CN106588869B - Dialkyl group replaces naphtho- sulphur dibenzofuran monomer and preparation method thereof and replaces polymer and its application of naphtho- sulphur dibenzofuran unit containing dialkyl group - Google Patents

Dialkyl group replaces naphtho- sulphur dibenzofuran monomer and preparation method thereof and replaces polymer and its application of naphtho- sulphur dibenzofuran unit containing dialkyl group Download PDF

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CN106588869B
CN106588869B CN201611009969.0A CN201611009969A CN106588869B CN 106588869 B CN106588869 B CN 106588869B CN 201611009969 A CN201611009969 A CN 201611009969A CN 106588869 B CN106588869 B CN 106588869B
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dialkyl group
thiophene
naphtho
monomer
dibenzo
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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

Replace naphtho- sulphur dibenzofuran monomer and preparation method thereof the invention discloses dialkyl group and replaces polymer and its application of naphtho- sulphur dibenzofuran unit containing dialkyl group.Dialkyl group replaces in naphtho- sulphur dibenzofuran monomer, there are strong electrophilic unit-SO2-, is conducive to mention high molecular electron affinity;The introducing of the condensed cyclic structure and alkyl of Asymmetrical substitute while advantageously reducing the electron affinity of monomer, substantially improves the dissolubility of monomer in organic solvent.Dialkyl group replaces naphtho- sulphur dibenzofuran monomer to pass through Suzuki, Stille or Yamamoto polymerization reaction obtains the homopolymer or copolymer for replacing naphtho- sulphur dibenzofuran unit containing dialkyl group, obtained polymer has good dissolubility in organic solvent, it is suitble to solution processing, has a wide range of applications in preparing electroluminescent device, organic photovoltaic cell and organic field effect tube.

Description

Dialkyl group replaces naphtho- sulphur dibenzofuran monomer and preparation method thereof to replace naphthalene with containing dialkyl group And polymer and its application of sulphur dibenzofuran unit
Technical field
The present invention relates to organic photoelectrical material technical fields, and in particular to dialkyl group replaces naphtho- sulphur dibenzofuran monomer and its system Preparation Method and polymer and its application for replacing naphtho- sulphur dibenzofuran unit containing dialkyl group.
Background technique
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 have all obtained swift and violent development And gradually move towards industrialization.Organic electronic product has many advantages, such as cheap, and body is light to be taken, and it is latent to make it have very big market Power.Therefore, there is the organic electronic product of market attractiveness to have attracted numerous in the world research institution and Research Team for exploitation Concern and investment.And among these, developing the link that new and effective stable material undoubtedly becomes crucial.
S, S- dioxo-dibenzothiophene (SO) are the short of electricity subelement having many advantages, such as, strong electron-withdrawing group group- SO2The electron affinity of molecule, higher electron mobility can be improved, and S atom has reached highest price and is good for state, tool There is inoxidizability;-SO2Introducing will not substantially reduce the fluorescence quantum efficiency etc. of material, the especially-S containing 3,7- substitution, The polymer of S- dioxo-dibenzothiophene unit shows superior electroluminescent properties, and luminescent device is in very big electric current It is demonstrated by superior spectrum stability in density and heat-treatment temperature range, and people is caused widely to pay close attention to.But due to S, The dissolubility of S- dioxo-dibenzothiophene unit is poor, it is difficult to obtain high S, the polymerization of S- dioxo-dibenzothiophene unit content Object, and since the flatness of 3,7- substitution-S, S- dioxo-dibenzothiophene unit is preferable, obtained polymer send out coloured light sky blue, It is insufficient as being shown slightly for full-color EL display material.The angle chemically synthesized, S, S- dioxo-dibenzothiophene is unlike fluorenes or click Azoles is easy to be modified at C-9 or N-9 like that, thus greatly limits its application in field of photovoltaic materials.Cause This develops new method to be modified S, and S- dioxo-dibenzothiophene unit just seems very necessary.
The present invention develops novel dialkyl group and replaces naphtho- sulphur 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, but also for more Blue saturation blue light, can fully meet the requirement that full color flat panel is shown.Replace S, S- dioxy-dibenzo thiophene additionally, due to dialkyl group The space steric effect of pheno unit replaces the copolymer of naphtho- sulphur dibenzofuran unit and the triplet of homopolymer based on dialkyl group And electron mobility will all obviously increase, as phosphorescent light body material and electron acceptor material in white-light illuminating and solar cell Aspect will have very big application potential.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to which providing dialkyl group replaces naphtho- sulphur dibenzofuran monomer and its system Preparation Method.The monomer synthesizing and purifying be easy, low in raw material price, be conducive to mass production;Meanwhile asymmetric condensed cyclic structure and length The introducing of alkyl chain reduce monomer coplanarity, improve dissolubility, in terms of play critical effect.
The object of the invention is also to provide the conjugation for the structural unit for replacing naphtho- sulphur dibenzofuran monomer containing the dialkyl group Polymer.
The object of the invention is also to provide replace the conjugated polymer of naphtho- sulphur dibenzofuran unit to exist containing the dialkyl group Prepare the application in electroluminescent device, organic photovoltaic cell and organic field effect tube.
Dialkyl group replaces naphtho- sulphur dibenzofuran monomer, has following chemical structural formula:
In formula, X is Br or I atom;R is the straight chain or branched alkyl of carbon atom number 1-30.
The dialkyl group replaces the preparation method of naphtho- sulphur dibenzofuran monomer, includes the following steps:
(1) under chloroform environment, with bromine by dibenzo [b, d] thiophene bromination at 2- bromine dibenzo [b, d] thiophene;
(2) 2- bromine dibenzo [b, d] thiophene is dissolved in THF, at -70~-80 DEG C, dropwise addition butyl lithium, reaction 2~ 3 hours;Then it maintains the temperature under the conditions of -70~-80 DEG C, 2- isopropoxy -4,4,5,5- tetramethyls -1,3,2- dioxy is added Then miscellaneous borine is warmed to room temperature reaction 18~24 hours after the reaction was continued 1~2 hour;2- (dibenzo [b, d] thiophene-is made 2- yl) -4,4,5,5- tetramethyl -1,3,2- dioxaborinate;
(3) in toluene solvant, with 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyls -1,3,2- dioxy Miscellaneous borine and the bromo- 2- naphthoate of methyl 1- are reaction raw materials, and under alkaline environment, closing palladium with four (triphenylphosphines) is catalysis Methyl 1- (two is made by Suzuki, Stille or Yamamoto polymerization reaction 12~18 hours at 120~150 DEG C in agent Benzo [b, d] thiophene -2- base) -2- naphthoate;
(4) methyl 1- (dibenzo [b, d] thiophene -2- base) -2- naphthoate is dissolved in THF, alkyl bromination is added dropwise Magnesium, 100~120 DEG C back flow reaction 12~18 hours, be made 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane)-isopropanol;
(5) 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane)-isopropanol is dissolved in methylene chloride, concentration is added dropwise For 46.5%~48% Eorontrifluoride etherate solution, 0~5 DEG C progress ring closure reaction 1~2 hour, 14,14- dioxane is made Base -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene;
(6) be oxidant with hydrogen peroxide in acetic acid solvent, by 14,14- dialkyl group -14H- benzo [b] benzo [5, 6] fluorenes [1,2-d] thiophene is oxidized to monomer 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- bis- Oxygen;
(7) 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy is used in sulfuric acid Bromo-succinimide bromination obtains the dialkyl group and replaces naphtho- sulphur dibenzofuran monomer.
Further, in step (1), the brominated temperature is no more than 5 DEG C, and the brominated time is 12~18 hours.
Further, in step (2), the molar ratio of 2- bromine dibenzo [b, the d] thiophene and butyl lithium is 1:1.5~1: 2。
Further, in step (2), 2- bromine dibenzo [b, the d] thiophene and 2- isopropoxy -4,4,5,5- tetramethyls The mass ratio of base -1,3,2- dioxaborinate is 1:0.9~1:1.5.
Further, in step (3), the 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyls -1,3,2- The molar ratio of dioxaborinate and the bromo- 2- naphthoate of methyl 1- is 1:1.2~1:1.5.
Further, in step (4), methyl 1- (dibenzo [b, d] thiophene -2- the base) -2- naphthoate and alkyl The molar ratio of magnesium bromide is 1:3~1:5.
Further, in step (5), 2- (1- (dibenzo [b, the d] thiophene -2- base) naphthalane -2- base) isopropanol 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- benzo [b] benzo [5,6] fluorenes [1, the 2-d] thiophene The molar ratio of 9,9- dioxy and bromo-succinimide is 1:2~1:2.5.
Further, in step (7), the bromination reaction is reacted 18~24 hours at 0~5 DEG C.
Replace the polymer of the structural unit of naphtho- sulphur dibenzofuran monomer containing dialkyl group, there is following chemical structural formula:
In formula: R is the straight chain or branched alkyl of carbon atom number 1-30, and x, y are molar fraction, 0 < x≤1, x+y=1, Polymerization degree n=1~300;
Wherein: one of Ar has the following structure:
In formula, R1For the straight chain or branched alkyl of carbon atom number 1-30.
It is described containing dialkyl group replace naphtho- sulphur dibenzofuran monomer structural 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 the utility model has the advantages that
(1) monomer of the present invention increases asymmetrical condensed cyclic structure simultaneously on the basis of S, S- dioxo-dibenzothiophene unit Long alkyl chain is introduced, while reducing the flatness of monomer, increases the solvent borne of monomer and its polymer, is improved prepared The luminescent saturation degree and molecular weight of polymer reduce polymer molecule chain end group defect, improve the filming performance of polymer.
(2) the present invention provides the synthetic route that effective dialkyl group replaces naphtho- sulphur dibenzofuran monomer, synthesizing and purifying is easy, Low in raw material price is conducive to scale preparation production.
(3) the present invention is based on the conjugated polymer dissolubilities in organic solvent that dialkyl group replaces naphtho- sulphur dibenzofuran monomer It is good, device can be prepared with Solution processing techniques;Simultaneously as its conduct of the good electron deficient performance guarantee of polymer obtained The balance of electrons and holes injection transmission when luminescent layer, to significantly improve the luminous efficiency of device.
Detailed description of the invention
Fig. 1 is the nuclear-magnetism figure that dialkyl group replaces naphtho- sulphur 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 embodiment is only used for that the present invention is further explained, without limiting 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 is added (400mL), ice bath (5 DEG C) are protected from light down, and the mixed liquor of bromine (35mL, 753mmol) and 115mL chloroform is slowly dropped to reaction It in solution, finishes, is reacted 12 hours in room temperature strong stirring.Bisulfite saturated aqueous solution of sodium 200mL is added into reaction flask Quenching reaction.Reaction mixture is filtered, filter residue is successively with saturation aqueous solution of sodium bisulfite, water and ethanol washing 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.Elemental analysis 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 fluorene (M-1) of 2,7- bis-
Under argon gas protection, in 500mL three-necked flask, 2,7- dibromo fluorenes (32.4g, 100mmol) is added and dimethyl is sub- Sulfone (250mL) under strong stirring, is added tetrabutylammonium bromide (1.61g, 5mmol), be then slowly added dropwise sodium hydroxide (40g, 1000mmol) 50wt% aqueous solution finishes, and reacts 2 hours, property injection 1- bromooctane (57.9g, 300mmol) again.Continue After reaction 10 hours, stop reaction, reaction solution be poured into water, aqueous hydrochloric acid solution is added and is neutralized, is extracted with dichloromethane, It is washed 7 times with saturated common salt, it is dry, after being spin-dried for solvent, crude product is purified with column chromatography method, uses silica gel as fixation Phase, uses petroleum ether as mobile phase, obtains white solid 43.8g after purification, 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.Elemental analysis result: C29H40Br2, Theoretical value: C, 63.51%;H, 7.31%.Actual measured value: C, 63.53%;H, 7.42%.
Embodiment 3
The preparation of bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- the base) -9,9- dioctyl fluorenes (M-2) of 2,7-
Under argon gas protection, in 500mL long there-necked flask, bromo- 9, the 9- dioctyl fluorene (21.9g, 40mmol) of 2,7- bis- is added With anhydrous tetrahydro furan 250mL, reaction solution is cooled to -78 DEG C with liquid nitrogen, the hexane solution into n-BuLi is slowly added dropwise (48mL, 2.5M, 120mmol) is kept after stirring 2 hours at -78 DEG C, disposable to inject 2- isopropyl -4,4,5,5- tetramethyls - 1,3,2- dioxaborinate (26g, 140mmol), allows it to be warmed to room temperature naturally, the reaction was continued 20h.Aqueous ammonium chloride solution is added to quench It goes out reaction, rotary evaporation falls most of solvent, and reaction mixture is poured into water, and is extracted with dichloromethane, and washes 5 times, separation Organic phase dries, filters after being spin-dried for solvent, is purified with column chromatography method to crude product, uses silica gel as stationary phase, use stone Oily ether/methylene chloride obtains white solid 43.8g, yield: 80% as mobile phase after purification.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.Member Element 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 carbazole
Carbazole (24.7g, 0.1mol) is added in 500mL three-necked flask, dimethylformamide 200mL, stirring to dissolution, NBS (49.84g, 0.28mol) 120mL DMF dissolves, and NBS solution is slowly added dropwise to 0 DEG C in ice bath, and reaction is protected from light, and is dripped Bi Hou allows temperature to rise to room temperature automatically, reacts 6 hours.Reaction solution is added drop-wise in water and is precipitated, suction filtration obtains crude product Afterwards, object will be filtered to be recrystallized with dehydrated alcohol, dries, 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).Elemental analysis result (%): C12H7NBr2, Calculated value: 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- octylcarbazol (M-3) of 3,6- bis-
3,6- dibromo carbazole (16.25g, 0.05mol), toluene (100mL), the tetrabutyl are added in 250mL three-necked flask 50wt%KOH (11mL) solution is slowly added dropwise in ammonium bromide (0.8g, 3.5mmol), stirring and dissolving, after again plus n-C8H17Br (19.3g, 0.1mol) adds water to terminate reaction after heating reaction for 24 hours, and washing separation goes out organic phase, water phase CH2Cl2After extraction Washing twice, merges organic phase, with anhydrous MgSO4It is dry.Vacuum distillation obtains light yellow solid after removing 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).Elemental analysis knot Fruit (%): C20H23Br2N, calculated value: 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- tetramethyl -1,3,2- dioxaborinate-diyl)-N- octylcarbazol (M-4)
The ether 250mL that the bromo- N- octylcarbazol (13.11g, 30mmol) of 3,6- bis- is added in three-necked flask, newly steams, is stirred It mixes and is completely dissolved to clear liquid.Reaction solution is cooled to -78 DEG C, n-BuLi (2.5M, 75mmol) is slowly added dropwise, Continue stirring 2 hours at -78 DEG C, reaction solution is white paste at this time.Then cold-trap is removed to be slowly increased to react at room temperature by it, Reaction solution is faint yellow clear liquid.Reaction be cooled to -78 DEG C again, be then added at one time 2- isopropoxy-(4,4,5, 5- tetramethyl) -1,3,2- ethylenedioxy borates (37mL, 180mmol), are stirred 2 hours, then temperature is risen to room at -78 DEG C Reaction was completed after 24 hours for temperature reaction.It is extracted with ether, it is saturated common salt water washing 4 times, dry with anhydrous magnesium sulfate.After filtering, Solvent is distilled off, product petroleum ether/ethyl acetate (10:1) is eluant, eluent column Chromatographic purification, white crystal is obtained, 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).Elemental analysis result (%): C32H47B2NO4, calculated value: 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 bis- octyloxy benzene of 1,4-
Under argon gas protection, hydroquinone (2.2g, 20mmol) is added in 250mL three-necked flask, is saturated KOH aqueous solution 5mL, ethyl alcohol 100mL, then stirring is warming up to reflux to dissolving, and reacts 1 hour, dropwise addition bromooctane under reflux state (9.65g, 50mmol), after being added dropwise, continue back flow reaction 8 hours, be cooled to room temperature, there are a large amount of flakey substances to be precipitated in bottle, take out Pure products can be obtained with ethyl alcohol recrystallization in filter, obtained crude product.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 Analyse result (%): C22H38O2, calculated value: 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- bis- octyloxy benzene (M-5) of 2,5- of 1,4- bis-
It takes-two octyloxy benzene (3.35g, 0.01mol) of Isosorbide-5-Nitrae to be dissolved in 100mL carbon tetrachloride, is quickly stirred to react, keeps away When ice bath is cooled to 5 DEG C, bromine (4g, 0.025mol) is slowly added dropwise in light, is stirred to react overnight, is then poured into reaction solution full And NaHSO3It in solution, is extracted with ethyl acetate, washes, anhydrous magnesium sulfate is dry, steams solvent, and crude product is with petroleum ether/bis- Chloromethanes (10:1) is eluant, eluent column Chromatographic purification, obtains white needle-like crystals with Gossypol recrystallized from chloroform.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).Elemental analysis result (%): C22H36Br2O2, calculated value: C, 53.67;H,7.37;O,6.50; Test value: C, 53.52;H,7.29;O,6.38.
Embodiment 9
2,2 '-((the octyloxy) -1,4- of 2,5- bis- phenyl) two (4,4,5,5- tetramethyl -1,3,2- dioxaborinate) (M- 6) preparation
The bromo- bis- octyloxy benzene (7.48g, 0.015mol) of 2,5- of 1,4- bis- is taken to be dissolved in the ether that 300mL re-distillation is crossed In, be cooled to -78 DEG C under nitrogen atmosphere, be slowly added dropwise n-BuLi (hexane solution of 15.1mL, 2.5mol/L, 0.038mol), addition 2- isopropyl -4,4 after -78 DEG C of heat preservation 2h, 5,5- tetramethyls -1,3,2- dioxaborinate (7.75mL, 0.0375mol), 48h is reacted at room temperature.After reaction with ether and distilled water extraction, washing, anhydrous magnesium sulfate drying.It steams Solvent out, n-hexane are 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.Elemental analysis 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 flask, dibenzo [b, d] thiophene (22g, 0.12mol), iron powder (0.33g, 6mmol), three is added Chloromethanes 200mL.Ice-water bath is cooling, and bromine (6.2mL, 0.12mol) syringe is injected flask.When dropwise addition bottle in temperature not More than 5 DEG C.Reaction 12 hours, stops reaction, and filtering, 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).Elemental analysis result (%): C12H7BrS, calculated value: 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- base) -4,4,5,5- tetramethyl -1,3,2- dioxaborinate
2- bromine dibenzo [b, d] thiophene (12.0g, 45.6mmol) is dissolved in the anhydrous THF of purification (200mL) ,- The n-BuLi (57mL, 91.2mmol) of 1.6mol/L is gradually added dropwise at 78 DEG C, reacts 2 hours, 2- isopropoxy-is then added dropwise 4,4,5,5- tetramethyls -1,3,2- dioxaborinate 11.03g, the reaction was continued at -78 DEG C 1 hour, is warming up to room temperature reaction 24 Hour.Reaction mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, adds anhydrous slufuric acid Magnesium is dry.After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selects petroleum ether/dichloro with silica gel column chromatography purification Methane=5/1, v/v), yellow oily liquid 8.2g is obtained, 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).Elemental analysis result (%): C18H19BO2S, calculated value: 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- base) -2- naphthoate
In 500mL three-necked flask, 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyls -1,3,2- bis- is added Oxa- borine (7.7g, 24.82mmol), 200mL toluene stirring and dissolving are then 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) close palladium (1.43g, 1.24mmol), are heated to 150 DEG C, reaction 12h.After reaction solution is concentrated, with silica gel column chromatography (eluant, eluent selects petroleum ether, methylene chloride=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).Elemental analysis result (%): C24H16O2S, calculated value: 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- base) naphthalane -2- base) isopropanol
Methyl 1- (dibenzo [b, d] thiophene -2- base) -2- naphthoate (5.0g, 13.6mmol) is dissolved in purification In anhydrous THF (150mL), 1.6mol/L methyl-magnesium-bromide (25.4g, 40.7mmol) is added dropwise dropwise, is warming up to 100 DEG C and heats back Stream reacts 12h.It is cooled to room temperature, reaction mixture is poured into water, be extracted with ethyl acetate, organic layer saline solution is complete It is dry with anhydrous magnesium sulfate after washing.After solution concentration, with silica gel column chromatography, (eluant, eluent selects petroleum ether, methylene chloride=1/ 1, v/v) white solid 2.5g, is obtained, yield: 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).Elemental analysis result (%): C25H20OS, calculated value: 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- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene
2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane -2- base) isopropanol (2.3g, 6.24mmol) is dissolved in dichloro In methane 150mL, it is added 0.5mL Eorontrifluoride etherate solution (concentration 46.5%), 3 DEG C of reaction 1h.After solution concentration, use Silica gel column chromatography method purification, obtains white solid.Twice with ethyl alcohol recrystallization, white crystal 1.8g is filtered to obtain, yield: 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).Elemental analysis result (%): C25H18S, calculated value: 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- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy
In 250mL three-necked flask, 14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene is added (10.5g, 30mmol) and acetic acid (100mL), is added with stirring 30mL H2O2, it is small that reaction is heated to the lower reaction 2 of 100 DEG C of reflux When, reaction terminates, and solvent is removed in rotation, and crude product with methanol is recrystallized, and obtains white solid, yield: 85% after purification.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).Elemental analysis result (%): C25H18O2S, calculated value: 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- sulphur dibenzofuran (M-7)
In 500mL single-necked flask, 14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene is added 9,9- dioxies (15.3g, 40mmol) and sulfuric acid (200mL) are protected from light and NBS (17.8g, 100mmol) are added, reacts at room temperature.With The test of silica gel plate contact plate stops reaction, reaction solution is added slowly to sulfurous until most of raw material is converted into disubstituted product In the ice water solution of sour hydrogen sodium, there are a large amount of solids to be precipitated, filters, successively washed with sodium bicarbonate aqueous solution, water and methanol.With stone Oily ether/methylene chloride is that eluant, eluent carries out column chromatography, 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).Member Element analysis result (%): C25H16Br2O2S, calculated value: 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 of preparation replaces naphtho- sulphur dibenzofuran monomer1H NMR spectra, from fig. 1, it can be seen that having 10 on phenyl ring In addition a H has 6 H, complies fully with the structure of molecule at δ 1.96ppm, illustrate that the white solid of synthesis is target molecule.
Embodiment 17
9,9- dioctyl substituted fluorene-co-14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9, The synthesis of 9- dioxy polymer (P1)
Under argon gas protection, 2,7- bis- (4,4,5,5- tetramethyls -1,3,2- ethylenedioxy boron are added in the two-mouth bottle of 50mL Acid esters-diyl) -9,9- bis- (octyl) fluorenes (M-2) (321.3mg, 0.5mmol), 2,7- bis- bromo- 9,9- bis- (octyl) fluorenes (M-1) (268.4mg, 0.49mmol), dialkyl group replace naphtho- sulphur dibenzofuran (M-7) (5.40mg, 0.01mmol) and palladium acetate (2.24mg, 0.01mmol) and tricyclohexyl phosphine (7.01mg, 0.025mmol), argon gas protection is lower to inject 12mL toluene, stirring half After hour, when being heated to 80 DEG C of reflux, tetraethyl ammonium hydroxide (20wt%) aqueous solution (4mL) is injected, under an argon atmosphere instead After answering 24 hours, phenyl boric acid (18.3mg, 0.15mmol) sealing end is added, bromobenzene (0.3mL, 3mmol) is added again in the reaction was continued 8h Secondary sealing end stops reaction after 8h, is cooled to room temperature;Product is precipitated out in methyl alcohol, methanol and acetone respectively extract 48 respectively Hour removes oligomer and catalyst;Then it is precipitated in methyl alcohol repeatedly after being dissolved in toluene;Using column chromatography method into one Separating-purifying polymer is walked, faint yellow fibrous solids 298mg, yield: 85% are obtained after vacuum drying.
Fig. 2 gives the thermogravimetric curve of polymer P 1, and as can be seen from Figure 2, the thermal 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- sulphur dibenzofuran unit, so polymer mainly shows the electroluminescent light of polyfluorene Spectrogram, maximum emission peak position is at 434nm.
Embodiment 18
3,6- bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate-diyl)-N- octylcarbazol-co-14,14- diformazan The synthesis of base -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy polymer (P2)
Under argon gas protection, 3,6- bis- (4,4,5,5- tetramethyls -1,3,2- dioxa boron are added in the two-mouth bottle of 50mL Alkane-diyl)-N- octylcarbazol (M-4) (265.7mg, 0.5mmol), 3,6- bis- bromo- N- octylcarbazols (M-3) (214.2mg, 0.49mmol), dialkyl group replace naphtho- sulphur dibenzofuran (M-7) (5.40mg, 0.01mmol) and tricyclohexyl phosphine (7.01mg, 0.025mmol), argon gas protection is lower injects 8mL toluene, after stirring half an hour, when being heated to 82 DEG C of reflux, injects tetraethyl hydrogen-oxygen Change ammonium (30wt%) aqueous solution (2mL), after reacting 36 hours under an argon atmosphere, is added phenyl boric acid (19.5mg, 0.16mmol) Sealing end, the reaction was continued 10h are added bromobenzene (0.35mL, 3.5mmol) and block again, stop reaction after 10h, be cooled to room temperature;It will Product is precipitated out in methyl alcohol, uses 48 hours removing oligomer of methanol and acetone extraction and catalyst respectively;Then in toluene It is precipitated in methyl alcohol repeatedly after middle dissolution;Using the further separating-purifying polymer of column chromatography method, obtained 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 thermal 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
2,5- bis- octyloxy benzene-co-14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- The synthesis of dioxy polymer (P3)
Under argon gas protection, be added 2,2 '-(2,5- bis- (octyloxies)-Isosorbide-5-Nitrae-phenyl) two in the two-mouth bottle of 50mL (4,4, 5,5- tetramethyls -1,3,2- dioxaborinate) (M-6) (293.2mg, 0.5mmol), bromo- 2,5-, the bis- octyloxy benzene (M- of Isosorbide-5-Nitrae-two 5) (241.2mg, 0.49mmol), dialkyl group replace naphtho- sulphur dibenzofuran (M-7) (5.40mg, 0.01mmol) and palladium acetate (5.40mg, 0.01mmol) and tricyclohexyl phosphine (7.01mg, 0.025mmol), argon gas protection is lower to inject 12mL toluene, stirring half After hour, when being heated to 85 DEG C of reflux, tetraethyl ammonium hydroxide (20wt%) aqueous solution (4mL) is injected, under an argon atmosphere instead After answering 48 hours, phenyl boric acid (20.7mg, 0.17mmol) sealing end is added, the reaction was continued 12h, addition bromobenzene (0.4mL, 4mmol) It blocks again, stops reaction after 12h, be cooled to room temperature;Product is precipitated out in methyl alcohol, uses methanol and acetone extraction respectively 48 hours removing oligomer and catalyst;Then it is precipitated in methyl alcohol repeatedly after being dissolved in toluene;Using column chromatography method into One step separating-purifying polymer, obtains light green fibrous solids 280mg, yield: 64% after vacuum drying.
Fig. 2 gives the thermogravimetric curve of polymer P 3, and as can be seen from Figure 2, the thermal 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 conjugated polymer P1~P3 of preparation is enumerated as shown in table 1.
The composition and performance of 1 conjugated polymer P1~P3 of table
As shown in Table 1, the molecular weight of the conjugated polymer prepared based on fluorenes and benzene is bigger, with carbazole for main system The molecular weight of standby conjugated polymer is smaller, the main reason is that carbazole is lower compared with the activity of fluorenes and benzene;It is contracted by Suzuki The poly- coefficient of dispersion for reacting all conjugated polymers being prepared is relatively narrow, and the coefficient of dispersion is between 1.9-2.2, all polymerizations The photoluminescence quantum efficiencies of object are higher, and photoluminescence quantum efficiencies are between 59-70%.
The following are the preparations for replacing naphtho- sulphur dibenzofuran polymer light-emitting device based on the dialkyl group
Embodiment 20
Based on polymer 9,9- dioctyl substituted fluorene-co-14,14- dimethyl -14H- benzo [b] benzo [5,6] fluorenes [1, 2-d] thiophene 9,9- dioxy polymer (P1) electroluminescent device preparation
It is first successively to use acetone, washing on 15 Ω/ tin indium oxide (ITO) glass in the square resistance of well in advance Agent, deionized water and isopropanol ultrasonic cleaning, plasma treatment 10 minutes;Spin coating is doped with polystyrolsulfon acid on ITO Polyethoxy thiophene (PEDOT:PSS) film, with a thickness of 150nm.PEDOT:PSS film is 8 hours dry at 80 DEG C in vacuum drying oven; The xylene solution (1wt%) of polymer P 1 is then spin-coated on to the surface of PEDOT:PSS film, with a thickness of 80nm;Finally sending out The metal Al layer of a thin layer CsF (1.5nm) and 120nm thickness are successively deposited on photosphere.
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 shine, so performance is relatively low.
The work of further device optimization is also carrying out, in single layer device structure, since carrier transport is uneven, Increase hole transmission layer or electron transfer layer in the device structure, while improving carrier transport balance, will can effectively swash Son is limited in luminescent layer, to greatly improve device light emitting efficiency.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention should all For equivalent substitute mode, it is included within the scope of the present invention.

Claims (10)

1. dialkyl group replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that have following chemical structural formula:
In formula, X is Br or I atom;R is the straight chain or branched alkyl of carbon atom number 1-30.
2. the preparation method that dialkyl group described in claim 1 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that including walking as follows It is rapid:
(1) under chloroform environment, with bromine by dibenzo [b, d] thiophene bromination at 2- bromine dibenzo [b, d] thiophene;
(2) 2- bromine dibenzo [b, d] thiophene is dissolved in THF, at -70~-80 DEG C, butyl lithium is added dropwise, reaction 2~3 is small When;Then it maintains the temperature under the conditions of -70~-80 DEG C, 2- isopropoxy -4,4,5,5- tetramethyls -1,3,2- dioxa is added Then borine is warmed to room temperature reaction 18~24 hours after the reaction was continued 1~2 hour;2- (dibenzo [b, d] thiophene -2- is made Base) -4,4,5,5- tetramethyl -1,3,2- dioxaborinate;
(3) in toluene solvant, with 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyls -1,3,2- dioxa boron Alkane and the bromo- 2- naphthoate of methyl 1- are reaction raw materials, under alkaline environment, using four (triphenylphosphines) conjunction palladium as catalyst, By Suzuki coupling reaction 12~18 hours at 120~150 DEG C, methyl 1- (dibenzo [b, d] thiophene -2- base) -2- is made Naphthoate;
(4) methyl 1- (dibenzo [b, d] thiophene -2- base) -2- naphthoate is dissolved in THF, methyl-magnesium-bromide is added dropwise, 100~120 DEG C back flow reaction 12~18 hours, be made 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane)-isopropanol;
(5) 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane)-isopropanol is dissolved in methylene chloride, concentration, which is added dropwise, is 46.5%~48% Eorontrifluoride etherate solution carries out ring closure reaction 1~2 hour at 0~5 DEG C, and 14,14- dioxane is made Base -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene;
It (6) is oxidant with hydrogen peroxide in acetic acid solvent, by 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene is oxidized to monomer 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy;
(7) 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1,2-d] thiophene 9,9- dioxy is used into bromo in sulfuric acid Succimide bromination obtains the dialkyl group and replaces naphtho- sulphur dibenzofuran monomer.
3. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step (1) in, the brominated temperature is no more than 5 DEG C, and the brominated time is 12~18 hours.
4. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step (2) in, the molar ratio of 2- bromine dibenzo [b, the d] thiophene and butyl lithium is 1:1.5~1:2;The 2- bromine dibenzo [b, d] The mass ratio of thiophene and 2- isopropoxy -4,4,5,5- tetramethyl -1,3,2- dioxaborinate is 1:0.9~1:1.5.
5. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step (3) in, the 2- (dibenzo [b, d] thiophene -2- base) -4,4,5,5- tetramethyls -1,3,2- dioxaborinate and methyl 1- are bromo- The molar ratio of 2- naphthoate is 1:1.2~1:1.5;In step (4), the methyl 1- (dibenzo [b, d] thiophene -2- base) - The molar ratio of 2- naphthoate and methyl-magnesium-bromide is 1:3~1:5.
6. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step (5) in, the material of 2- (1- (dibenzo [b, d] thiophene -2- base) naphthalane -2- base) isopropanol and Eorontrifluoride etherate solution Liquor ratio is 4:1~4.5:1g/mL.
7. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step (6) in, the oxidation reaction is reacted 2~5 hours at 100~120 DEG C.
8. the preparation method that dialkyl group according to claim 2 replaces naphtho- sulphur dibenzofuran monomer, which is characterized in that step (7) in, 14,14- dialkyl group -14H- benzo [b] benzo [5,6] fluorenes [1, the 2-d] thiophene 9,9- dioxy 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. replacing the polymer of the structural unit of naphtho- sulphur dibenzofuran monomer containing dialkyl group described in claim 1, which is characterized in that With following chemical structural formula:
In formula: R is the straight chain or branched alkyl of carbon atom number 1-30, and x, y are molar fraction, 0 < x≤1, x+y=1, polymerization Spend n=1~300;
Wherein, Ar one of has the following structure:
In formula, R1For the straight chain or branched alkyl of carbon atom number 1-30.
10. polymer as claimed in claim 9 is preparing electroluminescent device, organic photovoltaic cell and organic field effect tube In application.
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