CN106588869A - Dialkyl-substituted naphtho-dioxodibenzothiophene monomer and preparation method thereof and polymer containing dialkyl-substituted naphtho-dioxodibenzothiophene unit and application of polymer - Google Patents

Dialkyl-substituted naphtho-dioxodibenzothiophene monomer and preparation method thereof and polymer containing dialkyl-substituted naphtho-dioxodibenzothiophene unit and application of polymer Download PDF

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CN106588869A
CN106588869A CN201611009969.0A CN201611009969A CN106588869A CN 106588869 A CN106588869 A CN 106588869A CN 201611009969 A CN201611009969 A CN 201611009969A CN 106588869 A CN106588869 A CN 106588869A
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thiophene
monomer
dibenzo
naphtho
dialkyl group
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CN106588869B (en
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郭婷
傅登豪
应磊
杨伟
彭俊彪
曹镛
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Jilin Optical and Electronic Materials Co Ltd
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South China University of Technology SCUT
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Abstract

The invention discloses a dialkyl-substituted naphtho-dioxodibenzothiophene monomer and a preparation method thereof and a polymer containing a dialkyl-substituted naphtho-dioxodibenzothiophene unit and the application of the polymer. A high-absorption electron unit -SO2- exists in the dialkyl-substituted naphtho-dioxodibenzothiophene monomer, and thus the electron affinity of a molecule can be improved. Through introducing of an unsymmetrical substituting condensed ring structure and an alkyl group, the electron affinity of the monomer can be lowered, and meanwhile, solubleness of the monomer in organic solvent is improved greatly. The dialkyl-substituted naphtho-dioxodibenzothiophene monomer obtains a homopolymer or a copolymer containing the dialkyl-substituted naphtho-dioxodibenzothiophene unit through Suzuki or Stille or Yamamoto polymerization reaction, and the obtained polymer has good solubleness in the organic solvent, is suitable for solution processing, and has wide application prospects in preparation of electroluminescent devices, organic solar cells and organic field effect transistors.

Description

Dialkyl group replaces naphtho- sulfur dibenzofuran monomer and preparation method thereof to replace naphthalene with containing dialkyl group And polymer and its application of sulfur dibenzofuran unit
Technical field
The present invention relates to organic photoelectrical material technical field, and in particular to dialkyl group replaces naphtho- sulfur dibenzofuran monomer and its system Preparation Method and the polymer and its application that replace naphtho- sulfur dibenzofuran unit containing dialkyl group.
Background technology
In the past twenty years, organic electronic and photoelectronic industry, including organic/polymer LED, it is organic The fields such as field-effect transistor, organic photovoltaic cell, nonlinear optics, biosensor and laser are obtained for swift and violent development And gradually move towards industrialization.Organic electronic product has cheap, and body is light the advantages of take so as to latent with very big market Power.Therefore, organic electronic product of the exploitation with market attractiveness has attracted research institutions and Research Team numerous in the world Concern and input.And among these, developing the link that new and effective stable material undoubtedly becomes crucial.
S, S- dioxo-dibenzothiophene (SO) is a short of electricity subelement having many advantages, such as, strong electron-withdrawing group group- SO2- high molecular electron affinity, higher electron mobility can be put forward, and S atom has reached the strong state of highest price, tool There is non-oxidizability；-SO2- introducing essentially without the fluorescence quantum efficiency etc. for reducing material, particularly containing 3,7- replacement-S, The polymer of S- dioxo-dibenzothiophene units shows superior electroluminescent properties, and its luminescent device is in very big electric current Superior spectrum stability is demonstrated by density and heat-treatment temperature range, and causes people widely to pay close attention to.But due to S, The dissolubility of S- dioxo-dibenzothiophene units is poor, it is difficult to obtain high S, the polymerization of S- dioxo-dibenzothiophene unit contents Thing, and due to 3,7- replacement-S, preferably, the polymer for obtaining sends out coloured light sky blue to the flatness of S- dioxo-dibenzothiophene units, It is not enough as showing slightly for full-color EL display material.The angle for chemically synthesizing, S, S- dioxo-dibenzothiophene is unlike fluorenes or click Azoles is easily modified like that in C-9 or N-9 positions, thus greatly limit its application in field of photovoltaic materials.Cause This, develops new method come the S that is modified, and S- dioxo-dibenzothiophene units just seem very necessary.
The present invention develops new dialkyl group and replaces naphtho- sulfur dibenzofuran monomer and preparation method thereof and polymer and its application. Polymer containing the monomer has good dissolubility, is suitable for solution processing；Its luminescent device not only efficient stable, and for more Blue saturation blue light, can fully meet the requirement that full color flat panel shows.Replace S, S- dioxies-dibenzo thiophene additionally, due to dialkyl group The space steric effect of fen unit, the copolymer of naphtho- sulfur dibenzofuran unit and the triplet of homopolymer are replaced based on dialkyl group And electron mobility all will substantially increase, it is as phosphorescent light body material and electron acceptor material in white-light illuminating and solar cell Aspect will have very big application potential.
The content of the invention
Present invention aims to the deficiencies in the prior art, there is provided dialkyl group replaces naphtho- sulfur dibenzofuran monomer and its system Preparation Method.The monomer synthesizing and purifying is easy, low in raw material price, is conducive to a large amount of productions；Meanwhile, asymmetric condensed cyclic structure and length The introducing of alkyl chain plays critical effect at aspects such as reduction monomer coplanarity, raising dissolubility, machinabilitys.
The present invention also aims to provide the conjugation of the construction unit for replacing naphtho- sulfur dibenzofuran monomer containing the dialkyl group Polymer.
The present invention also aims to provide replace the conjugated polymer of naphtho- sulfur dibenzofuran unit to exist containing described dialkyl group Prepare the application in electroluminescent device, organic photovoltaic cell and organic field effect tube.
Dialkyl group replaces naphtho- sulfur dibenzofuran monomer, with following chemical structural formula：
In formula, X is Br or I atoms；R is the straight chain or branched alkyl of carbon number 1-30.
The dialkyl group replaces the preparation method of naphtho- sulfur dibenzofuran monomer, comprises the steps：
(1) under chloroform environment, with bromine by dibenzo [b, d] thiophene bromination into 2- bromine dibenzo [b, d] thiophene；
(2) 2- bromine dibenzo [b, d] thiophene is dissolved in THF, at -70～-80 DEG C, Deca butyl lithium, reaction 2～ 3 hours；Then maintain the temperature under the conditions of -70～-80 DEG C, add 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- dioxies Miscellaneous borine, after continuing to react 1～2 hour, is then warmed to room temperature reaction 18～24 hours；Prepared 2- (dibenzo [b, d] thiophene- 2- yls) -4,4,5,5- tetramethyl -1,3,2- dioxaborinates；
(3) in toluene solvant, with 2- (dibenzo [b, d] thiophene -2- bases) -4,4,5,5- tetramethyl -1,3,2- dioxies Miscellaneous borine and the bromo- 2- naphthoates of methyl 1- are reaction raw materials, under alkaline environment, palladium are closed as catalysis with four (triphenylphosphines) Agent, Suzuki, Stille or Yamamoto polyreaction is passed through 12～18 hours at 120～150 DEG C, and methyl 1- (two is obtained Benzo [b, d] thiophene -2- bases) -2- naphthoates；
(4) methyl 1- (dibenzo [b, d] thiophene -2- bases) -2- naphthoates are dissolved in THF, Deca alkyl bromination Magnesium, 100～120 DEG C of back flow reaction 12～18 hours are obtained 2- (1- (dibenzo [b, d] thiophene -2- bases) naphthalane)-isopropanol；
(5) 2- (1- (dibenzo [b, d] thiophene -2- bases) naphthalane)-isopropanol is dissolved in dichloromethane, Deca concentration For 46.5%～48% Eorontrifluoride etherate solution, 0～5 DEG C carries out ring closure reaction 1～2 hour, and 14,14- dioxanes are obtained Base -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene；
(6) be oxidant with hydrogen peroxide in acetate solvate, by 14,14- dialkyl group -14H- benzos [b] benzos [5, 6] fluorenes [1,2-d] thiophene is oxidized to monomer 14,14- dialkyl group -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- bis- Oxygen；
(7) 14,14- dialkyl group -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxies are used in sulphuric acid Bromo-succinimide bromination, obtains the dialkyl group and replaces naphtho- sulfur dibenzofuran monomer.
Further, in step (1), the temperature of the bromination is less than 5 DEG C, and the time of bromination is 12～18 hours.
Further, in step (2), 2- bromines dibenzo [b, the d] thiophene is 1 with the mol ratio of butyl lithium:1.5～1: 2。
Further, in step (2), 2- bromines dibenzo [b, the d] thiophene and 2- isopropoxy -4,4,5,5- tetramethyls The mass ratio of base -1,3,2- dioxaborinates is 1:0.9～1:1.5.
Further, in step (3), the 2- (dibenzo [b, d] thiophene -2- bases) -4,4,5,5- tetramethyl -1,3,2- The mol ratio of dioxaborinate and the bromo- 2- naphthoates of methyl 1- is 1:1.2～1:1.5.
Further, in step (4), methyl 1- (dibenzo [b, d] thiophene -2- the bases) -2- naphthoates and alkyl The mol ratio of magnesium bromide is 1:3～1:5.
Further, in step (5), 2- (1- (dibenzo [b, the d] thiophene -2- bases) naphthalane -2- bases) isopropanols with The solid-liquid ratio of Eorontrifluoride etherate solution is 4:1～4.5:1g/mL.
Further, in step (6), the oxidation reaction is reacted 2～5 hours at 100～120 DEG C.
Further, in step (7), 14,14- dialkyl group -14H- benzos [b] benzo [5,6] fluorenes [1, the 2-d] thiophene 9,9- dioxies are 1 with the molar ratio of bromo-succinimide:2～1:2.5.
Further, in step (7), the bromination reaction is reacted 18～24 hours at 0～5 DEG C.
Replace the polymer of the construction unit of naphtho- sulfur dibenzofuran monomer containing dialkyl group, with following chemical structural formula：
In formula：R for carbon number 1-30 straight chain or branched alkyl, x, y are molar fraction, 0 ＜ x≤1, x+y=1, Polymerization degree n=1～300；
Wherein：Ar has one of following structure：
In formula, R1For the straight chain or branched alkyl of carbon number 1-30.
It is described containing dialkyl group replace naphtho- sulfur dibenzofuran monomer construction unit polymer prepare electroluminescent device, Application in organic photovoltaic cell and organic field effect tube.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) monomer of the present invention increases asymmetrical condensed cyclic structure simultaneously on the basis of S, S- dioxo-dibenzothiophene units Long alkyl chain is introduced, while reducing the flatness of monomer, increases the solvent borne of monomer and its polymer, improve prepared The luminescent saturation degree of polymer and molecular weight, reduce polymer molecular chain end group defect, improve the filming performance of polymer.
(2) the invention provides effectively dialkyl group replaces the synthetic route of naphtho- sulfur dibenzofuran monomer, synthesizing and purifying is easy, Low in raw material price, is conducive to scale to prepare production.
(3) present invention replaces the conjugated polymer dissolubility in organic solvent of naphtho- sulfur dibenzofuran monomer based on dialkyl group It is good, device can be prepared with Solution processing techniques；Simultaneously as obtained polymer good electron deficiency performance guarantee its conduct Electronics and the balance of hole injection transmission during luminescent layer, so as to significantly improve the luminous efficiency of device.
Description of the drawings
Fig. 1 is the nuclear-magnetism figure that dialkyl group replaces naphtho- sulfur dibenzofuran monomer；
Fig. 2 is the thermogravimetric curve of polymer P 1, P2 and P3；
Fig. 3 is the electroluminescent spectrum of polymer P 1；
Fig. 4 is the electro-chemical test curve of polymer P 2.
Specific embodiment
Following examples are only used for that the present invention is expanded on further, and do not limit the present invention.
Embodiment 1
The preparation of 2,7- dibromo fluorenes
In the there-necked flask of 1000mL, fluorenes (60g, 301mmol), iron powder (0.84g, 15mmol) and chloroform are added (400mL), under ice bath (5 DEG C) lucifuge, the mixed liquor of bromine (35mL, 753mmol) and 115mL chloroforms is slowly dropped to into reaction In solution, finish, react 12 hours in room temperature strong stirring.Bisulfite saturated aqueous solution of sodium 200mL is added toward reaction bulb Reaction is quenched.Reaction mixture is carried out into sucking filtration, filtering residue successively uses saturation aqueous solution of sodium bisulfite, water and washing with alcohol three It is secondary, after filter residue and drying, use CHCl3Recrystallization carries out purification process, obtains white crystal 77.8g, yield：80%.1H NMR (300MHz,CDCl3)(ppm):7.54 (d, 2H), 7.44 (d, 2H), 7.31 (d, 2H), 3.86 (m, 2H).13C NMR(75MHz, CDCl3)(ppm):152.91,144.49,134.89,128.91,121.31,119.53,76.54.Elementary analysiss result: C13H8Br2, theoretical value:C, 48.14%；H, 2.46%.Actual measured value:C, 48.21%；H, 2.63%.
Embodiment 2
The preparation of the bromo- 9,9- dioctyl fluorenes (M-1) of 2,7- bis-
Under argon protection, in 500mL there-necked flasks, add 2,7- dibromo fluorenes (32.4g, 100mmol) and dimethyl sub- Sulfone (250mL), under strong stirring, add tetrabutyl ammonium bromide (1.61g, 5mmol), be then slowly added dropwise sodium hydroxide (40g, 1000mmol) 50wt% aqueous solutions, finish, reaction 2 hours, again property injection 1- bromooctanes (57.9g, 300mmol).Continue After reaction 10 hours, stopped reaction is poured into water reactant liquor, adds aqueous hydrochloric acid solution to be neutralized, and is extracted with dichloromethane, Washed 7 times with saturated common salt, be dried, after being spin-dried for solvent, crude product is purified with column chromatography method, with silica gel as fixation Phase, with petroleum ether as mobile phase, obtains after purification white solid 43.8g, yield：80%.1H NMR(300MHz,CDCl3) (ppm):7.53 (d, 2H), 7.46 (d, 2H), 7.41 (d, 2H), 1.94 (m, 4H), 1.20-1.04 (m, 20H), 0.84 (t, 6H), 0.53 (m, 4H).13C NMR(75MHz,CDCl3)(ppm):152.96,139.46,130.54,126.56,121.87, 121.54,56.11,40.52,32.17,30.26,29.54,24.04,23.01,14.51.Elementary analysiss result：C29H40Br2, Theoretical value：C, 63.51%；H, 7.31%.Actual measured value：C, 63.53%；H, 7.42%.
Embodiment 3
The preparation of double (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- the bases) -9,9- dioctyl fluorenes (M-2) of 2,7-
Under argon protection, in the long there-necked flasks of 500mL, bromo- 9, the 9- dioctyl fluorenes (21.9g, 40mmol) of 2,7- bis- are added With anhydrous tetrahydro furan 250mL, reactant liquor is cooled to into -78 DEG C with liquid nitrogen, is slowly added dropwise the hexane solution into n-BuLi (48mL, 2.5M, 120mmol), after stirring 2 hours at being kept for -78 DEG C, disposable injection 2- isopropyl -4,4,5,5- tetramethyls - 1,3,2- dioxaborinate (26g, 140mmol), allows it to be warmed to room temperature naturally, continues to react 20h.Aqueous ammonium chloride solution is added to quench Go out reaction, rotary evaporation falls most of solvent, and reactant mixture is poured into water, and extracted with dichloromethane, wash 5 times, separate Organic faciess, are dried, and filtration is spin-dried for after solvent, and crude product is purified with column chromatography method, with silica gel as fixing phase, uses stone Oily ether/dichloromethane obtains after purification white solid 43.8g, yield as mobile phase：80%.1H NMR(300MHz,CDCl3) (ppm):7.80 (d, 2H), 7.73 (s, 2H), 7.72 (d, 2H), 1.98 (m, 4H), 1.38 (s, 24H), 1.21-1.01 (m, 20H), 0.80 (t, 6H), 0.55 (m, 4H).13C NMR (75MHz, CDCl3)(ppm):150.85,144.31,134.03, 129.28,119.76,84.10,55.56,40.48,32.17,30.32,29.57,25.32,23.97,22.98,14.47.Unit Plain analysis result：C41H64O4B2, theoretical value：C, 76.73%；H, 10.05%.Actual measured value：C, 76.43%；H, 9.91%.
Embodiment 4
The preparation of 3,6- dibromo carbazoles
Carbazole (24.7g, 0.1mol), dimethylformamide 200mL is added to stir to dissolving in 500mL there-necked flasks, NBS (49.84g, 0.28mol) 120mL DMF dissolve, and ice bath is slowly added dropwise NBS solution to 0 DEG C, reacts lucifuge, drips Bi Hou, allows temperature to rise to room temperature automatically, reacts 6 hours.Reactant liquor is added drop-wise in water and is precipitated, sucking filtration obtains crude product Afterwards, by sucking filtration thing dehydrated alcohol recrystallization, drying obtains white needle-like crystals, yield：85%.1H NMR(300MHz,CDCl3) δ(ppm):8.11(d,2H),8.03(s,1H),7.51(m,2H),7.29(t,2H).Elementary analysiss result (%)：C12H7NBr2, Value of calculation：C, 44.31%；H, 2.15%；N, 4.31%；Test value：C,44.28；H,2.20；N, 4.26%.
Embodiment 5
The preparation of the bromo- N- octylcarbazols (M-3) of 3,6- bis-
3,6- dibromo carbazoles (16.25g, 0.05mol), toluene (100mL), the tetrabutyl are added in 250mL there-necked flasks Ammonium bromide (0.8g, 3.5mmol), stirring and dissolving is slowly added dropwise 50wt%KOH (11mL) solution, after again plus n-C8H17Br (19.3g, 0.1mol), after reacting by heating 24h, add water terminating reaction, and organic faciess are isolated in washing, and water mutually uses CH2Cl2After extraction Washing twice, merges organic faciess, uses anhydrous MgSO4It is dried.Vacuum distillation to be removed and obtain light yellow solid after solvent, uses petroleum ether It is recrystallized to give white powdery solids.Yield：95%.1H NMR(300MHz,CDCl3)δ(ppm):8.18(s,2H),7.56 (d,2H),7.24(d,2H),4.21(t,2H),1.83(t,2H)1.33-1.24(m,10H),0.85(t,3H).Elementary analysiss are tied Really (%)：C20H23Br2N, value of calculation：C,54.94；H,5.30；N,3.20；Test value：C,54.88；H,5.20；N, 3.26%.
Embodiment 6
The preparation of 3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl)-N- octylcarbazols (M-4)
The bromo- N- octylcarbazols (13.11g, 30mmol) of 3,6- bis-, the new ether 250mL for steaming are added in there-necked flask, is stirred Mix and be completely dissolved to clear liquid.Reactant liquor is cooled to into -78 DEG C, n-BuLi (2.5M, 75mmol) is slowly added dropwise, Continue to stir 2 hours at -78 DEG C, now reactant liquor is white paste.Then remove cold-trap and be slowly increased to room temperature reaction by it, Reactant liquor is faint yellow clear liquid.Reaction be cooled to -78 DEG C again, then disposably add 2- isopropoxies-(4,4,5, 5- tetramethyls) -1,3,2- ethylenedioxy borates (37mL, 180mmol), stir 2 hours at -78 DEG C, then temperature is risen to into room Temperature reaction terminates reaction after 24 hours.Extracted with ether, saturated common salt water washing 4 times, be dried with anhydrous magnesium sulfate.After filtration, Solvent, product petroleum ether/ethyl acetate (10 is distilled off：1) it is the purification of eluant column chromatography, obtains white crystal, yield： 45%.1H NMR(300MHz,CDCl3)δ(ppm):8.67(s,2H),7.91(d,2H),7.40(d,2H),4.31(t,2H), 1.88 (t, 2H), 1.31-0.96 (m, 34H), 0.85 (t, 3H).Elementary analysiss result (%)：C32H47B2NO4, value of calculation：C, 72.33；H,8.92；N,2.64；Test value：C,72.51；H,9.02；N,2.73.
Embodiment 7
The preparation of the octyloxy benzene of 1,4- bis-
Under argon protection, hydroquinone (2.2g, 20mmol), saturation KOH aqueous solution are added in 250mL there-necked flasks 5mL, ethanol 100mL, then stir to dissolving, are warming up to backflow, react 1 hour, Deca bromooctane under reflux state (9.65g, 50mmol), after completion of dropping, continue back flow reaction 8 hours, be cooled to room temperature, there are a large amount of flakey materials to separate out in bottle, take out Filter, the crude product ethyl alcohol recrystallization for obtaining is obtained pure products.1H NMR(300MHz,CDCl3)δ(ppm):7.03(d,4H), 4.08(t,4H),1.79-1.74(m,4H),1.46(m,4H),1.32-1.25(m,16H),0.92-0.88(m,6H).Element point Analysis result (%)：C22H38O2, value of calculation：C,78.99；H,11.45；O,9.56；Test value：C,77.88；H,11.39；O, 9.41。
Embodiment 8
The synthesis of the bromo- octyloxy benzene (M-5) of 2,5- bis- of 1,4- bis-
Take the octyloxy benzene of Isosorbide-5-Nitrae-two (3.35g, 0.01mol) to be dissolved in 100mL carbon tetrachloride, quick stirring reaction is kept away Light, when ice bath is cooled to 5 DEG C, is slowly added dropwise bromine (4g, 0.025mol), and stirring reaction overnight, then by reactant liquor is poured into full And NaHSO3In solution, it is extracted with ethyl acetate, washes, anhydrous magnesium sulfate is dried, and steams solvent, crude product petroleum ether/bis- Chloromethanes (10：1) it is the purification of eluant column chromatography, with Gossypol recrystallized from chloroform white needle-like crystals is obtained.1H NMR(300MHz, CDCl3)δ(ppm):7.20(s,2H),4.08(t,4H),1.79-1.74(m,4H),1.46(m,4H),1.32-1.25(m, 16H),0.92-0.88(m,6H).Elementary analysiss result (%)：C22H36Br2O2, value of calculation：C,53.67；H,7.37；O,6.50； Test value：C,53.52；H,7.29；O,6.38.
Embodiment 9
2,2 '-(2,5- bis- (octyloxy) -1,4- phenyl) two (4,4,5,5- tetramethyl -1,3,2- dioxaborinates) (M- 6) preparation
Take the bromo- octyloxy benzene (7.48g, 0.015mol) of 2,5- bis- of 1,4- bis- and be dissolved in the ether that 300mL re-distillations are crossed In, -78 DEG C are cooled under nitrogen atmosphere, be slowly added dropwise n-BuLi (hexane solution of 15.1mL, 2.5mol/L, 0.038mol), addition 2- isopropyl -4 after being incubated 2h at -78 DEG C, 4,5,5- tetramethyl -1,3,2- dioxaborinates (7.75mL, 0.0375mol), 48h is reacted under room temperature.Reaction is dried after terminating with ether and distilled water extraction, washing, anhydrous magnesium sulfate.Steam Go out solvent, normal hexane is recrystallized to give 3.1g white needle-like crystals, yield：35.1%.1H NMR(300MHz,CDCl3)δ (ppm):7.10(s,2H),3.97-3.93(t,4H),1.79-1.74(m,4H),1.57-1.50(m,4H),1.37-1.30(m, 40H),0.92-0.88(m,6H)。13C NMR(75MHz,CDCl3)δ(ppm):157.70,119.96,83.43,69.80, 31.88,29.68,29.51,29.35,25.08,24.85,22.67,14.07.Elementary analysiss result (%)：C34H60B2O6, meter Calculation value：C,69.63；H,10.31；O,16.37；Test value：C,69.55；H,10.19；O,16.23.
Embodiment 10
The preparation of 2- bromine dibenzo [b, d] thiophene
In 500mL there-necked flasks, add dibenzo [b, d] thiophene (22g, 0.12mol), iron powder (0.33g, 6mmol), three Chloromethanes 200mL.Ice-water bath is cooled down, and bromine (6.2mL, 0.12mol) is injected into flask with syringe.Temperature is not in bottle during Deca More than 5 DEG C.Reaction 12 hours, stopped reaction, filtration, Gossypol recrystallized from chloroform obtain white solid 19.5g, yield：62%.1H NMR (300MHz,CDCl3)δ(ppm):8.46 (d, 1H), 7.94 (d, 1H), 7.92 (d, 1H), 7.86 (d, 1H), 7.56 (t, 1H), 7.49(t,1H),744(d,1H).Elementary analysiss result (%)：C12H7BrS, value of calculation：C,54.77；H,2.68；S,12.18； Test value：C,54.68；H,2.55；S,12.04.
Embodiment 11
The preparation of 2- (dibenzo [b, d] thiophene -2- bases) -4,4,5,5- tetramethyl -1,3,2- dioxaborinates
2- bromine dibenzo [b, d] thiophene (12.0g, 45.6mmol) is dissolved in refined anhydrous THF (200mL) ,- The gradually n-BuLi (57mL, 91.2mmol) of Deca 1.6mol/L at 78 DEG C, reacts 2 hours, then Deca 2- isopropoxy- 4,4,5,5- tetramethyl -1,3,2- dioxaborinate 11.03g continue to react 1 hour at -78 DEG C, are warming up to room temperature reaction 24 Hour.Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer saline solution is washed completely, plus anhydrous slufuric acid Magnesium is dried.After solution concentration, thick pale yellow shape crude product is obtained, (eluant selects petroleum ether/dichloro with silica gel column chromatography purification Methane=5/1, v/v), obtain yellow oily liquid 8.2g, yield：58%.1H NMR(300MHz,CDCl3)δ(ppm):8.46 (d,1H),7.96(d,1H),7.94(d,1H),7.92(d,1H),7.56(t,1H),7.49(t,1H),7.44(t,1H),1.28 (t,12H).Elementary analysiss result (%)：C18H19BO2S, value of calculation：C,69.69；H,6.17；S,10.33；Test value：C, 69.57；H,6.02；S,10.14.
Embodiment 12
The preparation of methyl 1- (dibenzo [b, d] thiophene -2- bases) -2- naphthoates
In 500mL there-necked flasks, addition 2- (dibenzo [b, d] thiophene -2- bases) -4,4,5,5- tetramethyl -1,3,2- bis- Oxa- borine (7.7g, 24.82mmol), 200mL toluene stirring and dissolving is subsequently separately added into methyl 1- bromonaphthalene formic acid esters (8.55g, 32.3mmol), Na2CO3(13.15g, 124.11mmol), four butyl bromation amine (4mg, 12.4umol), organic base (10mL), deionized water 30mL, catalyst four (triphenylphosphine) closes palladium (1.43g, 1.24mmol), is heated to 150 DEG C, reaction 12h.After reactant liquor is concentrated, with silica gel column chromatography (eluant selects petroleum ether, dichloromethane=5/1, v/v), yellow is obtained Grease 5.5g, yield：60%.1H NMR(300MHz,CDCl3)δ(ppm):8.90(d,1H),8.45(d,1H),8.17(t, 1H),8.12(d,3H),7.99(d,1H),7.93(d,1H),7.82(s,1H),7.56(t,1H),7.51(t,1H),7.49(t, 1H),7.32(t,1H),3.90(t,3H).Elementary analysiss result (%)：C24H16O2S, value of calculation：C,78.24；H,4.38；S, 8.70；Test value：C,78.11；H,4.27；S,8.55.
Embodiment 13
The preparation of 2- (1- (dibenzo [b, d] thiophene -2- bases) naphthalane -2- bases) isopropanol
Methyl 1- (dibenzo [b, d] thiophene -2- bases) -2- naphthoates (5.0g, 13.6mmol) are dissolved in refined In anhydrous THF (150mL), dropwise Deca 1.6mol/L methyl-magnesium-bromide (25.4g, 40.7mmol), is warming up to 100 DEG C and heats back Stream, reacts 12h.Room temperature is cooled to, reactant mixture is poured into water, be extracted with ethyl acetate, organic layer is complete with saline solution After washing, it is dried with anhydrous magnesium sulfate.After solution concentration, with silica gel column chromatography, (eluant selects petroleum ether, dichloromethane=1/ 1, v/v) white solid 2.5g, yield, are obtained：50%.1H NMR(300MHz,CDCl3)δ(ppm):8.92(d,1H),8.45 (d,1H),8.12(t,3H),7.98(d,2H),7.93(d,1H),7.56(t,1H),7.48(d,2H),7.34(t,1H),7.09 (t,1H),5.52(s,1H),1.41(t,6H).Elementary analysiss result (%)：C25H20OS, value of calculation：C,81.49；H,5.47； S,8.70；Test value：C,81.32；H,5.31；S,8.55.
Embodiment 14
The preparation of 14,14- dimethyl -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene
2- (1- (dibenzo [b, d] thiophene -2- bases) naphthalane -2- bases) isopropanol (2.3g, 6.24mmol) is dissolved in into dichloro In methane 150mL, 0.5mL Eorontrifluoride etherate solution (concentration is 46.5%), 3 DEG C of reaction 1h are added.After solution concentration, use Silica gel column chromatography method is purified, and obtains white solid.With ethyl alcohol recrystallization twice, white crystal 1.8g, yield are filtered to obtain： 82.6%.1H NMR(300MHz,CDCl3)δ(ppm):8.85(d,1H),8.45(d,1H),8.08(t,1H),7.93(d,1H), 7.91(t,2H),7.88(d,1H),7.56(t,1H),7.49(t,1H),7.40(t,1H),7.29(t,1H),7.09(d,1H), 1.75(t,6H).Elementary analysiss result (%)：C25H18S, value of calculation：C,85.68；H,5.18；S,9.15；Test value：C, 85.53；H,5.10；S,9.04.
Embodiment 15
The preparation of 14,14- dimethyl -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxies
In 250mL there-necked flasks, 14,14- dimethyl -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene is added (10.5g, 30mmol) and acetic acid (100mL), stirring is lower to add 30mL H2O2, reaction is heated to into the lower reaction 2 of 100 DEG C of backflows little When, reaction terminates, and rotation goes solvent, crude product with methanol to carry out recrystallization, and white solid, yield are obtained after purification：85%.1H NMR (300MHz,CDCl3)δ(ppm):8.87(dd,2H),8.56(d,1H),7.98(m,2H),7.91(dd,2H),7.68(m, 2H),7.52(m,3H),1.96(t,6H).Elementary analysiss result (%)：C25H18O2S, value of calculation：C,78.51；H,4.74；S, 8.38；Test value：C,78.36；H,4.49；S,8.12.
Embodiment 16
Dialkyl group replaces the preparation of naphtho- sulfur dibenzofuran (M-7)
In 500mL single-necked flasks, 14,14- dimethyl -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene is added 9,9- dioxies (15.3g, 40mmol) and sulphuric acid (200mL), lucifuge adds NBS (17.8g, 100mmol), reacts under room temperature.With Silica gel plate point board test, to most of raw material disubstituted product is converted into, and reactant liquor is added slowly to sulfurous by stopped reaction In the ice water solution of sour hydrogen sodium, there are a large amount of solids to separate out, sucking filtration is washed successively with sodium bicarbonate aqueous solution, water and methanol.With stone Oily ether/dichloromethane carries out column chromatography for eluant, obtains white solid.Yield：70%.1H NMR(300MHz,CDCl3)δ (ppm):8.87(dd,2H),8.56(d,1H),7.91(dd,2H),7.68(m,2H),7.52(m,3H),1.96(t,6H).Unit Plain analysis result (%)：C25H16Br2O2S, value of calculation：C,55.58；H,2.99；S,5.93；Test value：C,55.39；H,2.84； S,5.81。
Fig. 1 is that the dialkyl group for preparing replaces naphtho- sulfur dibenzofuran monomer1H NMR spectras, from fig. 1, it can be seen that having 10 on phenyl ring Individual H, there is in addition 6 H at δ 1.96ppm, comply fully with the structure of molecule, illustrates that the white solid for synthesizing is target molecule.
Embodiment 17
9,9- dioctyl substituted fluorene-co-14,14- dimethyl -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene 9, The synthesis of 9- dioxy polymer (P1)
Under argon protection, 2,7- bis- (4,4,5,5- tetramethyl -1,3,2- ethylenedioxy boron are added in the two-mouth bottle of 50mL Acid esters-diyl) -9,9- bis- (octyl group) fluorenes (M-2) (321.3mg, 0.5mmol), 2,7- bis- bromo- 9,9- bis- (octyl group) fluorenes (M-1) (268.4mg, 0.49mmol), dialkyl group replaces naphtho- sulfur dibenzofuran (M-7) (5.40mg, 0.01mmol) and palladium (2.24mg, 0.01mmol) and tricyclohexyl phosphine (7.01mg, 0.025mmol), the lower injection 12mL toluene of argon protection, stirring half After hour, when being heated to 80 DEG C of backflows, tetraethyl ammonium hydroxide (20wt%) aqueous solution (4mL) is injected, under an argon atmosphere instead After answering 24 hours, phenylboric acid (18.3mg, 0.15mmol) end-blocking is added, continue to react 8h, add bromobenzene (0.3mL, 3mmol) again Secondary end-blocking, stopped reaction after 8h, is cooled to room temperature；Product is precipitated out in methyl alcohol, respectively the respectively extracting 48 of methanol and acetone Hour removes oligomer and catalyst；Then precipitate in methyl alcohol repeatedly after dissolving in toluene；Enter one using column chromatography method Step separating-purifying polymer, obtains faint yellow fibrous solids 298mg, yield after vacuum drying：85%.
Fig. 2 gives the thermogravimetric curve of polymer P 1, and as can be seen from Figure 2, the heat decomposition temperature of polymer P 1 is 412 DEG C, Illustrate that the polymer has good hot property, this is extremely important for preparing for electroluminescent device.
Fig. 3 gives the electroluminescent light spectrogram of polymer P 1, from figure 3, it can be seen that due in polymer dialkyl group take Low, the only 1mol% for the comparision contents of naphtho- sulfur dibenzofuran unit, so polymer mainly shows the electroluminescent light of polyfluorene Spectrogram, its maximum emission peak position is at 434nm.
Embodiment 18
3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl)-N- octylcarbazol-co-14,14- diformazans The synthesis of base -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy polymer (P2)
Under argon protection, 3,6- bis- (4,4,5,5- tetramethyl -1,3,2- dioxa boron are added in the two-mouth bottle of 50mL Alkane-diyl)-N- octylcarbazols (M-4) (265.7mg, 0.5mmol), 3,6- bis- bromo- N- octylcarbazols (M-3) (214.2mg, 0.49mmol), dialkyl group replace naphtho- sulfur dibenzofuran (M-7) (5.40mg, 0.01mmol) and tricyclohexyl phosphine (7.01mg, 0.025mmol), the lower injection 8mL toluene of argon protection, after stirring half an hour, when being heated to 82 DEG C of backflows, injects tetraethyl hydrogen-oxygen Change ammonium (30wt%) aqueous solution (2mL), after reacting 36 hours under an argon atmosphere, add phenylboric acid (19.5mg, 0.16mmol) End-blocking, continues to react 10h, adds bromobenzene (0.35mL, 3.5mmol) to block again, and stopped reaction after 10h is cooled to room temperature；Will Product is precipitated out in methyl alcohol, removes oligomer and catalyst within 48 hours with methanol and acetone extraction respectively；Then in toluene Precipitate in methyl alcohol repeatedly after middle dissolving；Using the further separating-purifying polymer of column chromatography method, obtain after vacuum drying light Yellow powdery solid 265mg, yield：63%.
Fig. 2 gives the thermogravimetric curve of polymer P 2, and as can be seen from Figure 2, the heat decomposition temperature of polymer P 2 is 410 DEG C, Illustrate that the polymer has good hot property, this is extremely important for preparing for electroluminescent device.
Fig. 4 gives the electro-chemical test curve of polymer P 2, and as can be seen from Figure 4, the oxidizing potential of polymer P 2 is 1.24V。
Embodiment 19
Octyloxy benzene-co-14,14- dimethyl -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] the thiophene 9,9- of 2,5- bis- The synthesis of dioxy polymer (P3)
Argon protection under, add in the two-mouth bottle of 50mL 2,2 '-(2,5- bis- (octyloxies)-Isosorbide-5-Nitrae-phenyl) two (4,4, 5,5- tetramethyl -1,3,2- dioxaborinates) (M-6) (293.2mg, 0.5mmol), the bromo- octyloxy benzene (M- of 2,5- bis- of Isosorbide-5-Nitrae-two 5) (241.2mg, 0.49mmol), dialkyl group replaces naphtho- sulfur dibenzofuran (M-7) (5.40mg, 0.01mmol) and palladium (5.40mg, 0.01mmol) and tricyclohexyl phosphine (7.01mg, 0.025mmol), the lower injection 12mL toluene of argon protection, stirring half After hour, when being heated to 85 DEG C of backflows, tetraethyl ammonium hydroxide (20wt%) aqueous solution (4mL) is injected, under an argon atmosphere instead After answering 48 hours, phenylboric acid (20.7mg, 0.17mmol) end-blocking is added, continue to react 12h, add bromobenzene (0.4mL, 4mmol) Block again, stopped reaction after 12h is cooled to room temperature；Product is precipitated out in methyl alcohol, respectively with methanol and acetone extraction Remove oligomer and catalyst within 48 hours；Then precipitate in methyl alcohol repeatedly after dissolving in toluene；Entered using column chromatography method One step separating-purifying polymer, obtains light green fibrous solids 280mg, yield after vacuum drying：64%.
Fig. 2 gives the thermogravimetric curve of polymer P 3, and as can be seen from Figure 2, the heat decomposition temperature of polymer P 3 is 411 DEG C, Illustrate that the polymer has good hot property, this is extremely important for preparing for electroluminescent device.
The composition and performance of the conjugated polymer P1～P3 of preparation is enumerated as shown in table 1.
The composition and performance of the conjugated polymer P1 of table 1～P3
As shown in Table 1, based on fluorenes and benzene body prepare conjugated polymer molecular weight than larger, the system based on carbazole The molecular weight of standby conjugated polymer, it is active relatively low than fluorenes and benzene that its main cause is carbazole；Contracted by Suzuki The poly- coefficient of dispersion for reacting all conjugated polymers for preparing is narrower, and the coefficient of dispersion is located between 1.9-2.2, all polymerizations The photoluminescence quantum efficiencies of thing are higher, and photoluminescence quantum efficiencies are located between 59-70%.
It is below the preparation for replacing naphtho- sulfur dibenzofuran polymer light-emitting device based on described dialkyl group
Embodiment 20
Based on polymer 9,9- dioctyl substituted fluorene-co-14,14- dimethyl -14H- benzos [b] benzo [5,6] fluorenes [1, 2-d] thiophene 9,9- dioxy polymer (P1) electroluminescent device preparation
It is on tin indium oxide (ITO) glass of 15 Ω/, acetone, washing first to be used successively in the square resistance of well in advance Agent, deionized water and isopropanol are cleaned by ultrasonic, plasma treatment 10 minutes；Spin coating is doped with polystyrolsulfon acid on ITO Polyethoxy thiophene (PEDOT:PSS) film, thickness is 150nm.PEDOT:PSS films are dried 8 hours in vacuum drying oven at 80 DEG C； Subsequently the xylene solution (1wt%) of polymer P 1 is spin-coated on into PEDOT:The surface of PSS films, thickness is 80nm；It is last to send out It is deposited with the thick metal Al layer of a thin layer CsF (1.5nm) and 120nm on photosphere successively.
Based on single layer device structure：ITO/PEDOT:PSS/emitter/CsF/Al, single layer device prepared by polymer P 1 Maximum lumen efficiency be 3.05cd/A, maximum external quantum efficiency is 3.57%, and due to single layer device structure, hole and electronics are passed Defeated imbalance, exciton is not effectively used to light, so performance is relatively low.
The further work of device optimization is also being carried out, in single layer device structure, due to carrier transport imbalance, therefore Increase hole transmission layer or electron transfer layer in the device structure, while improving carrier transport balance, effectively will can swash Son is limited in luminescent layer, so as to be greatly enhanced device light emitting efficiency.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment Limit, other any spirit and the changes, modification, replacement made under principle without departing from the present invention, combine, simplification all should For equivalent substitute mode, it is included within protection scope of the present invention.

Claims (10)

1. dialkyl group replaces naphtho- sulfur dibenzofuran monomer, it is characterised in that with following chemical structural formula：
In formula, X is Br or I atoms；R is the straight chain or branched alkyl of carbon number 1-30.
2. the dialkyl group described in claim 1 replaces the preparation method of naphtho- sulfur dibenzofuran monomer, it is characterised in that including following step Suddenly：
(1) under chloroform environment, with bromine by dibenzo [b, d] thiophene bromination into 2- bromine dibenzo [b, d] thiophene；
(2) 2- bromine dibenzo [b, d] thiophene is dissolved in THF, at -70～-80 DEG C, Deca butyl lithium, reaction 2～3 is little When；Then maintain the temperature under the conditions of -70～-80 DEG C, add 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- dioxas Borine, after continuing to react 1～2 hour, is then warmed to room temperature reaction 18～24 hours；Prepared 2- (dibenzo [b, d] thiophene -2- Base) -4,4,5,5- tetramethyl -1,3,2- dioxaborinates；
(3) in toluene solvant, with 2- (dibenzo [b, d] thiophene -2- bases) -4,4,5,5- tetramethyl -1,3,2- dioxa boron Alkane and the bromo- 2- naphthoates of methyl 1- are reaction raw materials, under alkaline environment, palladium are closed as catalyst with four (triphenylphosphines), Pass through Suzuki coupling reactions 12～18 hours at 120～150 DEG C, methyl 1- (dibenzo [b, d] thiophene -2- bases) -2- is obtained Naphthoate；
(4) methyl 1- (dibenzo [b, d] thiophene -2- bases) -2- naphthoates are dissolved in THF, Deca alkyl bromination magnesium, 100～120 DEG C of back flow reaction 12～18 hours, are obtained 2- (1- (dibenzo [b, d] thiophene -2- bases) naphthalane)-isopropanol；
(5) 2- (1- (dibenzo [b, d] thiophene -2- bases) naphthalane)-isopropanol is dissolved in dichloromethane, Deca concentration is 46.5%～48% Eorontrifluoride etherate solution, carries out ring closure reaction 1～2 hour at 0～5 DEG C, 14,14- dioxanes are obtained Base -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene；
(6) it is oxidant with hydrogen peroxide in acetate solvate, by 14,14- dialkyl group -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene is oxidized to monomer 14,14- dialkyl group -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxies；
(7) 14,14- dialkyl group -14H- benzos [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxies are used into bromo in sulphuric acid Succimide bromination, obtains the dialkyl group and replaces naphtho- sulfur dibenzofuran monomer.
3. dialkyl group according to claim 2 replaces the preparation method of naphtho- sulfur dibenzofuran monomer, it is characterised in that step (1) in, the temperature of the bromination is less than 5 DEG C, and the time of bromination is 12～18 hours.
4. dialkyl group according to claim 2 replaces the preparation method of naphtho- sulfur dibenzofuran monomer, it is characterised in that step (2) in, 2- bromines dibenzo [b, the d] thiophene is 1 with the mol ratio of butyl lithium:1.5～1:2；The 2- bromines dibenzo [b, d] Thiophene is 1 with the mass ratio of 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- dioxaborinates:0.9～1:1.5.
5. dialkyl group according to claim 2 replaces the preparation method of naphtho- sulfur dibenzofuran monomer, it is characterised in that step (3) in, the 2- (dibenzo [b, d] thiophene -2- bases) -4,4,5,5- tetramethyl -1,3,2- dioxaborinates and methyl 1- it is bromo- The mol ratio of 2- naphthoates is 1:1.2～1:1.5；In step (4), the methyl 1- (dibenzo [b, d] thiophene -2- bases) - 2- naphthoates are 1 with the mol ratio of alkyl bromination magnesium:3～1:5.
6. dialkyl group according to claim 2 replaces the preparation method of naphtho- sulfur dibenzofuran monomer, it is characterised in that step (5) in, the material of 2- (1- (dibenzo [b, the d] thiophene -2- bases) naphthalane -2- bases) isopropanols and Eorontrifluoride etherate solution Liquor ratio is 4:1～4.5:1g/mL.
7. dialkyl group according to claim 2 replaces the preparation method of naphtho- sulfur dibenzofuran monomer, it is characterised in that step (6) in, the oxidation reaction is reacted 2～5 hours at 100～120 DEG C.
8. dialkyl group according to claim 2 replaces the preparation method of naphtho- sulfur dibenzofuran monomer, it is characterised in that step (7) in, 14,14- dialkyl group -14H- benzos [b] benzo [5,6] fluorenes [1, the 2-d] thiophene 9,9- dioxies and bromo succinyl The molar ratio of imines is 1:2～1:2.5；The bromination reaction is reacted 18～24 hours at 0～5 DEG C.
9. the polymer of the construction unit of naphtho- sulfur dibenzofuran monomer is replaced containing the dialkyl group described in claim 1, it is characterised in that With following chemical structural formula：
In formula：R is the straight chain or branched alkyl of carbon number 1-30, and x, y are molar fraction, and 0 ＜ x≤1, x+y=1 is polymerized Degree n=1～300；
Wherein, Ar has one of following structure：
In formula, R1For the straight chain or branched alkyl of carbon number 1-30.
10. the polymer described in claim 9 is preparing electroluminescent device, organic photovoltaic cell and organic field effect tube In application.
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