CN106832229A - Polymer and its application containing the hexa-atomic sulfuryl condensed ring unit of dibenzo - Google Patents

Polymer and its application containing the hexa-atomic sulfuryl condensed ring unit of dibenzo Download PDF

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CN106832229A
CN106832229A CN201611125565.8A CN201611125565A CN106832229A CN 106832229 A CN106832229 A CN 106832229A CN 201611125565 A CN201611125565 A CN 201611125565A CN 106832229 A CN106832229 A CN 106832229A
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sulfuryl
hexa
atomic
polymer
condensed ring
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杨伟
彭沣
应磊
郭婷
何锐锋
彭俊彪
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South China University of Technology SCUT
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Abstract

The invention discloses the polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo and its application.Polymer of the present invention containing the hexa-atomic sulfuryl condensed ring unit of dibenzo, obtained by Suzuki, Stille or Yamamoto polymerisation by the hexa-atomic sulfuryl condensed ring monomer of dibenzo, the hexa-atomic sulfuryl condensed ring monomer of dibenzo has the advantages that simple structure, is readily synthesized, there be beneficial to raising electron affinity the presence of sulfuryl in monomer, promote the injection and transmission of electronics, with fluorescence efficiency and chemical stability high.Inventive polymers have good dissolubility in organic solvent, are suitable for solution processing, are with a wide range of applications in organic photoelectric is particularly dark blue smooth field of organic electroluminescence.

Description

Polymer and its application containing the hexa-atomic sulfuryl condensed ring unit of dibenzo
Technical field
The present invention relates to organic photoelectrical material field, and in particular to polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo and Its application.
Background technology
The research of organic/polymer LED (O/PLED) starts from the last century 80, nineties, is a class with organic small Light emitting diode based on molecule and polymeric material, with light weight, actively luminous, visual angle is wide, low cost, low energy consumption, easy The advantages such as flexible and large size panel are made, is had broad application prospects in organic FPD and white-light illuminating field. Organic solar battery material is started in the nineties in last century, is the inexpensive green energy resource material of the new sustainable regeneration of a class Material, and large area flexible battery easily is prepared, there is huge application potential.Organic field effect tube is with organic semiconductor material Expect as the transistor device of active layer, receive with its low cost, flexible and the characteristics of broad area device can be prepared To extensive concern.Therefore, the concern and throwing of research institutions and Research Team numerous in the world have been attracted in organic photoelectric field Enter, and develop the focus received much concern in the material even more organic photoelectric field of new and effective stabilization.
The hexa-atomic sulfuryl condensed ring of dibenzo is ternary and ring, there is that simple structure, synthesis step be short, yield is high and cost of material The advantage for being easy to industrialization such as cheap.By S, oxidation of thiophene five-membered ring becomes hexatomic ring, as two in S- dioxo-dibenzothiophenes The hexa-atomic sulfuryl condensed ring of benzo.With S, S- dioxo-dibenzothiophenes are the same, and the hexa-atomic sulfuryl condensed ring of dibenzo can be in the multiple of phenyl ring Site modification obtains polymerized monomer；Sulphur atom is in highest chemical valence state in sulfuryl, with stronger chemistry and heat endurance；Together When due to the presence of sulfuryl, the electron affinity of the unit is improved, and the electron mobility of material is also strengthened so that based on this Polymer there is ambipolar feature.Additionally, compared to S, S- dioxo-dibenzothiophene units, the hexa-atomic sulfuryl of dibenzo is thick Ring element has the advantages that its is unique：1) hexatomic ring is nonplanar structure in the hexa-atomic sulfuryl condensed ring unit of dibenzo, two phenyl ring Dihedral angle is about 145 °, weakens its conjugacy, emission spectrum blue shift；2) 9 atoms in the hexa-atomic sulfuryl condensed ring unit of dibenzo It is sp3Hydridization so that the conjugacy of whole condensed ring weakens, while 9 atom changes are various, can obtain miscellaneous difference It is conjugated the derivative of intensity, it is easy to obtain different emission spectrum and be particularly dark blue photoemissive polymer.Above advantage causes two The hexa-atomic sulfuryl condensed ring unit of benzo is particularly dark blue smooth electroluminescent device and intermediate band gap polymer too in organic photoelectric field It is positive to have good application prospect in battery donor material.
Recently, some small molecule emitter materials for being based on the hexa-atomic sulfuryl condensed ring of dibenzo are reported.The strong problem combination of Soviet Union's bodyguard Into 10, the 10- dioxies-spiral shell [fluorenes -9,9- thianthrenes] of 2 ', 7 ' position brominations, and it is coupled with electron rich unit triphenylamine, carbazole, is obtained To blue light/dark blue photoemissive small molecule, wherein with the TPA-SO2 of triphen amine coupling in ITO (95nm)/HATCN (5nm)/NPB Current efficiency is under the device architecture of (30nm)/TCTA (10nm)/EML (30nm)/TPBI (30nm)/LiF (1nm) Al (90nm) 5.46cd/A, chromaticity coordinates is (0.154,0.168) [Chem.Mater., 2015,27,1100-1109.].Hereafter, report again Based on bromo- 5,5 ', 10,10 '-four oxygen thianthrenes of 2-, there is the efficient yellowish green photoemissive small molecule fluorescent material of TADF effects [Adv.Mater.2016,28,181-187.].Lee and Santos are also reported based on 2,7- bis- bromo- 9,9'- dimethyl-S, S- The external quantum efficiency high with TADF effects of dioxy thioxanthene small molecule emitter material [Organic Electronics, 2016,29,160-164；J.Mater.Chem.C,2016,4,3815-3824.].
Compared with small molecule emitter material, polymer luminescent material is more readily processed (spin coating, inkjet printing etc.), device system Make simple；Material glass transition temperature is high, it is not easy to crystallize, and device stability is improved；Can by changing comonomer ratio, Main chain or side-chain structure adjust the emission spectrum of polymer, realize the luminous of red-green-blue.And contain the hexa-atomic sulfone of dibenzo The polymer of base condensed ring unit has good dissolubility, is suitable for solution processing, has good fluorescence light as luminescent material Spectrum and efficiency higher.
The content of the invention
The invention provides hexa-atomic sulfuryl condensed ring monomer of dibenzo and preparation method thereof, and by the hexa-atomic sulfuryl condensed ring of dibenzo Monomer is incorporated into conjugated polymer, polymer of the synthesis main chain containing the hexa-atomic sulfuryl condensed ring unit of dibenzo.
The present invention provides the polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo, and is applied to making organic electroluminescence hair Optical device, organic solar batteries or organic field effect tube.
Polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo, main chain hexa-atomic sulfuryl condensed ring unit containing dibenzo, with such as Lower chemical structural formula：
In formula, x, y are the molar fraction of unit component, are met：0<X≤1, x+y=1；Polymerization degree n=1~300；
Y is C (R)2, C=N (R), C=C (R)2、Si(R)2Or SO2；R be expressed as H, D, the alkyl of carbon number 1~30 or The alkyl substituting aromatic base of cycloalkyl, carbon number 6~30；
Ar for carbon number 6~60 alkyl substituting aromatic base or carbon number 4~60 alkyl substitution aromatic heterocyclic, be as One or more of lower chemical constitution or following chemical constitution derivative：
Wherein, R1、R2Respectively H, D, the alkyl or cycloalkyl of carbon number 1~30, the alkyl of carbon number 6~30 take For aryl；
Z1、Z2, be H, D, F, itrile group, nitro, acyl group, alkoxy, carbonyl or sulfuryl.
Further, the monomer of the hexa-atomic sulfuryl condensed ring unit of the dibenzo has following chemical structural formula：
In formula, X is Br or I atoms；Y is C (R)2, C=N (R), C=C (R)2、Si(R)2Or SO2；R is expressed as H, D, carbon The alkyl or cycloalkyl of atomicity 1~30, the alkyl substituting aromatic base of carbon number 6~30.
Further, the preparation method of the monomer of the hexa-atomic sulfuryl condensed ring unit of the dibenzo comprises the following steps：
The hexa-atomic sulfuryl condensed ring dissolution of raw material of dibenzo in concentrated sulfuric acid, adds N- bromo-succinimides (NBS), normal temperature Reaction；After reaction terminates, extraction, dry, purification obtain the hexa-atomic sulfuryl condensed ring monomer of dibenzo containing meta bromo；Prepared Journey is as follows：
Further, the hexa-atomic sulfuryl condensed ring raw material of the dibenzo and the mol ratio of N- bromo-succinimides are 1: 2.2。
Further, the time of the reaction is 24 hours.
Further, the preparation method of the hexa-atomic sulfuryl condensed ring monomer of the dibenzo comprises the following steps：
The bromo- 2 iodobenzene thiophenols of 4- react under the catalysis of palladium and triphenylphosphine, and catalytic reaction obtains 2,7- dibromo thiophenes Anthracene；Again in acetic acid, hydrogen peroxide oxidation, obtain containing two sulfuryls the hexa-atomic sulfuryl condensed ring monomer of dibenzo --- 2,7- bis- is bromo- Four oxygen thianthrene monomers；Preparation process is as follows：
Further, the temperature of the catalytic reaction is 60-80 DEG C, and the time of reaction is 24 hours.
Further, the temperature of the hydrogen peroxide oxidation is 80-100 DEG C, and the time of oxidation is 8 hours.
The polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo is making organic electroluminescence device, organic solar Application in battery or organic field effect tube.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) the invention provides the synthetic route of the hexa-atomic sulfuryl condensed ring monomer of simple and effective dibenzo, and cost of material Cheap, synthetic route is short, and reaction yield is high, and monomer is easy to purification, is conducive to large-scale production；
(2) present invention is modified by multiple sites of the phenyl ring in the hexa-atomic sulfuryl condensed ring of dibenzo, obtains different The hexa-atomic sulfuryl condensed ring polymerized monomer of dibenzo；
(3) the hexa-atomic sulfuryl condensed ring monomer of dibenzo of the invention is due to the presence of sulfuryl so that the electron affinity of monomer Improve, electron mobility is also strengthened, and improves the electronic transmission performance of obtained polymer, and polymer has ambipolar Feature；
(4) in the hexa-atomic sulfuryl condensed ring of dibenzo of the present invention, the 9 atoms change in hexatomic ring is various, can obtain species The hexa-atomic sulfuryl fused-ring derivatives of dibenzo of various different conjugate lengths；
(5) in Inventive polymers, the hexa-atomic sulfuryl condensed ring unit of dibenzo is introduced, imparts polymer preferably thermally-stabilised Property；
(6) hexatomic ring in the hexa-atomic sulfuryl condensed ring monomer of dibenzo of the present invention is 9 in nonplanar structure, and hexatomic ring Atom is sp3Hydridization so that the conjugacy of whole condensed ring weakens, it is easy to obtains efficient dark blue photoemissive polymer, is The research and development of the dark blue photoemissive electroluminescent organic material of high efficiency provide a kind of new approaches.
Brief description of the drawings
Fig. 1 is the thermal gravimetric analysis curve of polymer P 1, P3 and P5；
Fig. 2 is the differential scanning calorimetric curve of polymer P 1, P3 and P5；
Fig. 3 is the uv-visible absorption spectra in polymer P 1, P3 and P5 films；
Fig. 4 is the photoluminescence spectra in polymer P 1, P3 and P5 films；
Fig. 5 is the Cyclic voltamogram curve of polymer P 1, P3 and P5；
Fig. 6 is the Devices Electroluminescent curve of polymer P 1, P3 and P5；
Fig. 7 is the device luminous efficiency-current density plot of polymer P 1, P3 and P5；
Fig. 8 is the device voltage-current density-brightness curve of polymer P 1, P3 and P5；
Fig. 9 is the uv-visible absorption spectra of the film of polymer P 30 and polymer P 30 in chloroformic solution.
Specific embodiment
The invention will be further elaborated with accompanying drawing with reference to embodiments, but the invention is not restricted to following examples.
Embodiment 1
Bromo- 9,9'- dimethyl-S, the S- dioxy thioxanthenes (M-1) of 3,6- bis-
The synthesis of bromo- 9,9'- dimethyl-S, the S- dioxy thioxanthenes (M-1) of 3,6- bis-：Under nitrogen protection, by 9,9'- diformazans Base-S, S- dioxy thioxanthene (1g, 3.87mmol) is dissolved in the 10ml concentrated sulfuric acids, lower point of 3 addition N- bromo succinyl of lucifuge state Imines (NBS, 1.52g, 8.54mmol), reacts 24 hours under normal temperature；Reaction solution is poured into 100ml frozen water, dichloromethane is used Extraction product, organic phase is washed 3 times with saturated nacl aqueous solution；It is spin-dried for solvent, the mixing of crude product tetrahydrofuran/n-hexane Solvent recrystallization 3 times, obtains clear crystal shape product (1.01g, yield 62%).1H NMR(500MHz,CDCl3)δ8.29(d, 2H),7.72(dd,2H),7.60(d,2H),1.85(s,6H)。
Embodiment 2
Bromo- 9,9'- dimethyl-S, the S- dioxy thioxanthenes (M-2) of 2,7- bis-
(1) synthesis of the bromo- 9,9'- dimethyl thioxanthenes (1) of 2,7- bis-：Nitrogen protection under, by 9,9'- dimethyl thioxanthene (1g, 4.42mmol) it is dissolved in 10ml acetic acid, the bromine (0.56ml, 11mmol) for being dissolved in 2ml acetic acid, reaction solution nature is added dropwise under ice bath Continuation is warmed to room temperature to react 6 hours；Gone out reaction with solution of sodium bisulfite essence, dichloromethane extraction product, saturated sodium-chloride is molten Liquid washing organic phase 3 times；Be spin-dried for solvent, crude product petroleum ether makees the purification of eluant, eluent column chromatography, obtain white solid (1.32g, Yield 78%).1H NMR(500MHz,CDCl3)δ7.62(d,2H),7.32(dd,2H),7.28(d,2H),1.64(s,6H)。
(2) synthesis of bromo- 9,9'- dimethyl-S, the S- dioxy thioxanthenes (M-2) of 2,7- bis-：Nitrogen protection under, by 2,7- bis-- 9,9'- dimethyl thioxanthenes (1g, 2.60mmol) are dissolved in 20ml acetic acid, are heated with stirring to 100 DEG C, are slowly added dropwise 30wt% dioxygens The aqueous solution (2ml, 20mmol), 100 DEG C are continued to react 8 hours；Cooling reaction solution, stops stirring, stands 10h, is filtrated to get thick Product, then recrystallized 3 times with tetrahydrofuran/n-hexane mixed solvent, obtain clear crystal shape product (0.81g, yield 75%) 。1H NMR(500MHz,CDCl3)δ8.03(d,2H),7.87(d,2H),7.67(dd,2H),1.87(s,6H)。
Embodiment 3
2 ', 7 '-two bromo- 10,10- dioxies-spiral shells [fluorenes -9,9- thianthrenes] (M-3)
The synthesis of (1) 2 ', 7 '-two bromo- spiral shells [fluorenes -9,9- thianthrenes] (2)：Nitrogen protection under, by 2- bromo biphenyls (1.17g, Tetrahydrofuran solution (5ml) 5mmol) is slowly dropped in magnesium chips (0.19g, 8mmol), is heated to 65 DEG C and is flowed back 4 hours, is obtained To xenyl grignard reagent；2,7- dibromos thioxanthones (1g, 2.70mmol) are added to the biphenyl grignard reagent for having prepared again In, back flow reaction 8 hours at 65 DEG C；After reaction solution cooling, tetrahydrofuran is spin-dried for, gained solid is dissolved in vinegar without treatment In acid, 118 DEG C of back flow reactions are heated to 12 hours under nitrogen protection；Reaction is finished, and reaction solution is poured slowly into frozen water, suction filtration Obtain filter residue.Dry method loading, petroleum ether makees the purification of eluant, eluent column chromatography, obtains white solid (0.82g, yield：60%).1H NMR(500MHz,CDCl3)δ7.80(d,2H),7.52(d,2H),7.30(dd,2H),7.26(m,6H),6.60(s,2H)。
The synthesis of (2) 2 ', 7 '-two bromo- 10,10- dioxies spiral shells [fluorenes -9,9- thianthrenes] (M-3)：Under nitrogen protection, by 2 ', 7 '-two bromo- spiral shells [fluorenes -9,9- thianthrenes] (1g, 1.98mmol) are dissolved in 40ml acetic acid/tetrahydrofuran (volume ratio 1:1) mixed solvent In, 70 DEG C are heated with stirring to, 30wt% hydrogen peroxide solutions (2ml, 20mmol) are slowly added dropwise, 70 DEG C are continued to react 8 hours；Cooling Reaction solution, stops stirring, stands 10 hours, is filtrated to get crude product, then recrystallize 3 with tetrahydrofuran/n-hexane mixed solvent Time, obtain the product (0.87g, yield 82%) of clear crystal shape.1H NMR(500MHz,CDCl3) δ 8.08 (d, J=8.5Hz, 2H), 7.88 (d, 2H), 7.61 (dd, 2H), 7.48 (td, J=7.6,2H), 7.38-7.26 (m, 4H), 6.66 (d, 2H).
Embodiment 4
Bromo- 5,5 ', 10,10 '-four oxygen thianthrenes (M-4) of 2,7- bis-
(1) synthesis of 2,7- dibromos thianthrene (3)：Under nitrogen protection, by the bromo- 2 iodobenzene thiophenols (1g, 3.17mmol) of 4-, vinegar Sour palladium (72mg, 0.32mmol), triphenylphosphine (0.26g, 1mmol) and sodium tert-butoxide (0.77g, 8mmol) add 10ml anhydrous In toluene, reacted 24 hours at being heated to 80 DEG C；Dichloromethane extraction product is used after reaction solution cooling, saturated common salt water washing has Machine phase three times；Solvent is spin-dried for, crude product petroleum ether makees the purification of eluant, eluent column chromatography, obtains white solid (0.49g, yield 83%)；(mass spectrum-APCI：373.9).
(2) synthesis of bromo- 5,5 ', 10,10 '-four oxygen thianthrenes (M-4) of 2,7- bis-：Under nitrogen protection, by 2,7- dibromo thianthrenes (1g, 2.67mmol) is dissolved in 20ml acetic acid, is heated with stirring to 100 DEG C, be slowly added dropwise 30wt% hydrogen peroxide solutions (4ml, 40mmol), 100 DEG C are continued to react 8 hours；Cooling reaction solution, stops stirring, stands 10h, is filtrated to get crude product, then with four Hydrogen furans/n-hexane mixed solvent is recrystallized 3 times, obtains clear crystal shape product (0.91g, yield 78%)；(mass spectrum-APCI： 437.9)。
Embodiment 5
2,7- bis- bromo- 9- (the third methylene dicyanoethyl)-S, S- dioxies thioxanthene (M-5)
(1) the bromo- 9- of 2,7- bis- (the third methylene dicyanoethyl)-S, the synthesis of S- dioxies thioxanthene (M-5)：Under nitrogen protection, by 2, The bromo- S of 7- bis-, S- dioxies thioxanthones (1g, 2.49mmol) and the third dicyan (0.18g, 2.74mmol) are dissolved in 10ml dimethyl sulfoxide (DMSO)s In, reacted 5 hours at 110 DEG C；After reaction stops cooling, suction filtration obtains red solid, and filter residue is rinsed 3 times with acetonitrile, obtains thick Product；Crude product is recrystallized with tetrahydrofuran/alcohol mixed solvent can obtain product (0.96g, yield 86%)；(mass spectrum- APCI：449.8).
Embodiment 6
The preparation of poly- (2,7- fluorenes-co-3,6-S, S- dioxy thioxanthene) (P1-P6)
The synthesis of polymer P 1：Nitrogen protection under, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) - 9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (147.9mg, 0.27mmol) and 3, Bromo- 9,9'- dimethyl-S, the S- dioxy thioxanthenes (12.5mg, 0.03mmol) of 6- bis- are dissolved in 8mL toluene, add tetraethyl Aqueous hydroxylamine solution (1ml, wt%=25%), palladium (1mg), tricyclohexyl phosphine (2mg).85 DEG C are heated to react 24 hours Afterwards, add phenyl boric acid (20mg) to block 6 hours, add bromobenzene (0.2ml) and block 6 hours.Reaction stops, and after cooling, will have Machine phase precipitating is filtered in methyl alcohol (200ml), after slightly drying, crude product priority methyl alcohol, acetone, n-hexane extracting.Use toluene Dissolving polymer, with toluene as eluent, column chromatography purification is carried out with neutral alumina.The toluene solution of concentrated polymer, then In methanol solution, filtering is dried secondary precipitating, obtains near-white fibrous polymer.
Polymer P 1：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (147.9mg, 0.27mmol) and bromo- 9, the 9'- bis- of 3,6- bis- Methyl-S, S- dioxy thioxanthene (12.5mg, 0.03mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.56(br,ArH), 7.94(br,ArH),7.89(br,ArH),7.85(br,ArH),7.68(br,ArH),2.13(br,CH2),2.02(br, CH3),1.26-1.05(br,CH2),0.85-0.75(br,CH3)。
Polymer P 2：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (131.6mg, 0.24mmol) and bromo- 9, the 9'- bis- of 3,6- bis- Methyl-S, S- dioxy thioxanthene (25.0mg, 0.06mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.56(br,ArH), 7.93(br,ArH),7.90(br,ArH),7.85(br,ArH),7.69(br,ArH),2.13(br,CH2),2.01(br, CH3),1.26-1.05(br,CH2),0.90-0.70(br,CH3)。
Polymer P 3：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (115.2mg, 0.21mmol) and bromo- 9, the 9'- bis- of 3,6- bis- Methyl-S, S- dioxy thioxanthene (37.4mg, 0.09mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.56(br,ArH), 7.94(br,ArH),7.89(br,ArH),7.85(br,ArH),7.68(br,ArH),2.12(br,CH2),2.01(br, CH3),1.26-1.05(br,CH2),0.85-0.75(br,CH3)。
Polymer P 4：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (98.7mg, 0.18mmol) and bromo- 9, the 9'- bis- of 3,6- bis- Methyl-S, S- dioxy thioxanthene (49.9mg, 0.12mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.55(br,ArH), 7.94(br,ArH),7.89(br,ArH),7.85(br,ArH),7.67(br,ArH),2.12(br,CH2),2.01(br, CH3),1.25-1.05(br,CH2),0.85-0.75(br,CH3)。
Polymer P 5：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (82.3mg, 0.15mmol) and bromo- 9, the 9'- bis- of 3,6- bis- Methyl-S, S- dioxy thioxanthene (62.4mg, 0.15mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.55(br,ArH), 7.94(br,ArH),7.89(br,ArH),7.85(br,ArH),7.68(br,ArH),2.12(br,CH2),2.01(br, CH3),1.26-1.05(br,CH2),0.85-0.75(br,CH3)。
Polymer P 6：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (65.8mg, 0.12mmol) and bromo- 9, the 9'- bis- of 3,6- bis- Methyl-S, S- dioxy thioxanthene (74.9mg, 0.18mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.55(br,ArH), 7.93(br,ArH),7.88(br,ArH),7.85(br,ArH),7.67(br,ArH),2.11(br,CH2),2.01(br, CH3),1.26-1.05(br,CH2),0.85-0.75(br,CH3)。
Wherein, the thermal gravimetric analysis curve of polymer P 1, P3 and P5 is as shown in figure 1, as shown in Figure 1, polymer P 1, P3 and P5 Heat decomposition temperature (Td, mass loss 5%) more than 400 DEG C, illustrate that polymer has more rigid molecular backbone, impart The preferable heat endurance of polymer.
The differential scanning calorimetric curve of polymer P 1, P3 and P5 as shown in Fig. 2 as shown in Figure 2, with 9,9'- dimethyl- The increase of S, S- dioxy thioxanthene content, the glass transition temperature (Tg) of polymer gradually steps up (88 DEG C to 140 DEG C), illustrates 9, The introducing of 9'- dimethyl-S, S- dioxy thioxanthene can effectively improve the heat endurance of polymer.
Uv-visible absorption spectra in polymer P 1, P3 and P5 films is as shown in figure 3, polymer is only as shown in Figure 3 There is an absworption peak wide, and absorption peak is all between 360~385nm, this is the transition suction of polymer molecule backbone π-π * Receive；As the raising of 9,9'- dimethyl-S, S- dioxy thioxanthene content, absworption peak occur obvious blue shift, this is due to unconjugated 9,9'- dimethyl-S, S- dioxy thioxanthene monomers have interrupted the conjugate length of main polymer chain so that main polymer chain conjugated degree Reduce.
Photoluminescence spectra in polymer P 1, P3 and P5 films is as shown in figure 4, as shown in Figure 4, all polymer are in Existing deep blue emission, emission peak is 426 and 446nm, a width of 44nm of half-peak of emission peak, and it is unconjugated inhale electrical unit 9, 9'- dimethyl-S, S- dioxy thioxanthene content increase will not derivative spectomstry blue shift and widthization.
The Cyclic voltamogram curve of polymer P 1, P3 and P5 as shown in figure 5, as shown in Figure 5, polymer P 1, P3 and P5 Oxidizing potential and reduction potential gradually move to right, HOMO and lumo energy are gradually reduced, and are illustrated with 9,9'- dimethyl-S, S- The increase of dioxy thioxanthene unit content, the electronegativity of polymer gradually increases, and is conducive to improving the electronic transmission performance of polymer.
Embodiment 7
The preparation of poly- (2,7- fluorenes-co-2,7-S, S- dioxy thioxanthene) (P7-P12)
The synthetic method of polymer P 7-P12 is identical with the synthetic method of polymer P 1 in embodiment 6, and difference is：Will be single Bromo- 9,9'- dimethyl-S, S- the dioxy thioxanthenes of body 3,6- bis- change bromo- 9,9'- dimethyl-S, S- the dioxy thioxanthenes of 2,7- bis- into.
Polymer P 7：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (147.9mg, 0.27mmol) and bromo- 9, the 9'- bis- of 2,7- bis- Methyl-S, S- dioxy thioxanthene (12.5mg, 0.03mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.33(br,ArH), 8.05(br,ArH),7.92-7.78(br,ArH),7.76-7.63(br,ArH),7.61(br,ArH),2.11(br,CH2), 1.26-1.05(br,CH2),0.82(br,CH3)。
Polymer P 8：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (131.6mg, 0.24mmol) and bromo- 9, the 9'- bis- of 2,7- bis- Methyl-S, S- dioxy thioxanthene (25.0mg, 0.06mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.34(br,ArH), 8.05(br,ArH),7.90-7.78(br,ArH),7.75-7.62(br,ArH),7.61(br,ArH),2.11(br,CH2), 1.26-1.05(br,CH2),0.82(br,CH3)。
Polymer P 9：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (115.2mg, 0.21mmol) and bromo- 9, the 9'- bis- of 2,7- bis- Methyl-S, S- dioxy thioxanthene (37.4mg, 0.09mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.33(br,ArH), 8.05(br,ArH),7.90-7.78(br,ArH),7.75-7.62(br,ArH),7.60(br,ArH),2.11(br,CH2), 1.26-1.05(br,CH2),0.82(br,CH3)。
Polymer P 10：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (98.7mg, 0.18mmol) and bromo- 9, the 9'- bis- of 2,7- bis- Methyl-S, S- dioxy thioxanthene (50.0mg, 0.12mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.33(br,ArH), 8.04(br,ArH),7.90-7.78(br,ArH),7.75-7.62(br,ArH),7.60(br,ArH),2.11(br,CH2), 1.26-1.05(br,CH2),0.82(br,CH3)。
Polymer P 11：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (82.3mg, 0.15mmol) and bromo- 9, the 9'- bis- of 2,7- bis- Methyl-S, S- dioxy thioxanthene (62.4mg, 0.15mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.33(br,ArH), 8.04(br,ArH),7.90-7.78(br,ArH),7.75-7.62(br,ArH),7.60(br,ArH),2.10(br,CH2), 1.26-1.05(br,CH2),0.81(br,CH3)。
Polymer P 12：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (65.8mg, 0.12mmol) and bromo- 9, the 9'- bis- of 2,7- bis- Methyl-S, S- dioxy thioxanthene (74.9mg, 0.18mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.33(br,ArH), 8.04(br,ArH),7.92-7.78(br,ArH),7.75-7.63(br,ArH),7.61(br,ArH),2.11(br,CH2), 1.26-1.05(br,CH2),0.81(br,CH3)。
Likewise, the polymer for obtaining introduces 9,9'- dimethyl-S, S- dioxy thioxanthene condensed ring unit, have polymer There is heat endurance and electronic transmission performance higher higher.
Embodiment 8
The preparation of poly- (2,7- fluorenes-co-2 ', 7 ' -10,10- dioxies-spiral shell [fluorenes -9,9- thianthrenes]) (P13-18)
The synthesis of polymer P 13：Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- borines Base) double (4- (the 2- ethyl hexanes epoxide) phenyl) fluorenes (248.0mg, 0.3mmol) of -9,9-, double (4- (the 2- second of 2,7- bis- bromo- 9,9- Base hexane epoxide) phenyl) fluorenes (197.8mg, 0.27mmol) and 2 ', 7 '-two bromo- 10,10- dioxies-spiral shells [fluorenes -9,9- thianthrenes] (16.1mg, 0.03mmol) is dissolved in 8mL toluene, adds tetraethyl aqueous hydroxylamine solution (1ml, wt%=25%), acetic acid Palladium (1mg), tricyclohexyl phosphine (2mg).Be heated to 85 DEG C reaction 24 hours after, add phenyl boric acid (20mg) block 6 hours, then add Enter bromobenzene (0.2ml) to block 6 hours.Reaction stops, and after cooling, by organic phase precipitating in methyl alcohol (200ml), filtering is slightly dry After dry, crude product priority methyl alcohol, acetone, n-hexane extracting.Polymer is dissolved with toluene, with toluene as eluent, with neutrality Aluminum oxide carries out column chromatography purification.The toluene solution of concentrated polymer, in methanol solution, filtering is dried precipitating, is obtained again Near-white fibrous polymer.
Polymer P 13：Double (4- (the 2- ethyl hexyls of 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- Alkoxy) phenyl) fluorenes (248.0mg, 0.3mmol), double (4- (the 2- ethyl hexanes epoxide) phenyl) fluorenes of 2,7- bis- bromo- 9,9- (197.8mg, 0.27mmol) and 2 ', 7 '-two bromo- 10,10- dioxies-spiral shells [fluorenes -9,9- thianthrenes] (16.1mg, 0.03mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.25(br,ArH),7.80(br,ArH),7.75(br,ArH),7.69(br,ArH), 7.63(br,ArH),7.59(br,ArH),7.55-7.51(br,ArH),7.44-7.40(br,ArH),7.24(br,ArH), 7.15(br,ArH),7.10(br,ArH),7.04(br,ArH),6.92(br,ArH),6.75(br,ArH),3.78(br, CH2),1.67(br,CH),1.48-1.28(br,CH2),0.88(br,CH3)。
Polymer P 14：Double (4- (the 2- ethyl hexyls of 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- Alkoxy) phenyl) fluorenes (248.0mg, 0.3mmol), double (4- (the 2- ethyl hexanes epoxide) phenyl) fluorenes of 2,7- bis- bromo- 9,9- (175.8mg, 0.24mmol) and 2 ', 7 '-two bromo- 10,10- dioxies-spiral shells [fluorenes -9,9- thianthrenes] (32.3mg, 0.06mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.25 (br, ArH), 7.80 (br, ArH), 7.75 (br, ArH), 7.69 (br, ArH), 7.63(br,ArH),7.59(br,ArH),7.55-7.51(br,ArH),7.44-7.40(br,ArH),7.24(br,ArH), 7.15(br,ArH),7.10(br,ArH),7.04(br,ArH),6.90(br,ArH),6.75(br,ArH),3.77(br, CH2),1.68(br,CH),1.48-1.26(br,CH2),0.88(br,CH3)。
Polymer P 15：Double (4- (the 2- ethyl hexyls of 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- Alkoxy) phenyl) fluorenes (248.0mg, 0.3mmol), double (4- (the 2- ethyl hexanes epoxide) phenyl) fluorenes of 2,7- bis- bromo- 9,9- (153.9mg, 0.21mmol) and 2 ', 7 '-two bromo- 10,10- dioxies-spiral shells [fluorenes -9,9- thianthrenes] (48.4mg, 0.09mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.25(br,ArH),7.79(br,ArH),7.75(br,ArH),7.68(br,ArH), 7.63(br,ArH),7.59(br,ArH),7.55-7.47(br,ArH),7.43-7.39(br,ArH),7.24(br,ArH), 7.15(br,ArH),7.09(br,ArH),7.04(br,ArH),6.90(br,ArH),6.74(br,ArH),3.77(br, CH2),1.67(br,CH),1.48-1.28(br,CH2),0.88(br,CH3)。
Polymer P 16：Double (4- (the 2- ethyl hexyls of 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- Alkoxy) phenyl) fluorenes (248.0mg, 0.3mmol), double (4- (the 2- ethyl hexanes epoxide) phenyl) fluorenes of 2,7- bis- bromo- 9,9- (131.9mg, 0.18mmol) and 2 ', 7 '-two bromo- 10,10- dioxies-spiral shells [fluorenes -9,9- thianthrenes] (64.6mg, 0.12mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.25(br,ArH),7.79(br,ArH),7.75(br,ArH),7.69(br,ArH), 7.63(br,ArH),7.59(br,ArH),7.55-7.47(br,ArH),7.44-7.39(br,ArH),7.24(br,ArH), 7.15(br,ArH),7.09(br,ArH),7.04(br,ArH),6.90(br,ArH),6.75(br,ArH),3.77(br, CH2),1.67(br,CH),1.48-1.28(br,CH2),0.88(br,CH3)。
Polymer P 17：Double (4- (the 2- ethyl hexyls of 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- Alkoxy) phenyl) fluorenes (248.0mg, 0.3mmol), double (4- (the 2- ethyl hexanes epoxide) phenyl) fluorenes of 2,7- bis- bromo- 9,9- (109.9mg, 0.15mmol) and 2 ', 7 '-two bromo- 10,10- dioxies-spiral shells [fluorenes -9,9- thianthrenes] (80.7mg, 0.15mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.24(br,ArH),7.79(br,ArH),7.75(br,ArH),7.69(br,ArH), 7.63(br,ArH),7.59(br,ArH),7.55-7.48(br,ArH),7.43-7.39(br,ArH),7.24(br,ArH), 7.15(br,ArH),7.09(br,ArH),7.04(br,ArH),6.90(br,ArH),6.73(br,ArH),3.78(br, CH2),1.68(br,CH),1.49-1.26(br,CH2),0.88(br,CH3)。
Polymer P 18：Double (4- (the 2- ethyl hexyls of 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- Alkoxy) phenyl) fluorenes (248.0mg, 0.3mmol), double (4- (the 2- ethyl hexanes epoxide) phenyl) fluorenes of 2,7- bis- bromo- 9,9- (87.9mg, 0.12mmol) and 2 ', 7 '-two bromo- 10,10- dioxies-spiral shells [fluorenes -9,9- thianthrenes] (96.9mg, 0.18mmol).1H NMR(500MHz,CDCl3)δ(ppm):8.25(br,ArH),7.80(br,ArH),7.75(br,ArH),7.69(br,ArH), 7.63(br,ArH),7.59(br,ArH),7.57-7.47(br,ArH),7.44-7.37(br,ArH),7.24(br,ArH), 7.15(br,ArH),7.08(br,ArH),7.04(br,ArH),6.92(br,ArH),6.73(br,ArH),3.76(br, CH2),1.67(br,CH),1.48-1.28(br,CH2),0.88(br,CH3)。
Likewise, the polymer for obtaining introduces 10,10- dioxies-spiral shell [fluorenes -9,9- thianthrenes] condensed ring unit, make polymer With heat endurance and electronic transmission performance higher higher.
Embodiment 9
The preparation of poly- (the oxygen thianthrenes of 2,7- fluorenes-co-2,7- four) (P19-P23)
The synthesis of polymer P 19：Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- borines Base) -9,9- di-n-octyls fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (154.7mg, 0.282mmol) with 2,7- bis- bromo- 5,5 ', 10,10 '-four oxygen thianthrenes (7.9mg, 0.018mmol) are dissolved in 10mL toluene, then Add tetraethyl aqueous hydroxylamine solution (1ml, wt%=25%), palladium (1mg) and tricyclohexyl phosphine (2mg).It is heated to 85 DEG C After reaction 24 hours, add phenyl boric acid (20mg) to block 6 hours, add bromobenzene (0.2ml) and block 6 hours.Reaction stops, cold But after, by organic phase precipitating in methyl alcohol (200ml), filtering, after slightly drying, crude product priority methyl alcohol, acetone, n-hexane is taken out Carry.Polymer is dissolved with toluene, with toluene as eluent, column chromatography purification is carried out with neutral alumina.The first of concentrated polymer Benzole soln, in methanol solution, filtering is dried precipitating, obtains pistac fibrous polymer again.
Polymer P 19：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (154.7mg, 0.282mmol) and 2,7- bis- bromo- 5,5 ', 10,10 '-four oxygen thianthrenes (7.9mg, 0.018mmol).(GPC：Number-average molecular weight Mn=9.52 × 104, polydispersity coefficient PDI= 2.08)
Polymer P 20：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (148.1mg, 0.27mmol) and 2,7- bis- bromo- 5,5 ', 10,10 '-four oxygen thianthrenes (13.1mg, 0.03mmol).(GPC：Mn=11.05 × 104, PDI=2.25)
Polymer P 21：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (141.5mg, 0.258mmol) and 2,7- bis- bromo- 5,5 ', 10,10 '-four oxygen thianthrenes (18.4mg, 0.042mmol).(GPC：Mn=13.20 × 104, PDI=1.97)
Polymer P 22：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (131.6mg, 0.24mmol) and 2,7- bis- bromo- 5,5 ', 10,10 '-four oxygen thianthrenes (26.3mg, 0.06mmol).(GPC：Mn=8.35 × 104, PDI=1.86)
Polymer P 23：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls) -9,9- di-n-octyl fluorenes (192.6mg, 0.3mmol), 2,7- bis- bromo- 9,9- di-n-octyls fluorenes (115.2mg, 0.21mmol) and 2,7- bis- bromo- 5,5 ', 10,10 '-four oxygen thianthrenes (39.4mg, 0.09mmol).(GPC：Mn=14.50 × 104, PDI=2.37)
Likewise, the polymer for obtaining introduces 5,5 ', 10,10 '-four oxygen thianthrene condensed ring units, make polymer have compared with Heat endurance high and electronic transmission performance higher.
Embodiment 10
The preparation of poly- (2,7- carbazoles-co-2,7-S, S- dioxy thioxanthene) (P24-P28)
The synthesis of polymer P 24：Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- borines Base)-N-9 '-heptadecyl carbazole (197.3mg, 0.3mmol), 2,7- bis- bromo- N-9 '-heptadecyl carbazole (152.1mg, 0.27mmol) with 2,7- bis- bromo- 9- (the third methylene dicyanoethyl)-S, S- dioxies thioxanthene (13.5mg, 0.03mmol) are dissolved in 10mL In toluene, tetraethyl aqueous hydroxylamine solution (1ml, wt%=25%), palladium (1mg), tricyclohexyl phosphine (2mg) are added.Plus After heat is reacted 24 hours to 85 DEG C, add phenyl boric acid (20mg) to block 6 hours, add bromobenzene (0.2ml) and block 6 hours.Instead Should stop, after cooling, by organic phase precipitating in methyl alcohol (200ml), filtering, after slightly drying, crude product priority methyl alcohol, third Ketone, n-hexane extracting.Polymer is dissolved with toluene, with toluene as eluent, column chromatography purification is carried out with neutral alumina.Concentration The toluene solution of polymer, in methanol solution, filtering is dried precipitating, obtains faint yellow fibrous polymer again.
Polymer P 24：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl carbazole (197.3mg, 0.3mmol), 2,7- bis- bromo- N-9 '-heptadecyl carbazole (152.1mg, 0.27mmol) and the bromo- 9- of 2,7- bis- (the third methylene dicyanoethyl)-S, S- dioxies thioxanthene (13.5mg, 0.03mmol).(GPC：Mn=9.58 × 104, PDI=2.44)
Polymer P 25：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl carbazole (197.3mg, 0.3mmol), 2,7- bis- bromo- N-9 '-heptadecyl carbazole (135.2mg, 0.24mmol) and the bromo- 9- of 2,7- bis- (the third methylene dicyanoethyl)-S, S- dioxies thioxanthene (27.0mg, 0.06mmol).(GPC：Mn=8.51 × 104, PDI=2.21)
Polymer P 26：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl carbazole (197.3mg, 0.3mmol), 2,7- bis- bromo- N-9 '-heptadecyl carbazole (101.4mg, 0.18mmol) and the bromo- 9- of 2,7- bis- (the third methylene dicyanoethyl)-S, S- dioxies thioxanthene (54.0mg, 0.12mmol).(GPC：Mn=6.39 × 104, PDI=2.40)
Polymer P 27：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl carbazole (197.3mg, 0.3mmol), 2,7- bis- bromo- N-9 '-heptadecyl carbazole (67.6mg, 0.12mmol) and the bromo- 9- (third of 2,7- bis- Methylene dicyanoethyl)-S, S- dioxies thioxanthene (81.0mg, 0.18mmol).(GPC：Mn=7.52 × 104, PDI=2.16)
Polymer P 28：2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl carbazole (197.3mg, 0.3mmol) and 2,7- bis- bromo- 9- (the third methylene dicyanoethyl)-S, S- dioxies thioxanthene (135.0mg, 0.30mmol). (GPC：Mn=3.33 × 104, PDI=2.06)
Likewise, the polymer for obtaining introduces 9- (the third methylene dicyanoethyl)-S, S- dioxy thioxanthene condensed ring unit, make polymerization Thing has heat endurance and electronic transmission performance higher higher.
Embodiment 11
The preparation of poly- (the oxygen thianthrenes of 2,7- carbazoles-alt-2,7- four) (P29)
Under nitrogen protection, by 2,7- bis- (4,4,5,5- tetramethyl -1,3- dioxy -2- boryls)-N-9 '-heptadecyl click Azoles (197.3mg, 0.3mmol) and bromo- 5,5 ', 10,10 '-four oxygen thianthrenes (131.4mg, 0.3mmol) of 2,7- bis- are dissolved in 12mL In toluene, tetraethyl aqueous hydroxylamine solution (1ml, wt%=25%), palladium (1mg), tricyclohexyl phosphine (2mg) are added.Rise Warm to 85 DEG C are reacted 24 hours, are subsequently adding phenyl boric acid (20mg) and are blocked 6 hours, are added bromobenzene (0.2ml) and are blocked 6 hours. Reaction stops, after cooling, by organic phase precipitating in methyl alcohol (300ml), and filtering, after slightly drying, crude product priority methyl alcohol, third Ketone, n-hexane extracting.Polymer is dissolved with toluene, with toluene as eluent, column chromatography purification is carried out with neutral alumina.Concentration Dissolved with the toluene solution of polymer, in methanol solution, filtering is dried precipitating, obtains orange red fibrous polymer again, (GPC：Mn=3.66 × 104, PDI=2.48).
The polymer for obtaining has heat endurance and electronic transmission performance higher higher.
Embodiment 12
Poly- (indeno [the 1,2-b of benzo two:5,6-b '] the oxygen thianthrenes of-Dithiophene-alt-2,7- four) (P30) preparation
Under nitrogen protection, by 2,7- bis- (tin trimethyl) -4,9- dihydro -4,4,9,9- tetra- (4- hexyls phenyl)-benzos two Indeno [1,2-b:5,6-b ']-Dithiophene (369.9mg, 0.3mmol) and 2,7- bis- bromo- 5,5 ', 10,10 '-four oxygen thianthrenes (131.4mg, 0.3mmol) is dissolved in 12ml dry toluenes, adds three (dibenzalacetone) two palladium (4mg) and three (2- Tolyl) phosphine (8mg).Reacted 24 hours at 100 DEG C, first time end-blocking, reaction 6 are carried out with 2- (tributyl tin) thiophene (20mg) After hour, second end-blocking is carried out with 2- bromothiophenes (30mg), continue to react 6 hours.Terminate reaction, question response drops to room temperature Afterwards, by reaction solution precipitating in methyl alcohol, the polymer being filtrated to get successively carries out soxhlet type with methyl alcohol, acetone, is with chloroform Eluant, eluent carries out column chromatography, dries, and obtains orange red fibrous polymer.(GPC：Mn=4.03 × 104, PDI=2.21)
The polymer for obtaining has heat endurance and electronic transmission performance higher higher.
Embodiment 13
Poly- (indeno [the 1,2-b of benzo two:5,6-b ']-Dithiophene-alt-2,7- (methylene dicyanoethyls of 9- third)-S, S- dioxies Thioxanthene) (P31) preparation
The synthetic method of polymer P 31 is identical with the synthetic method of polymer P 30 in embodiment 12, and difference is：Will be single Bromo- 5,5 ', 10,10 '-four oxygen thianthrenes of body 2,7- bis- change 2,7- bis- bromo- 9- (the third methylene dicyanoethyl)-S, S- dioxy thioxanthene into.Instead Orange cellulose shaped polymer, (GPC should be obtained：Mn=2.88 × 104, PDI=1.89).
The polymer for obtaining has heat endurance and electronic transmission performance higher higher.
Embodiment 14
The preparation of polymer electroluminescent device
The square resistance for taking well in advance is tin indium oxide (ITO) glass of 10 Ω, successively with acetone, detergent, go from Sub- water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes.The polyethoxy for having polystyrolsulfon acid is mixed in spin coating on ITO Thiophene (PEDOT:PSS) film, thickness is 40nm.PEDOT:PSS films are dried 8 hours in the vacuum drying oven at 80 DEG C.Then will be poly- The xylene solution (1wt.%) of compound is spin-coated on PEDOT:The surface of PSS films, thickness is 80nm；Finally luminescent layer on successively One layer of 1.5nm of evaporation thick CsF and the thick metal Al layers of 120nm, device architecture：ITO/PEDOT:PSS/ polymer/CsF/Al.
The performance of the electroluminescent device that polymer P 1, P3, P5, P7, P9 and P11 is prepared respectively is as shown in table 1.
The polymer electroluminescent device performance of table 1
As shown in Table 1, the polymer based on 3,6- and 2,7- substitution 9,9'- dimethyl-S, S- dioxy thioxanthene all shows Good electroluminescent properties.All polymer devices have and very low open bright voltage (3.2V) and maximum device brightness higher (more than 2500 candelas/square metre).Replace the increase of 9,9'- dimethyl-S, S- dioxy thioxanthene content with 3,6- or 2,7-, Polymer device maximum lumen efficiency and maximum external quantum efficiency gradually increase；Meanwhile, Device chromaticity coordinates CIEyIt is gradually reduced, it is real Existing CIEy≤ 0.1 deep blue emission.
Device max-flow based on the polymer P 5 that 3,6- substitutions 9,9'- dimethyl-S, S- dioxy thioxanthene content is 25% Obvious results rate is 1.64 candelas/ampere, maximum external quantum efficiency position 3.36%, 2686 candelas of high-high brightness position/square metre, color Coordinate is (0.16,0.07), is the dark blue photopolymer of high efficiency.
Wherein, the Devices Electroluminescent curve of polymer P 1, P3 and P5 is as shown in fig. 6, it will be appreciated from fig. 6 that all polymer Deep blue emission is all presented, transmitting main peak has acromion to launch in 425 and 450nm in 480 and 520nm；From polymer P 1 to P5, with the increase of 9,9'- dimethyl-S, S- dioxy thioxanthene unit content, the transmitting of 425nm strengthens, 450nm, 480nm and The transmitting of 520nm weakens, while emission spectrum narrows, illustrating the introducing of 9,9'- dimethyl-S, S- dioxy thioxanthene unit can make The electroluminescent spectrum blue shift of polyfluorene and narrow, realize the transmitting of dark blue light.
Device luminous efficiency-the current density plot of polymer P 1, P3 and P5 as shown in fig. 7, as shown in Figure 7, with 9, The increase of 9'- dimethyl-S, S- dioxy thioxanthene unit content, the luminous efficiency of polymer device is improved significantly.
Device voltage-current density-the brightness curve of polymer P 1, P3 and P5 as shown in figure 8, as shown in Figure 8, polymer Bright voltage and brightness higher are opened with relatively low, material filming is illustrated preferably, energy level is relative to be matched, with good fluorescence Characteristic.
The uv-visible absorption spectra of the film of polymer P 30 and polymer P 30 in chloroformic solution is as shown in figure 9, by Fig. 9 Understand, the absworption peak of polymer has obvious wideization in the case where filminess is than solution state, illustrates polymer under filminess There is strong intermolecular interaction；The optical band gap for calculating polymer according to ABSORPTION EDGE is 2.35eV, can be medium as one Band gap organic solar batteries donor.

Claims (7)

1. the polymer of the hexa-atomic sulfuryl condensed ring unit of dibenzo is contained, it is characterised in that main chain hexa-atomic sulfuryl condensed ring list containing dibenzo Unit, the structural formula of polymer is as follows：
In formula, x, y are the molar fraction of unit component, are met:0<X≤1, x+y=1；Polymerization degree n=1~300；
Y is C (R)2, C=N (R), C=C (R)2、Si(R)2Or SO2；R is expressed as the alkyl or cycloalkanes of H, D, carbon number 1~30 The alkyl substituting aromatic base of base, carbon number 6~30；
Ar is one or more of following chemical constitution or following chemical constitution derivative：
Wherein, R1、R2Respectively H, D, the alkyl or cycloalkyl of carbon number 1~30, the alkyl substitution virtue of carbon number 6~30 Base；
Z1、Z2It is H, D, F, itrile group, nitro, acyl group, alkoxy, carbonyl or sulfuryl.
2. the polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo according to claim 1, it is characterised in that the hexichol And the monomer of hexa-atomic sulfuryl condensed ring unit has following chemical structural formula：
In formula, X is Br or I atoms；Y is C (R)2, C=N (R), C=C (R)2、Si(R)2Or SO2；R is expressed as H, D, carbon number 1~30 alkyl or cycloalkyl, the alkyl substituting aromatic base of carbon number 6~30.
3. the polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo according to claim 1, it is characterised in that the hexichol And the preparation method of the monomer of hexa-atomic sulfuryl condensed ring unit comprises the following steps：
The hexa-atomic sulfuryl condensed ring dissolution of raw material of dibenzo in concentrated sulfuric acid, adds N- bromo-succinimides, normal-temperature reaction；Reaction After end, extraction, dry, purification obtain the hexa-atomic sulfuryl condensed ring monomer of dibenzo of meta bromo.
4. the polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo according to claim 3, it is characterised in that the hexichol And hexa-atomic sulfuryl condensed ring raw material and the mol ratio of N- bromo-succinimides are 1:2.2；The time of the reaction is 24 hours.
5. the polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo according to claim 1, it is characterised in that the hexichol And the preparation method of the monomer of hexa-atomic sulfuryl condensed ring unit comprises the following steps：
Under the catalysis of palladium and triphenylphosphine, catalytic reaction obtains 2,7- dibromo thianthrenes to the bromo- 2- iodobenzenes thiophenols of 4-；Again in vinegar In acid, hydrogen peroxide oxidation obtains the bromo- four oxygen thianthrene monomers of 2,7- bis- containing two sulfuryls.
6. the polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo according to claim 5, it is characterised in that the catalysis The temperature of reaction is 60-80 DEG C, and the time of reaction is 24 hours；The temperature of the hydrogen peroxide oxidation is 80-100 DEG C, oxidation Time is 8 hours.
7. the polymer containing the hexa-atomic sulfuryl condensed ring unit of dibenzo described in claim 1 make organic electroluminescence device, Application in organic solar batteries or organic field effect tube.
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CN107674184A (en) * 2017-10-23 2018-02-09 华南协同创新研究院 Water/alcohol soluble polymer containing 9,9,10,10 4 oxygen thianthrenes and preparation method and application
CN107987255A (en) * 2017-11-22 2018-05-04 华南协同创新研究院 Containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring unit polymer and its preparation method and application
CN108084407A (en) * 2017-12-13 2018-05-29 华南协同创新研究院 Polymer of seven yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene and preparation method and application
CN108276561A (en) * 2018-01-23 2018-07-13 华南协同创新研究院 A kind of polymer and the preparation method and application thereof of dioxy containing 12,12--benzothioxanthene unit
CN108409945A (en) * 2018-03-02 2018-08-17 华南协同创新研究院 Containing S, the polymer and its preparation method and application of S- dioxies-thioxanthene derivative unit
CN108586289A (en) * 2018-05-04 2018-09-28 西北大学 The aryl anthracene phenanthrene class electroluminescent organic material and its preparation method and application of malononitrile substitution

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
CN107674184A (en) * 2017-10-23 2018-02-09 华南协同创新研究院 Water/alcohol soluble polymer containing 9,9,10,10 4 oxygen thianthrenes and preparation method and application
CN107987255A (en) * 2017-11-22 2018-05-04 华南协同创新研究院 Containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring unit polymer and its preparation method and application
CN107987255B (en) * 2017-11-22 2019-12-03 华南协同创新研究院 Containing tetra- oxygen of 9,9,10,10--thianthrene, five yuan of condensed ring unit polymer and its preparation method and application
CN108084407A (en) * 2017-12-13 2018-05-29 华南协同创新研究院 Polymer of seven yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene and preparation method and application
CN108084407B (en) * 2017-12-13 2019-12-03 华南协同创新研究院 The polymer and the preparation method and application thereof of seven yuan of condensed ring units containing tetra- oxygen of 9,9,10,10--thianthrene
CN108276561A (en) * 2018-01-23 2018-07-13 华南协同创新研究院 A kind of polymer and the preparation method and application thereof of dioxy containing 12,12--benzothioxanthene unit
CN108276561B (en) * 2018-01-23 2020-08-25 华南协同创新研究院 Polymer containing 12, 12-dioxo-benzothioxanthene unit and preparation method and application thereof
CN108409945A (en) * 2018-03-02 2018-08-17 华南协同创新研究院 Containing S, the polymer and its preparation method and application of S- dioxies-thioxanthene derivative unit
CN108409945B (en) * 2018-03-02 2020-08-25 华南协同创新研究院 Polymer containing S, S-dioxo-thioxanthene derivative unit and preparation method and application thereof
CN108586289A (en) * 2018-05-04 2018-09-28 西北大学 The aryl anthracene phenanthrene class electroluminescent organic material and its preparation method and application of malononitrile substitution
CN108586289B (en) * 2018-05-04 2020-12-29 西北大学 Malononitrile substituted aryl anthracene phenanthrene organic electroluminescent material and preparation method and application thereof

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