise, and when reaction 5 is small, vinegar is added dropwise
Sour 9.4g, reaction overnight, drop to room temperature, add water quenching to go out, and then dichloromethane extracts, and adds anhydrous magnesium sulfate to dry, Buchner funnel
Filtering, is drained with vacuum pump to obtain yellow solid 4.33g, crossing column with petroleum ether obtains white solid 2.9g, adds after filtrate is rotated
Recrystallizing methanol obtains white solid 2- tert-butyl anthracene 2.52g, 146-148 DEG C of fusing point, yield 60%.1H NMR(600MHz,
CDCl3) δ 8.36 (d, J=10.1Hz, 2H), 7.99-7.95 (m, 2H), 7.94 (d, J=9.0Hz, 1H), 7.88 (d, J=
0.8Hz, 1H), 7.56 (dd, J=8.9,1.9Hz, 1H), 7.44-7.39 (m, 2H), 1.44 (s, 9H)
2- tert-butyl anthracenes (3.739g, 16mmol) are added in the single-necked flask of 250ml, then add chloroform 70ml, room
The lower stirring and dissolving of temperature, bromine (5.15g, 32mmol) and chloroform 35ml are added in the constant pressure funnel of 100ml, carries out lucifuge, and
Snorkel in constant pressure funnel is passed through in sodium hydroxide solution with pipe, when stirring 4 is small at room temperature.Add sodium hydroxide solution
It is quenched, organic layer is washed with salt after layering, adds anhydrous magnesium sulfate to dry, solvent is rotated after filtered on buchner funnel, uses vacuum
Pumping is done, and petroleum ether crosses column, with ethyl alcohol recrystallization, obtains yellow needles 5.38g, 133-136 DEG C of fusing point, yield 86%.1H
NMR(600MHz,CDCl3) δ 8.58-8.53 (m, 2H), 8.50 (d, J=9.2Hz, 1H), 8.48 (d, J=1.6Hz, 1H),
7.72 (dd, J=9.2,1.7Hz, 1H), 7.62-7.57 (m, 2H), 1.49 (s, 9H)13C NMR(151MHz,CDCl3)δ
150.24,131.15,131.02,130.69,129.80,128.17,128.10,127.24,127.07,127.01,123.38,
123.07,122.68,35.34,30.87.
In polymerization pipe add 2- tert-butyl groups -9,10- dibromoanthracene (0.25g, 0.638mmol), activation magnesium (0.0153g,
0.638mmol), argon gas is changed three times, injection tetrahydrofuran 2ml, ultrasound disappears to magnesium at 60 DEG C, injects toluene 25ml, heating removes
Fall tetrahydrofuran, micro- back flow reaction 2 days, adds water quenching to go out, organic layer is separated, and rotates solvent, crosses silicagel column, is washed with methanol
Three times, yellow powder 0.0526g, yield 35.2% are obtained.
Embodiment 4
The preparation of 2,6- di-t-butyl -9,10- dibromoanthracenes, synthetic route are as follows：
Anthracene (10g, 56.1mmol), the tert-butyl alcohol (12.47g, 168.2mmol), trifluoroacetic acid are added in single-necked flask
70ml, when back flow reaction 16 is small, rises cooling, adds sodium acid carbonate processing, adds water 150ml, petroleum ether 150ml, by organic layer
Separation, add methylene chloride to obtain settled solution, spins off solvent, and petroleum ether crosses silicagel column for eluant, eluent, adds petroleum ether and dichloromethane
Recrystallization, obtains colorless crystalline thing 2,7- di-tert-butyl anthracene 13g, 248-251 DEG C of fusing point, yield 79.8%.1H NMR(600MHz,
CDCl3) δ 8.31 (s, 2H), 7.92 (d, J=8.9Hz, 2H), 7.86 (d, J=1.7Hz, 2H), 7.53 (dd, J=8.9,
1.9Hz,2H),1.44(s,18H).
2,7- di-tert-butyl anthracenes (2.69g, 9.26mmol) are added in single port bottle, chloroform 54ml, adds in constant pressure funnel
Enter bromine (3.1g, 19.4mmol) and chloroform 31ml, be slowly added dropwise, be then stirred at room temperature 24 it is small when, add sodium hydrogensulfite to be quenched,
Washing, adds anhydrous magnesium sulfate drying, with solvent is rotated after filtered on buchner funnel, vacuum pump drains to obtain light green solid
4.13g, obtains light green solid 3.56g after crossing silicagel column, adds ethanol 280ml and toluene 60ml to recrystallize to obtain the green crystalline thing of bulk
2.6g, 204-206 DEG C of fusing point, yield 63%.1H NMR(600MHz,CDCl3) δ 8.50 (d, J=9.2Hz, 2H), 8.45 (d, J
=1.6Hz, 2H), 7.70 (dd, J=9.2,1.8Hz, 2H), 1.48 (s, 18H)13C NMR(151MHz,CDCl3)δ149.78,
130.65,129.88,128.00,126.88,122.94,122.59,35.29,30.88.
2,7- di-t-butyls -9,10- dibromoanthracene (0.25g, 0.558mmol), the magnesium of activation are added in polymerization pipe
(0.0134g, 0.558mmol), changes argon gas three times, injection tetrahydrofuran 2ml, and ultrasound disappears to magnesium at 60 DEG C, injects toluene
Tetrahydrofuran is removed in 25ml, heating, and micro- back flow reaction 2 days, adds water quenching to go out, organic layer is separated, and rotates solvent, crosses silica gel
Column, is washed three times with methanol, obtains yellow powder 0.0606g, yield 37.4%.
Embodiment 5
The preparation of 2,3,6,7- tetra- octyl group -9,10- dibromoanthracenes, synthetic route are as follows：
The Mg for taking (0.44mol, 10.56g) to activate, adds 1-2 iodine in the three-necked flask of 500ml, changes argon gas three times,
70ml anhydrous ethers are injected, (0.4mol, 77.2g) bromooctane is injected in constant pressure funnel, after being first put into 4ml initiation reactions, are delayed
Slowly remaining bromooctane is added dropwise, about 1h is dripped off, then 40 degree of reflux 0.5h.Take (0.5g, 0.92mmol) Ni (dppp) Cl2In another
In the three-necked flask of 500ml, after ventilation, the green reagent prepared is transferred in constant pressure funnel by pipe, is injected
(0.1mol, 24.2g) 3,4- dibromo thiophenes and 40ml anhydrous ethers, are slowly added dropwise grignard reagent, add rear back flow reaction 4h, room
Temperature is stirred overnight.Take the 40ml concentrated sulfuric acids to enter in frozen water, reaction solution is poured into and is wherein quenched, then extracted with dichloromethane, brine,
Sodium bicarbonate aqueous solution, brine are respectively washed once, add anhydrous magnesium sulfate to dry, and with filtered on buchner funnel, filtrate are spin-dried for, vacuum pump
Drain, petroleum ether crosses column and obtains yellow oil 32.85g, and colourless transparent liquid 3,4- dioctyl thiophene are obtained after vacuum distillation
27.7g, yield 89.8%.
Weigh 3,4- dioctyls thiophene (5.85g, 18.96mmol) and be dissolved in 90ml dichloromethane simultaneously ice bath, weigh m-
CP BA (11.55g, 85%, 56.89mmol) are dissolved in 80ml dichloromethane, and are added in constant pressure funnel and be slowly added dropwise, then
Washed twice with dichloromethane, be then slowly ramped to room temperature, when stirring reaction 28 is small, diluted with dichloromethane, the sulfurous of 1M
Sour hydrogen sodium 355ml is washed twice, and washed once with saturated sodium bicarbonate aqueous solution, washing, and salt washing, adds anhydrous magnesium sulfate to do
It is dry, with filtered on buchner funnel, solvent is rotated, is drained to obtain 5.99g clear yellow viscous things, thick yield 92.8% with vacuum pump.
Weigh 3,4- dioctyl thiophene -1,1- dioxide (5.99g, 17.6mmol), add 1,4-benzoquinone (0.634g,
5.87mmol), glacial acetic acid 240ml is added, when reflux 24 is small after low temperature ventilation, rotary evaporation 180ml solvents, add methylene chloride dilute
Release, be washed with water three times, add anhydrous magnesium sulfate to dry, with filtered on buchner funnel, rotate solvent, drained to obtain brown with oil pump
Grease, uses petroleum ether:Dichloromethane=4:1 crosses column for eluant, eluent, drains to obtain yellow solid, adds absolute ethyl alcohol to recrystallize, obtains
To 2,3,7,8- tetra- octyl group anthraquinone 1.16g of yellow needles, 92 DEG C of fusing point, yield 30.1%.1H NMR(600MHz,CDCl3)δ
8.03 (d, J=5.9Hz, 4H), 2.79-2.67 (m, 8H), 1.63 (tt, J=34.4,17.1Hz, 8H), 1.45-1.38 (m,
8H), 1.29 (dd, J=14.5,4.5Hz, 32H), 0.91-0.85 (m, 12H)
Take tetra- octyl group anthraquinones (3.815g, 5.806mmol) of 2,3,7,8-, sodium borohydride (1.076g, 28.44mmol), nothing
Water alchlor (2.121g, 15.9mmol), tetrahydrofuran 190ml, is refluxed overnight, is cooled to room temperature, and rotary evaporation falls solvent,
Add toluene to dissolve, wash, add anhydrous magnesium sulfate to dry, with filtered on buchner funnel, rotate filtrate, drain to obtain greenish yellow solid,
Column is crossed with petroleum ether, drains to obtain white solid 3.013g, with ethyl alcohol recrystallization, obtains 2,3,7,8- tetra- octyl group anthracene of white solid
2.814g, 64-65 DEG C of fusing point, yield 77.3%.1H NMR(600MHz,CDCl3)δ8.17(s,2H),7.69(s,4H),2.88–
2.68 (m, 8H), 1.71 (dt, J=15.3,7.7Hz, 8H), 1.49-1.42 (m, 8H), 1.41-1.22 (m, 32H), 0.89 (t,
J=6.7Hz, 12H)
2,3,7,8- tetra- octyl group anthracenes (1.582g, 2.5mmol) are taken, chlorination imitates 32ml, and bromine is added in constant pressure funnel
(0.839g, 5.25mmol) and 16ml chloroforms, are slowly added dropwise, snorkel leads to 1M sodium hydroxide solutions, reaction unit lucifuge, room temperature
Stir 4 it is small when, add sodium hydrogensulfite to be quenched, wash, add anhydrous magnesium sulfate to dry, filtered on buchner funnel, rotates solvent, with true
Empty pumping does to obtain yellow solid 2.775g, and column is crossed with petroleum ether, rotates solvent, and vacuum pump is drained to obtain yellow solid
1.139g, with ethyl alcohol recrystallization, obtains yellow crystals 0.872g, 90-92 DEG C of fusing point, yield 44%.1H NMR(600MHz,
CDCl3) δ 8.25 (s, 4H), 2.86-2.81 (m, 8H), 1.74 (dt, J=15.4,7.7Hz, 8H), 1.51-1.43 (m, 8H),
1.39 (dt, J=14.9,6.5Hz, 8H), 1.36-1.29 (m, 24H), 0.89 (t, J=6.9Hz, 12H)
Tetra- octyl group -9,10- dibromoanthracenes (0.25g, 0.319mmol) of 2,3,7,8-, the magnesium of activation are added in polymerization pipe
(0.0076g, 0.319mmol), changes argon gas three times, injection tetrahydrofuran 2ml, and ultrasound disappears to magnesium at 60 DEG C, injects toluene
Tetrahydrofuran is removed in 25ml, heating, and micro- back flow reaction 2 days, adds water quenching to go out, organic layer is separated, and rotates solvent, crosses silica gel
Column, is washed three times with methanol, obtains yellow powder 0.0840g, yield 42%.
Claims (5)
1. a kind of poly- anthracene compound, it is characterised in that structure is as follows：
R1~R4Long-chain for identical either different C1~C20 is connected in a manner of alkyl or alkoxy with aryl.
2. poly- anthracene compound according to claim 1, it is characterised in that its structure for it is following any one：
3. the preparation method of the poly- anthracene compound of claim 1 or 2, it is characterised in that first anamorphic zone not isoplastic 9,10-
Dibromoanthracene, is then made grignard reagent by 9,10- dibromoanthracenes and reactive magnesium, finally carries out free radical condensation polymerization under the high temperature conditions
Into poly- 9,10- anthracenes.
4. the preparation method according to claim 3 or 4, it is characterised in that comprise the following steps that：
The magnesium of not isoplastic 9, the 10- dibromoanthracenes of band and activation is added in polymerization pipe, argon gas is changed and injects tetrahydrofuran afterwards several times,
Ultrasound disappears to magnesium at 50 DEG C~70 DEG C, injects toluene or trimethylbenzene, heats and removes tetrahydrofuran, micro- back flow reaction 1~3 day,
Add water quenching to go out, organic layer is separated, rotate solvent, cross silicagel column, washed with methanol, that is, obtain purpose product.
5. application of the poly- anthracene compound of claim 1 or 2 in polymer LED.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3431221A (en) * | 1965-01-26 | 1969-03-04 | Us Army | Catalyzed wurtz-fittig synthesis |
| JPS6320326A (en) * | 1986-07-11 | 1988-01-28 | Kao Corp | Polyanthracene and its production |
| CN1820062A (en) * | 2003-07-10 | 2006-08-16 | 默克专利股份有限公司 | Substituted anthracenes |
| CN103476822A (en) * | 2011-04-07 | 2013-12-25 | 同济大学 | Polyanthrylene materials and methods for their preparation and use |
-
2017
- 2017-11-06 CN CN201711079975.8A patent/CN107973900A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3431221A (en) * | 1965-01-26 | 1969-03-04 | Us Army | Catalyzed wurtz-fittig synthesis |
| JPS6320326A (en) * | 1986-07-11 | 1988-01-28 | Kao Corp | Polyanthracene and its production |
| CN1820062A (en) * | 2003-07-10 | 2006-08-16 | 默克专利股份有限公司 | Substituted anthracenes |
| CN103476822A (en) * | 2011-04-07 | 2013-12-25 | 同济大学 | Polyanthrylene materials and methods for their preparation and use |
Non-Patent Citations (1)
| Title |
|---|
| SOUNDARAM JEEVARATHINAM ANANTHAKRISHNAN ET AL.: "A Novel Donor–Donor Polymeric Dyad of Poly(3-Hexylthiophene-Block- Oligo(anthracene-9,10-Diyl): Synthesis, Solid-State Packing, and Electronic Properties", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》 * |
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