CN103224486A - S,S-dioxo-dibenzothiophene monomer containing polar substituent groups, water/alcohol soluble polymers thereof, and application thereof - Google Patents

S,S-dioxo-dibenzothiophene monomer containing polar substituent groups, water/alcohol soluble polymers thereof, and application thereof Download PDF

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CN103224486A
CN103224486A CN2013101167233A CN201310116723A CN103224486A CN 103224486 A CN103224486 A CN 103224486A CN 2013101167233 A CN2013101167233 A CN 2013101167233A CN 201310116723 A CN201310116723 A CN 201310116723A CN 103224486 A CN103224486 A CN 103224486A
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dibenzothiophene
dioxy
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CN103224486B (en
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杨伟
应磊
肖慧萍
余磊
何瑞锋
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses a S,S-dioxo-dibenzothiophene monomer containing polar substituent groups, water/alcohol soluble polymers thereof, and an application thereof The water/alcohol soluble linear polymers of the S,S-dioxo-dibenzothiophene monomer containing the polar substituent groups and hyperbranched polymers can be used as a cathode interface modification layer of high work function metals, such as aluminium and gold, and thus applied in light-emitting diodes and photovoltaic cell devices. Compared with present polymers (PFN) used for cathode interface layers, the S,S-dioxo-dibenzothiophene unit polymers containing the polar groups has relatively low highest occupied molecular orbital (HOMO) energy level and can simultaneously play effects of electron injection and hole blocking. The polymer can be dissolved in methanol, N,N-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), water and other polar solvents, and thus phenomena of interface mixing do not occur between an electron transport layer and an active layer during constructing multilayer devices.

Description

Contain polar substitution group S, S-dioxy-dibenzothiophene monomer and water/alcohol soluble polymer thereof and application
Technical field
The present invention relates to based on polar functionalities S the unitary polymkeric substance of S-dioxy-dibenzothiophene; The invention still further relates to based on polar functionalities S, the unitary polymkeric substance of S-dioxy-dibenzothiophene is as the application of embellishing cathode interface layer in photodiode and photovoltaic cell device of water/pure dissolubility.
Background technology
For organic electroluminescence device (Organic Light-emitting diodes, OLEDs), for reaching better device effect, the structures that adopt multilayer film to pile up more, between anode and luminescent layer, add one deck hole transmission layer, between negative electrode and luminescent layer, add the last layer electron transfer layer, for example some alcohol/water miscible are the polyelectrolyte and the neutral precursor thereof of main chain with poly-fluorenes, can improve metal from high work function effectively (as Al, Ag, Au) electronics to active coating injects, and can prepare multiwalled PLED device with solution method, performance meets or exceeds traditional with Ba/Al, and metals such as LiF/Al are the device of negative electrode.In addition, discover and adopt conjugated polyelectrolytes that the negative electrode of body heterojunction solar cell is modified, can reach the effect that improves device performance equally.The effect that this class polar polymkeric substance and polyelectrolyte are played comprises: can prevent the pollution of the metallic cathode of evaporation to active coating; The optimization active coating contacts with metal electrode, and the shunting resistance that improves device reduces series resistance; Effectively improve built-in electromotive force of device or the like.
" advanced function material " be 19(2009 (Adv.Funct.Mater.)) 2457 reported the homopolymerization that has hydroxyl on a series of neutral side chain amidos and copolymerization fluorenes as alcohol/water miscible electronics injecting material, the existence of hydroxyl can further increase the solvability of polymkeric substance in polar solvent on the amido.Utilize the electron injecting layer of polymkeric substance alcohol/aqueous solution spin coating can prepare high efficiency green glow, blue light and white light PLED device, in order to inquire into the relation between material structure and the performance from the angle of chemical structure, the author is by introducing the copolymerization units of electron rich respectively on the main chain of poly-fluorenes, the copolymerization units of electron deficiency and unconjugated copolymerization units have compared the electronics injection efficiency of the polymkeric substance of different backbone structures, the polymkeric substance that discovery has the electron rich main chain just can show the good electron injection efficiency, and the conjugated degree of main chain is little to the influence of material electronics injection efficiency.
" macromole " (Macromolecules) 44 (2011) 4204 reported that side chain contains poly-[(2 of diethanolamine (PCP-NOH) and phosphorous acid esters (PCP-EP), the 7-carbazole)-replace-1,4-(2, the 5-alkoxy benzene)] derivative, resulting conjugated polymers can be used as effective electron injecting layer and are used for the photodiode of high-work-function metal aluminium as negative electrode.When adopting PFO-DBT15 as luminescent layer, adopt PCP-NOH and PCP-EP to reach 1.01 and 0.88cd/A as the device luminous efficiency of electron injecting layer, surpassed the level of Ba/Al device 0.58cd/A.In addition, " polymer science magazine " (J.Polym.Sci) 49 (2011) 1263 reported a series of poly-[2, the 7-carbazole] side chain contains neutral amido, di-alcohol amido and phosphate-based, with and ionization after the polyelectrolyte derivative, finding that this [2, the 7-carbazole] class of birdsing of the same feather flock together is derived can be used as effective cathode interface layer and is applied to organic photovoltaic cell.When adopting PFO-DBT35:PC 61BM is during as photoactive layer, and the open circuit voltage and the short-circuit current of the polymkeric substance solar cell of preparation are improved simultaneously, makes its power-conversion efficiencies and improves more than 20% when adopting aluminium as negative electrode.
" materials chemistry magazine " (J.Mater.Chem.) 22 (2012) 4329 reported that side chain contains triphenylamine homopolymer (PTPA-EP and the PTPA-PO of bound phosphate groups 3Na 2), resulting water/pure dissolubility conjugated polymers can be used as interfacial layer and is used for reverse polymerization thing solar cell.Wherein, PTPA-EP can bring up to the lowest unocccupied molecular orbital energy level (LUMO) of ITO-4.3eV, is in close proximity to PC 71The lumo energy of BM, thus help electron collection more, adopt PCDTBT:PC 71BM can reach 5.27% as the reverse polymerization thing efficiency of solar cell of active coating, shows that it is used for the great potential of cathode interface layer.
Yet above-mentioned report does not all relate to based on polar functionalities S, and the unitary water/alcohol soluble polymer of S-dioxy-dibenzothiophene is as the relevant information of the application of embellishing cathode interface layer in photodiode and solar-energy photo-voltaic cell device.S, S-dioxy-dibenzothiophene has strong electron-withdrawing group group-SO 2-, have higher electron affinity and electronic mobility.Chemical material (Chem.Mater.) 20 (2008) 4499, " organic electronic " (Org.Electron.) 10 (2009) 901 and Chinese patent CN101255336 with S, S-dioxy-dibenzothiophene is introduced in the main polymer chain, obtain the blue light material of electroluminescent spectrum-stable, caused people's attention.The present invention is by being incorporated into S with polar group, S-dioxy-dibenzothiophene unit side chain, developed a series of based on S, the water/alcohol soluble polymer of S-dioxy-dibenzothiophene derivatives.This base polymer not only has excellent solubility property and Electron Injection Characteristics in environmentally friendly solvent, simultaneously because electron-withdrawing group-SO 2-introducing can further reduce simultaneously the highest occupied molecular orbital(HOMO) energy level of polymkeric substance, therefore also have the effect of hole blocking layer, will have very big application potential as the cathode interface material aspect Organic Light Emitting Diode and the solar cell.
Summary of the invention
The objective of the invention is to overcome the prior art above shortcomings, provide a class to contain polar substitution group S, S-dioxy-dibenzothiophene monomer reaches based on polar functionalities S, the simple linear polymer and the hyperbranched polymer of the unitary water of S-dioxy-dibenzothiophene/pure dissolubility.
Another object of the present invention is based on polar functionalities S with described, the simple linear polymer of the unitary water of S-dioxy-dibenzothiophene/pure dissolubility and hyperbranched polymer are used as high-work-function metal (as gold, aluminium) embellishing cathode interface layer, the application in photodiode and solar-energy photo-voltaic cell device.
Concrete technical scheme of the present invention is as follows:
One class polar substitution group replaces S, S-dioxy-dibenzothiophene monomer, and its structural formula is:
Figure BDA00003010959200031
In the formula, R is a hydrogen; Or-(CH 2) nX, n=1～30, X is diethylamino group, zwitter-ion group, diethanolamine group, Trimethylamine 99 group, bound phosphate groups and derivative thereof etc., the concrete structure formula for example:
Figure BDA00003010959200032
The described polar substitution group S that contains, the preparation method of S-dioxy-dibenzothiophene monomer comprises the steps:
(1) with the liquid bromine dibenzothiophene bromination is become 2,8-two bromo-dibenzothiophene earlier;
(2) will prepare 2,8-two bromo-S, S-dioxy-dibenzothiophene is dissolved in the refining anhydrous tetrahydro furan, add n-Butyl Lithium reaction 2 hours down at low temperature (as-78 ℃), add trimethyl borate then at low temperatures, rise to room temperature reaction again, obtain white crystal 2,8-hypoboric acid-dibenzothiophene;
(3) will obtain 2,8-hypoboric acid-dibenzothiophene places flask, adds excessive hydrogen peroxide, 50 ℃ of down reactions 5 hours, behind the purifying white solid 2,8-dihydroxyl-dibenzothiophene;
(4) under the protection of inert atmosphere, with 2,8-dihydroxyl-dibenzothiophene adds two excessive bromoalkanes and carries out alkylated reaction, obtains white solid 2,8-two (bromo alkoxyl group) dibenzothiophene;
(5) with 2,8-two (bromo alkoxyl group) dibenzothiophene is dissolved in the glacial acetic acid, behind the adding hydrogen peroxide oxidation, obtains white solid 2,8-dibromo alkoxyl group-S, S-dioxy-dibenzothiophene;
(6) with 2,8-dibromo alkoxyl group-S, S-dioxy-dibenzothiophene slow dropping liquid bromine in glacial acetic acid/trichloromethane mixed solvent carries out bromination, obtains white solid 3,7-two bromo-2,8-two (bromine alkoxyl group)-dibenzothiophene;
(7) with 3,7-two bromo-2, the alkoxyl group bromine of 8-two (bromine alkoxyl group)-dibenzothiophene side chain terminal and corresponding polar group reaction obtain polar group and replace S, S-dioxy-dibenzothiophene monomer.
One class polar functionalities S, the unitary simple linear polymer of S-dioxy-dibenzothiophene, its structure is:
Figure BDA00003010959200033
X, y are molar fraction, 0≤x≤0.7,0.3≤y≤1, and x+y=1, polymerization degree n: 1～300.Work as x=0, during y=1, described polymkeric substance is based on polar functionalities S, the homopolymer of S-dioxy-dibenzothiophene, and its structure is as follows:
Figure BDA00003010959200041
One class polar functionalities S, the hyperbranched polymer of S-dioxy-dibenzothiophene, chemical structure is as follows:
Figure BDA00003010959200042
X, y are molar fraction, 0≤x≤0.65,0.3≤y≤0.95, and x+y=0.95; The polymerization degree (n 1, n 2, n 3): 1～300.
In the formula, R is a hydrogen; Or-(CH 2) nX, n=1～30, X is diethylamino group, zwitter-ion group, diethanolamine group, Trimethylamine 99 group, bound phosphate groups and derivative thereof etc.
Described structural unit A is conjugation or non-conjugated structural unit:
Figure BDA00003010959200043
2, the 7-substituted fluorene;
Figure BDA00003010959200051
3, the 6-substituted fluorene;
2,7-replaces the spiral shell fluorenes;
Figure BDA00003010959200053
2,7-replaces the silicon fluorenes;
2, the 7-substituted carbazole;
3, the 6-substituted carbazole;
Figure BDA00003010959200056
3,9-substituted indole carbazole;
Figure BDA00003010959200057
2,8-substituted indole carbazole;
Figure BDA00003010959200061
3,9-substituted indole fluorenes;
Figure BDA00003010959200062
2,8-substituted indole fluorenes;
Figure BDA00003010959200063
1, the 4-substituted benzene;
2,2 '-replacement spiral shell fluorenes
Figure BDA00003010959200065
3,3-disubstituted indole-2-ketone
In the formula, R 2For carbonatoms is the straight or branched alkyl of 1-16.
B is conjugation or the non-conjugated structural unit with one of following chemical structural formula:
Figure BDA00003010959200066
Triphenylamine;
Triazine;
Figure BDA00003010959200071
1,3, the 5-trisubstituted benzene;
N-phenyl-3, the 6-carbazole;
Figure BDA00003010959200073
3,4,5-triphenyl-1,2,4-triazole;
Figure BDA00003010959200074
4, and 7-two (4 ', 4 "-two substituted diphenylamines) base-2,1, the 3-diazosulfide;
4, and 7-two (4 ', 4 "-two replacement triphenylamines) base-2,1, the 3-diazosulfide;
4, and 7-two (4 ', 4 "-two substituted diphenylamines) base-3,7-dibenzothiophene-S, S-dioxy;
4, and 7-two (4 ', 4 "-two replacement triphenylamines) base-3,7-dibenzothiophene-S, S-dioxy
Described based on polar functionalities S, unitary water/the alcohol soluble polymer of S-dioxy-dibenzothiophene is as the application of cathode interface material at Organic Light Emitting Diode or solar cell, to the polymer LED of multilayered structure, between luminescent layer and high-work-function metal electrode, insert the film of the described polymkeric substance of one deck; Or, between photovoltaic active coating and high-work-function metal electrode, insert the film of the described polymkeric substance of one deck to bulk heterojunction solar cell device.
Described polar functionalities S, unitary water/the alcohol soluble polymer of S-dioxy-dibenzothiophene can be used for preparing the embellishing cathode interface layer of luminescent device, be coated on the luminescent layer embellishing cathode interface layer (thickness is the 1-30 nanometer) of preparation luminescent device by spin coating, spray ink Printing or printing process with its water/methyl alcohol, DMSO isopolarity solution.Can adopt work function greater than (or equal'sing) 3.6 electron-volts stable metal (as aluminium, copper, silver, indium, nickel, lead, tin, carbon, graphite and alloy thereof) as negative electrode.Modify organic electroluminescent (electrophosphorescent or the electroluminescence) material interface of high work function cathodic metal and various emission wavelengths with the embellishing cathode interface layer, its photoelectric device is not subjected to the influence of metallic cathode work function, can obtain the quantum yield same or higher with the low workfunction metal negative electrode.
Described polar functionalities S, unitary water/the alcohol soluble polymer of S-dioxy-dibenzothiophene can be used for preparing the active interface decorative layer of organic/polymkeric substance photovoltaic device, make and realize ohmic contact between active coating and the cathodic metal, help near the effective collection of current carrier electrode, thereby the short-circuit current of raising device is to improve photoelectric transformation efficiency.Simultaneously, described polar group S, unitary water/the alcohol soluble polymer of S-dioxy-dibenzothiophene can effectively suppress the dark current of conjugated polymers/soccerballene bulk heterojunction solar cell device, thereby improves the open circuit voltage of device, can further improve the electricity conversion of device.
The present invention compared with prior art has following advantage:
(1) polar functionalities S of the present invention, S-dioxy-dibenzothiophene unit polymkeric substance can realize that to luminescent device and polymkeric substance photovoltaic device excellent electronics injects.
(2) polar functionalities S of the present invention, S-dioxy-dibenzothiophene unit polymkeric substance is compared with the existing polymkeric substance (PFN) that is used for the cathode interface layer, have the highest lower molecular orbital(MO) (HOMO) energy level that occupied, can play the effect of electronics injection/hole barrier simultaneously.
(3) polymkeric substance of the present invention is dissolvable in water methyl alcohol, N, in dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), the water isopolarity solvent, therefore the interface mixing phenomena can not take place between electron transfer layer and the active coating when constructing multilayer device.
(4) polymers soln of the present invention can be by rotation, and modes such as printing apply skim on organic light emission active coating or organic solar batteries active coating, need not long-time heating or ultraviolet lighting to change its solvability, and device preparation technology is simple.
(5) because high-work-function metals such as aluminium have excellent air and steam stability, with polar functionalities S of the present invention, the unitary conjugated polymers of S-dioxy-dibenzothiophene is modified the high-work-function metal cathode interface, the aerial good processing stability of forming of composite cathode, the stability of device is greatly improved, and in macromolecular LED demonstration and polymer solar battery the potential using value is arranged.
Description of drawings
Fig. 1 a and Fig. 1 b are respectively current density-voltage-luminosity graph of a relation and the luminous efficiency-current density graph of a relation based on red-light-emitting polymer MEH-PPV photodiode, device architecture is: ITO/PEDOT:PSS/MEH-PPV/ negative electrode (Al, PFN/Al, P1/Al, P10/Al or P12/Al).
Fig. 2 a and Fig. 2 b are respectively based on the current density-voltage of green glow polymer P-PPV photodiode-luminosity graph of a relation and luminous efficiency-current density graph of a relation, device architecture is: ITO/PEDOT:PSS/P-PPV/ negative electrode (Au, PFN/Au, P1/Au, P10/Au or P12/Au).
Fig. 3 is based on giving body polymer P FO-DBT35 bulk heterojunction solar cell device current density-voltage pattern, and device architecture is: ITO/PEDOT:PSS/PFO-DBT35:PC 61BM/ cathode interface layer (P1, P10 or P12)/Al.
Embodiment
Following examples are to the monomer of the present invention's proposition and the explanation of polymer manufacture, but the present invention will be not limited to listed example.
Embodiment 1:2,8-dihydroxyl-dibenzothiophene
Take by weighing dibenzothiophen (20 gram, 108.7 mmoles) and be dissolved in the trichloromethane, add 0.31 gram (54 mmole) reduced iron powder, lucifuge, under ice bath in this solution dropping liquid bromine (14 milliliters, 271.8 mmoles), at room temperature reacted 20 hours.Remove unreacted liquid bromine with saturated aqueous solution of sodium bisulfite neutralization then, reaction system is poured in the water, use dichloromethane extraction, saturated common salt washing, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, use the trichloromethane recrystallization.Obtain white crystal 2,8-two bromo-dibenzothiophene. 1H?NMR(300MHz,CDCl 3)δ(ppm):8.24(m,2H),7.71(m,2H),7.58(m,2H)。 13CNMR(75MHz,CDCl3)δ(ppm):138.99,136.55,130.68,125.08,124.58,119.01。ESI-MS:m/z342(M+)。Ultimate analysis calculated value [C 12H 6Br 2S] (%): C, 42.14; H, 1.77; S, 9.37; Found:C, 42.16; H, 1.83; S, 9.31.With 2,8-two bromo-S, S-dioxy-dibenzothiophene (3.42 grams, 10 mmoles) is dissolved in the refining anhydrous tetrahydro furan, add (12 milliliters of n-Butyl Lithiums down at-78 ℃, 30 mmoles), reacted 2 hours, add (10.41 milliliters of trimethyl borates down at-78 ℃ then, 50 mmoles), keep-78 ℃ of reactions 2 hours, rise to room temperature then, reacted 24 hours.Reaction solution is poured in the frozen water, added sulfuric acid, reacted 8 hours.Reaction system ethyl acetate extraction then, saturated common salt washing, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, use acetone recrystallization.Obtain white crystal 2,8-hypoboric acid-dibenzothiophene. 1HNMR(300MHz,CDCl 3)δ(ppm):7.90(d,2H),7.80(d,2H),7.31(d,2H),2.0(s,4H)。 13C?NMR(75MHz,CDCl3)δ(ppm):136.82,135.76,134.71,132.26,132.23,120.66。ESI-MS:m/z272(M+)。Ultimate analysis calculated value [C 12H 10B 2O 4S] (%): C, 53.01; H, 3.71; S, 11.79; Found:C, 53.08; H, 3.79; S, 11.83.With 2,8-hypoboric acid-dibenzothiophene (2.72 grams, 10 mmoles) places flask, adds excessive hydrogen peroxide, reacts 5 hours down at 50 ℃.Then reaction system is poured in the frozen water, filtered, the filter cake acetone recrystallization gets white solid. 1H?NMR(300MHz,CDCl 3)δ(ppm):7.69(d,2H),7.25(d,2H),6.78(d,2H),5.0(s,2H)。 13C?NMR(75MHz,CDCl 3)δ(ppm):155.49,133.76,132.56,123.29,118.85,111.48。ESI-MS:m/z216(M+)。Ultimate analysis calculated value [C 12H 8B 2O 2S] (%): C, 66.65; H, 3.73; S, 14.83; Found:C, 66.60; H, 3.77; S, 14.81.Its chemical equation is as follows:
Embodiment 2:3,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-borines)-2,8-two octyloxies-S, S-dioxy-dibenzothiophene
With 2,8-dihydroxyl-dibenzothiophene (10.8 grams, 50 mmoles) is dissolved in the N,N-dimethylacetamide, adds salt of wormwood (20.7 grams, 150 mmoles), is heated to backflow, stirs 2 hours under argon shield, adds the 1-bromooctane, reacts 24 hours.Then system is reduced to room temperature, remove by filter salt of wormwood, filtrate is poured in the frozen water, uses dichloromethane extraction, saturated common salt washing, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, N,N-dimethylacetamide is removed in underpressure distillation.Residue separates purify (is eluent with sherwood oil: ethyl acetate=10:1) with post. 1H?NMR(300MHz,CDCl 3)δ(ppm):8.22(d,2H),8.16(s,2H),7.06(d,2H),4.08(m,4H),1.73(m,4H),1.42(m,4H),1.29(m,8H),1.25(m,8H),0.88(t,6H)。 13C?NMR(75MHz,CDCl 3)δ(ppm):158.54,133.69,132.52,124.51,119.12,110.78,69.66,31.73,29.15,29.04,28.80,26.58,14.00。ESI-MS:m/z440(M+)。Ultimate analysis calculated value [C 28H 40O 2S] (%): C, 76.31; H, 9.15; S, 7.28; Found:C, 76.28; H, 9.19; S, 7.25.With 2,8-two octyloxies-dibenzothiophene (1.88 grams, 4.3 mmoles) are dissolved in the glacial acetic acid, are heated to backflow, add hydrogen peroxide (4.43 milliliters, 43 mmoles), react 1 hour.Then system is reduced to room temperature, reaction system is poured in the frozen water, use dichloromethane extraction, the set oil phase is washed with saturated common salt, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, N,N-dimethylacetamide is removed in underpressure distillation.Residue separates with post purifies (is eluent with sherwood oil: ethyl acetate=10:1), gets white solid. 1H?NMR(300MHz,CDCl 3)δ(ppm):7.93(d,2H),7.44(s,2H),7.03(d,2H),4.10(m,4H),1.74(m,4H),1.43(m,4H),1.30(m,8H),1.26(m,8H),0.89(t,6H)。 13C?NMR(75MHz,CDCl 3)δ(ppm):158.25,134.69,130.91,121.79,117.04,108.06,69.66,31.73,29.15,29.04,28.80,26.58,23.16,14.00。ESI-MS:m/z472(M+)。Ultimate analysis calculated value [C 28H 40O 4S] (%): C, 71.15; H, 8.53; S, 6.78; Found:C, 71.11; H, 8.56; S, 6.74.Take by weighing 2,8-two octyloxies-S, S-dioxy-dibenzothiophene (4.72 grams, 10 mmoles) be dissolved in glacial acetic acid: in mixed solvent trichloromethane=1:1(volume ratio), be heated to backflow, lucifuge, dropping liquid bromine in this solution (1 milliliter, 20 mmoles) reacted 24 hours.Then reaction system is reduced to room temperature, remove unreacted liquid bromine with saturated aqueous solution of sodium bisulfite neutralization, reaction system is poured in the water, use dichloromethane extraction, the set oil phase is washed with saturated common salt, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, residue separates with post purifies (is eluent with sherwood oil: ethyl acetate=40:1), gets white solid. 1H NMR, 13C NMR, ESI-MASS and ultimate analysis (EA) test shows is a target product 3,7-two bromo-2,8-two octyloxies-S, S-dioxy-dibenzothiophene. 1H NMR (300MHz, CDCl 3) δ (ppm): 7.80 (s, 2H), 6.95 (s, 2H), 4.12 (t, 4H), 1.90 (m, 4H), 1.57 (m, 4H), 1.38 (m, 8H), 1.32 (m, 8H), 0.91 (t, 6H). 13C NMR (75MHz, CDCl 3) δ (ppm): 159.87,131.82,130.17,126.50,114.48,104.43,69.93,31.77,29.26,29.18,28.92,26.00,22.64,14.08.ESI-MS:m/z630. ultimate analysis calculated value [C 28H 38O 4SBr 2] (%): C, 53.34; H, 6.08; S, 5.09; Found:C, 53.31; H, 6.11; S, 5.12.With resulting 3,7-two bromo-2,8-two octyloxies-S, S-dioxy-dibenzothiophene (0.631 gram, 1 mmole), connection boric acid pinacol ester (1.02 grams, 4 mmoles), Potassium ethanoate (1.2 gram), tetra-triphenylphosphine palladium (0.1 gram) and 1,4-dioxane (20 milliliters) refluxed 24 hours under inert atmosphere.Resulting mixing solutions is poured in the water, used dichloromethane extraction, the saturated common salt water washing of set oil phase, anhydrous magnesium sulfate drying after the employing silica gel column chromatography separates after concentrating, obtains white solid. 1H NMR, 13C NMR, MS and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Embodiment 3:3,7-two bromo-2,8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene and 3,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-borines)-2,8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene
Under the protection of inert atmosphere; with 2 of preparation, 8-dihydroxyl-dibenzothiophene (10.8 grams, 50 mmoles) is dissolved in N; in the N-N,N-DIMETHYLACETAMIDE; add salt of wormwood (20.7 grams, 150 mmoles), be heated to backflow; under argon shield, stirred 2 hours; add 1, the 6-dibromo-hexane reacted 24 hours.Then system is reduced to room temperature, remove by filter salt of wormwood, filtrate is poured in the frozen water, uses dichloromethane extraction, saturated common salt washing, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, N,N-dimethylacetamide is removed in underpressure distillation.Residue separates purify (is eluent with sherwood oil: ethyl acetate=10:1) with post and obtains 2,8-two (6-bromo-hexyloxy) dibenzothiophene. 1H?NMR(300MHz,CDCl 3)δ(ppm):8.22(d,2H),8.16(s,2H),7.06(d,2H),4.08(t,4H),3.30(t,4H),2.03(m,4H),1.60(m,4H),1.15(m,4H),0.57(m,4H)。With 2,8-dibromo hexyloxy-dibenzothiophene (2.33 grams, 4.3 mmoles) is dissolved in the glacial acetic acid, is heated to backflow, adds hydrogen peroxide (4.43 milliliters, 43 mmoles), reacts 1 hour.Then system is reduced to room temperature, reaction system is poured in the frozen water, use dichloromethane extraction, the set oil phase is washed with saturated common salt, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, N,N-dimethylacetamide is removed in underpressure distillation.Residue separates with post purifies (is eluent with sherwood oil: ethyl acetate=10:1), gets white solid 2,8-dibromo hexyloxy-S, S-dioxy-dibenzothiophene. 1H?NMR(300MHz,CDCl 3)δ(ppm):7.93(d,2H),7.44(s,2H),7.03(d,2H),4.08(t,4H),3.30(t,4H),2.03(m,4H),1.60(m,4H),1.15(m,4H),0.57(m,4H)。Take by weighing 2,8-two octyloxies-S, S-dioxy-dibenzothiophene (10.0 grams, 17.4 mmole) be dissolved in glacial acetic acid: in mixed solvent trichloromethane=1:1(volume ratio), be heated to backflow, lucifuge, dropping liquid bromine in this solution (1.8 milliliters, 34.8 mmoles) reacted 24 hours.Then reaction system is reduced to room temperature, remove unreacted liquid bromine with saturated aqueous solution of sodium bisulfite neutralization, reaction system is poured in the water, use dichloromethane extraction, the set oil phase is washed with saturated common salt, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, residue separates with post purifies (is eluent with sherwood oil: ethyl acetate=5:1), gets white solid 3,7-two bromo-2,8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene. 1H?NMR(300MHz,CDCl 3)δ(ppm):7.80(s,2H),6.95(s,2H),4.08(t,4H),3.30(t,4H),2.03(m,4H),1.60(m,4H),1.15(m,4H),0.57(m,4H)。With resulting white solid 3,7-two bromo-2,8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene (0.732 gram, 1 mmole), connection boric acid pinacol ester (1.02 grams, 4 mmoles), Potassium ethanoate (1.2 gram), tetra-triphenylphosphine palladium (0.1 gram) and 1, the 4-dioxane refluxed 24 hours under inert atmosphere.Resulting mixing solutions is poured in the water, used dichloromethane extraction, the saturated common salt water washing of set oil phase, anhydrous magnesium sulfate drying after the employing silica gel column chromatography separates after concentrating, obtains white solid. 1H NMR, 13C NMR, MS and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200121
Embodiment 4:3,7-two (9,9-dimethyl-9H-fluorenes-2-yl)-(2,8-two (6-bromine hexyloxy))-S, S-dioxydibenze thiophthene
With 3 of careful purifying, 7-two bromo-2,8-two (6-bromo-hexyloxy)-S; S-dioxy-dibenzothiophene (0.7322 gram; 1 mmole), 9,9-dimethyl fluorene-2-boric acid (1.16 grams; 4 mmoles); tetra-triphenylphosphine palladium (0.1 gram), aqueous sodium carbonate (2 mol, 10 milliliters); Tetrabutyl amonium bromide (0.1 gram) and toluene (30 milliliters) add in 250 milliliters of there-necked flasks, are warming up to 90 degree reactions 24 hours under protection of inert gas.Mixing solutions is poured in the frozen water, used dichloromethane extraction, the set oil phase is washed with saturated common salt, distillation washing, anhydrous magnesium sulfate drying.After organic solvent was spin-dried for, silica gel column chromatography obtained white solid product after separating. 1H NMR, 13C NMR, MS, results of elemental analyses show that resulting compound is a target product.
Figure BDA00003010959200122
Embodiment 5:3,7-dibromo [4,7-two (N-(4-bromophenyl))]-S, S-dioxydibenze thiophthene
In 250 milliliters of two-mouth bottles; add pentanoic (3.40 gram); 3; 7-two bromo-S, S-dioxy-dibenzothiophene (3.74 gram) and sodium tert-butoxide (8.69 gram) add toluene (100 milliliters) again; after under nitrogen protection, stirring half an hour; slowly drip 3-tertiary butyl phosphine (1.12 gram), add palladium (0.10 gram), heating reflux reaction 24 hours.Be cooled to room temperature, use dichloromethane extraction, remove solvent under reduced pressure after, obtain solid.Adorn post with silica gel, petrol ether/ethyl acetate (50:1) is made eluent and is carried out the column chromatography purification, obtains the yellow solid powder, productive rate: 70%.Then, in 500 milliliters of two-mouth bottles, add 4,7-two (N-(4-phenyl))-3,7-S, S-dioxy-dibenzothiophene (5.51 gram), tetrahydrofuran (THF) (150 milliliters) stirs, after ice bath is cooled to 0 ℃, slowly drip N-bromo-succinimide (7.5 gram), after dripping, slowly rose to room temperature reaction 24 hours, removal of solvent under reduced pressure obtains solid then, does carrier with silica gel, petrol ether/ethyl acetate (20:1) is made eluent, and column chromatography obtains yellow solid, productive rate after purifying: 72%. 1H NMR, 13C NMR, MS and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200131
Embodiment 6:3,7-two bromo-2, two (3-(N, N-dimethyl amido) the propoxy-)-S of 8-, S-dioxy-dibenzothiophene
Under nitrogen protection; in there-necked flask (250 milliliters), add 3; 7-two bromo-2; 8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene (0.732 gram, 1 mmole); Tetrabutyl amonium bromide (0.3 gram); aqueous sodium hydroxide solution (50%, 4 milliliter) and dimethyl sulfoxide (DMSO) (50 milliliters) stirred 1 hour.Add excessive N then, the aqueous solution of N-dimethyl chloride propylamin hydrochloride (2 grams, 13 mmoles) continues to stir and spends the night.Mixture is poured in the water, used dichloromethane extraction, anhydrous magnesium sulfate drying obtains white solid with product after with acetone mixed solution recrystallization after concentrating. 1H NMR, 13C NMR, MS and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Embodiment 7:3,7-two bromo-2,8-two (6-diethylamine hexyloxy)-S, S-dioxy-dibenzothiophene and zwitterionic derivative
Take by weighing 3,7-two bromo-2,8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene (7.32 grams, 10.0 mmoles) is dissolved in N, in the dinethylformamide, is heated to backflow, adds diethylamine under argon shield.Reacted 24 hours.Then reaction system is reduced to room temperature, reaction system is poured in the water, use dichloromethane extraction, the set oil phase is washed with saturated common salt, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, residue separates with post purifies (is eluent with the ethyl acetate), gets white solid 3,7-two bromo-2,8-two (6-diethylamine-hexyloxy)-S, S-dioxy-dibenzothiophene.Then, in 100 milliliters of there-necked flasks, add 3,7-two bromo-2,8-two (6-diethylamine-hexyloxy)-S, S-dioxy-dibenzothiophene (0.5 gram) adds tetrahydrofuran (THF) (20 milliliters), stirs under nitrogen protection.It is excessive 1 to add then, 4-butyl sulfonic acid lactone and N, and dinethylformamide (20 milliliters) slowly is warming up to 100 ° of C, stirs 5 days under nitrogen protection.Distill away tetrahydrofuran (THF) and excessive N, dinethylformamide, Ionized crude product precipitate in ethyl acetate (100 milliliters), filter, and be dry under vacuum with the chloroform washing, obtains pulverulent solids and be its zwitterionic derivative. 1H NMR, 13C NMR, MS and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200141
Embodiment 8:3,7-two bromo-2, two (6-(N, N-two (2-hydroxyethyl) amido)-the hexyloxy)-S of 8-, S-dioxy-dibenzothiophene
With 3,7-two bromo-2,8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene (7.32 grams, 10.0 mmoles) is dissolved in N, in the dinethylformamide, adds excessive diethanolamine, and reaction is 48 hours under argon shield and room temperature.The solvent in the reaction system is removed in decompression then, residual solids is spent the night vacuum-drying 24 hours at air drying.Obtain powdery white solid. 1H NMR, 13C NMR, MS and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200151
Embodiment 9:3,7-two bromo-2,8-(6,6 '-bromo two (N, N, N-trimethylammonium hexyl-1-ammonium))-S, S-dioxy-dibenzothiophene
With 3,7-two bromo-2,8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene (7.32 grams, 10.0 mmoles) is dissolved in N, in the dinethylformamide, adds the excessive Trimethylamine aqueous solution, and reaction is 48 hours under argon shield and room temperature.The solvent in the reaction system is removed in decompression then, residual solids is spent the night vacuum-drying 24 hours at air drying.Obtain powdery white solid. 1H NMR, 13C NMR, MS and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200152
Embodiment 10:3,7-two bromo-2,8-two (the phosphate-based hexyloxy of 6-)-S, S-dioxy-dibenzothiophene and 3,7-two bromo-2,8-two ((6-sodium phosphate base)-hexyloxy)-S, S-dioxy-dibenzothiophene
Under the protection of inert atmosphere, with 3,7-two bromo-2,8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene (7.32 grams, 10.0 mmoles) is dissolved in the triethyl-phosphite, is heated to 140 ° of C reactions and spends the night.Reaction is cooled to room temperature with mixing solutions after finishing, remaining solvent is removed in underpressure distillation, and crude product obtains white solid 3,7-two bromo-2 with chromatography column purification (ethyl acetate/petroleum ether=1:1 is an eluent), 8-two (the phosphate-based hexyloxy of 6-)-S, S-dioxy-dibenzothiophene.Then; with the white solid 3 that obtains; 7-two bromo-2,8-two (the phosphate-based hexyloxy of 6-)-S, S-dioxy-dibenzothiophene (2.0 gram) is dissolved among the DMF; add excessive aqueous sodium carbonate; flow through night next time in argon shield then, product is precipitated in normal hexane, filter; with the normal hexane washing, obtain the white powder solid after the vacuum-drying. 1H NMR, 13C NMR, MS and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200161
Embodiment 11: poly-[3,7-(two-2,8-two (N, N dimethylamine hexyloxy)-S, S-dioxy-dibenzothiophene] (P1) and zwitterionic derivative (P2)
Will be through 3 of careful purifying; 7-two bromo-2; 8-two (6-diethylamine-hexyloxy)-S, S-dioxy-dibenzothiophene (0.126 gram, 0.5 mmole) is dissolved in toluene and N; in the mixed solvent of dinethylformamide; under argon shield, add two (1, the 5-cyclooctadiene) nickel (2.5 milligrams), 1,5-cyclooctadiene (2.5 milligrams) and dipyridyl (10 milligrams) then; under Ar atmosphere, reflux and stirred 24 hours, add bromobenzene (0.3 milliliter) reaction 6 hours.Finish reaction, reaction system is reduced to room temperature, pour in the methyl alcohol and precipitate, filter, filtrate concentrates the back and precipitates in acetone, filters, and the gained filter cake spends the night at air drying, and then vacuum-drying is 24 hours, obtains the white powder solid. 1H NMR, 13C NMR and results of elemental analyses show the resulting target product that is.Then, resulting white powder solid (500 milligrams) is added in 100 milliliters of there-necked flasks, add tetrahydrofuran (THF) (20 milliliters), under nitrogen protection, stir.It is excessive 1 to add then, 4-butyl sulfonic acid lactone and N, and dinethylformamide (20 milliliters) slowly is warming up to 100 ° of C, stirs 5 days under nitrogen protection.Distill away tetrahydrofuran (THF) and excessive N, dinethylformamide, Ionized polymkeric substance precipitate in ethyl acetate (100 milliliters), filter, and be dry under vacuum with the chloroform washing, obtains pulverulent solids and be its zwitterionic derivative. 1H NMR, 13C NMR and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200162
Embodiment 12: poly-[3,7-two (2, two (the phosphate-based hexyloxy of the 6-)-S of 8-, S-dioxy-dibenzothiophene)-alt-2,2 '-(9,9 '-two spiral shell fluorenes)] (P3) and ionization derivative (P4)
Will be through 3 of careful purifying; 7-two bromo-2,8-two (the phosphate-based hexyloxy of 6-)-S, S-dioxy-dibenzothiophene (0.8465 gram; 1 mmole); 2,2 '-two (4,4; 5; 5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9; 9 '-spiro-bisfluorene (0.5683 gram; 1 mmole), is dissolved in the toluene, under argon shield, adds palladium (10 milligrams) then; the tricyclohexyl phosphine (20 milligrams) and the tetraethyl ammonium hydroxide aqueous solution (5 milliliters); after 24h is stirred in backflow under argon atmospher; add phenylo boric acid (20 milligrams), reacted 6 hours, add bromobenzene (0.3 milliliter) reaction 6 hours again.Finish reaction, reaction system reduced to room temperature, pour in the methyl alcohol and precipitate, filter, again with washing with acetone 24 hours to remove oligopolymer and catalyst residue, the products therefrom air drying spends the night, and follows vacuum-drying 24 hours, obtains yellow powder shape solid.Then, the white solid (100 milligrams) that obtains is dissolved in N, in the dinethylformamide; add excessive aqueous sodium carbonate, flow through night next time in argon shield then, product is precipitated in normal hexane; filter,, obtain the white powder solid after the vacuum-drying with the normal hexane washing. 1H NMR, 13C NMR and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200171
Embodiment 13: poly-[3,7-(2,8-two (6-octyloxy-S, S-dioxy-dibenzothiophene))]-alt-[3,7-two (2, two (3-(N, N-dimethyl propyl amine))-S of 8-, S-dioxy-dibenzothiophene)] (P5)
Will be through 3 of careful purifying, 7-two (4,4; 5; 5-tetramethyl--1,3,2-two oxa-borines)-2; 8-two octyloxies-S; S-dioxy-dibenzothiophene (0.7244 gram, 1 mmole), 3; 7-two bromo-2; two (3-(N, N-dimethyl amido) the propoxy-)-S of 8-, S-dioxy-dibenzothiophene (0.606 gram; 1 mmole) is dissolved in the toluene (15 milliliters); under argon shield, add palladium (15 milligrams) then; the tricyclohexyl phosphine (25 milligrams) and the tetraethyl ammonium hydroxide aqueous solution (5 milliliters) refluxing stirring under the Ar atmosphere after 48 hours, add phenylo boric acid (20 milligrams); reacted 6 hours, and added bromobenzene (0.5 milliliter) reaction 6 hours again.Finish reaction, reaction system reduced to room temperature, pour in the methyl alcohol and precipitate, filter, again with washing with acetone 24 hours to remove oligopolymer and catalyst residue, the products therefrom air drying spends the night, vacuum-drying 24 hours. 1H NMR, 13C NMR and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200181
Embodiment 14: gather [3,7-(2,8-two (6-(N, N-di-alcohol amido)-hexyloxy)-S, S-dioxy-dibenzothiophene)-alt-2,8-(6,6,12,12-four octyl groups-6,12-indoline [1,2-b] fluorenes)] (P7)
Will be through 3 of careful purifying, 7-two (4,4; 5,5-tetramethyl--1,3; 2-two oxa-borines)-2,8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene (0.8263 gram; 1 mmole), 3,7-two bromo-2; 8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene (0.6589 gram, 0.9 mmole) and 2; 8-two bromo-6; 6,12,12-four octyl groups-6; 12-indoline [1; 2-b] fluorenes (0.0861g, 0.1 mmole is available from U.S. Sigma-Aldrich company); be dissolved in the toluene; under argon shield, add palladium (10 milligrams) then; the tricyclohexyl phosphine (20 milligrams) and the tetraethyl ammonium hydroxide aqueous solution (5 milliliters) refluxing stirring under the Ar atmosphere after 24 hours, add phenylo boric acid (20 milligrams); reacted 6 hours, and added bromobenzene (0.3 milliliter) reaction 6 hours again.Finish reaction, reaction system reduced to room temperature, pour in the methyl alcohol and precipitate, filter, again with washing with acetone 24 hours to remove oligopolymer and catalyst residue, the products therefrom air drying spends the night, and follows vacuum-drying 24 hours, obtains yellow powder shape solid.Further with the product dissolving and the N that obtain, in the mixed solvent of dinethylformamide, add diethanolamine (0.5 gram), reaction is 48 hours under argon shield and room temperature.Then reaction system is poured in the water and precipitated, filter, the filter cake air drying spends the night, and then vacuum-drying is 24 hours. 1H NMR, 13C NMR and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Embodiment 15: polar functionalities S, S-dioxy-dibenzothiophene unit water/pure dissolubility non-conjugated polymeric thing (P10)
With 1-methyl isatin (1 mmole) and 2; 8-two ((6-bromine hexyloxy)-3,7-two (9,9-dimethyl-9H-fluorenes-2-yl)-S; S-dioxydibenze thiophthene (1 mmole) is dissolved in methylene dichloride (5 milliliters), slowly drips trifluoromethayl sulfonic acid (1 milliliter) under nitrogen protection.Reaction mixture at room temperature stirs to pour in the methyl alcohol after 12 hours and precipitates, and filters, and it is complete with methyl alcohol and washing with acetone to obtain white flocks, under vacuum dry 24 hours again, obtains the white fiber shaped polymer.Further the polymkeric substance (100 milligrams) that obtains is dissolved in and is dissolved in the triethyl-phosphite, be heated to 140 ° of C reactions and spend the night.Reaction is cooled to room temperature with mixing solutions after finishing, and remaining solvent is removed in underpressure distillation, obtains the white solid powder.Then, further the white solid (100 milligrams) that obtains is dissolved in N, in the dinethylformamide; add excessive aqueous sodium carbonate, flow through night next time in argon shield then, product is precipitated in normal hexane; filter,, obtain the white powder solid after the vacuum-drying with the normal hexane washing. 1H NMR, 13C NMR and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200201
Embodiment 16: poly-[2,7-(9, the 9-dioctyl) fluorenes]-co-[3,7-two (2,8-two (3-(N, N-dimethyl propyl amine)-S, S-dioxy-dibenzothiophene)] (P11)
Will be through 2 of careful purifying; 7-two (4; 4,5,5-tetramethyl--1; 3; 2-two oxa-borine-two bases)-9,9-two-octyl group fluorenes (0.3208 gram, 0.5 mmole); 2; 7-two bromo-9,9-dioctyl fluorene (0.2194 gram, 0.40 mmole) and 3; 7-two bromo-2; two (3-(N, N-dimethyl amido) the propoxy-)-S of 8-, S-dioxy-dibenzothiophene (0.0606 gram; 0.10 mmole) be dissolved in the toluene; under argon shield, add palladium (2.5 milligrams) then; the tricyclohexyl phosphine (2.5 milligrams) and the tetraethyl ammonium hydroxide aqueous solution (1 milliliter) refluxing stirring under the Ar atmosphere after 48 hours, add phenylo boric acid (20 milligrams); reacted 6 hours, and added bromobenzene (0.3 milliliter) reaction 6 hours again.Finish reaction, reaction system reduced to room temperature, pour in the methyl alcohol and precipitate, filter, again with washing with acetone 24 hours to remove oligopolymer and catalyst residue, the products therefrom air drying spends the night, and follows vacuum-drying 24 hours.H NMR, 13CNMR and results of elemental analyses show the resulting target product that is.In addition, can by regulate several compounds molar ratio 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-borine-two bases)-9,9-two-octyl group fluorenes: 2,7-two bromo-9, the 9-dioctyl fluorene: 3,7-two bromo-2, two (3-(N, N-dimethyl amido) the propoxy-)-S of 8-, S-dioxy-dibenzothiophene, preparation repeats above process, can obtain the derivative of the multipolymer of a series of different ratioss. 1H NMR, 13C NMR and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Embodiment 17: polar functionalities S, the unitary water of S-dioxy-dibenzothiophene/pure dissolubility hyperbranched polymer (P12)
Will be through 2 of careful purifying; 7-two-(4; 4,5,5-dimethyl-1; 3; 2-two oxa-borine-two bases)-two [9,9 '-dioctyl)] fluorenes (0.6426 gram, 1 mmole); (24.1 milligrams of three (4-bromobenzene) amine; 0.05 mmole), 3,7-two bromo-2; two (3-(the N of 8-; the N-dimethyl amido) propoxy-)-and S, S-dioxy-dibenzothiophene (0.5475 gram, 0.95 mmole); be dissolved in the toluene; under argon shield, add palladium (10 milligrams) then; the tricyclohexyl phosphine (20 milligrams) and the tetraethyl ammonium hydroxide aqueous solution (5 milliliters) refluxing stirring under the Ar atmosphere after 24 hours, add phenylo boric acid (20 milligrams); reacted 6 hours, and added bromobenzene (0.3 milliliter) reaction 6 hours again.Finish reaction, reaction system is reduced to room temperature, pour in the methyl alcohol and precipitate, filter, again with washing with acetone 24 hours to remove oligopolymer and catalyst residue, the products therefrom air drying spends the night, then vacuum-drying is 24 hours, and obtaining yellow powder shape solid is the hyperbranched polymer presoma.Then, resulting hyperbranched polymer presoma is dissolved among the THF, adds the Trimethylamine aqueous solution, at room temperature stirred 5 days, the solvent decompression is removed, obtain the white powder solid. 1HNMR, 13C NMR and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200211
Embodiment 18: polar functionalities S, the unitary water of S-dioxy-dibenzothiophene/pure dissolubility hyperbranched polymer (P14)
Add 3 in 50 milliliters of there-necked flasks, 7-two (4,4; 5,5-tetramethyl--1,3; 2-two oxa-borines)-2; 8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene (0.8263 gram, 1 mmole); 3; 7-dibromo [4,7-two (N-(4-bromophenyl))]-S, (8.7 milligrams of S-dioxydibenze thiophthenes; 0.01 mmole) and 3; 7-two bromo-2,8-two (6-bromo-hexyloxy)-S, S-dioxy-dibenzothiophene (0.7248 gram; 0.99 mmole); in toluene (15 milliliters) and the aqueous sodium carbonate (2 mol, 5 milliliters), under argon shield, add tetra-triphenylphosphine palladium (10 milligrams) then; under argon gas, reflux and stir after 48 hours; add phenylo boric acid (20 milligrams), reacted 6 hours, add bromobenzene (0.3 milliliter) reaction 6 hours again.Finish reaction, reaction system reduced to room temperature, pour in the methyl alcohol and precipitate, filter, again with washing with acetone 24 hours to remove oligopolymer and catalyst residue, the products therefrom air drying spends the night, and follows vacuum-drying 24 hours.Further with the product dissolving and the N that obtain, in the mixed solvent of dinethylformamide, add diethanolamine (0.5 gram), reaction is 48 hours under argon shield and room temperature.Then reaction system is poured in the water and precipitated, filter, the filter cake air drying spends the night, and then vacuum-drying is 24 hours, obtains the white powder solid product. 1HNMR, 13C NMR and results of elemental analyses show the resulting target product that is.Its chemical equation is as follows:
Figure BDA00003010959200231
The physical chemistry of table 1 polymkeric substance and electrochemical properties
Figure BDA00003010959200232
Figure BDA00003010959200241
With several polar functionalities S, the unitary water/alcohol soluble polymer of S-dioxy-dibenzothiophene (P1, P10 and P12) illustrates that for example polymkeric substance of the present invention is as the application of cathode interface layer in photodiode and photovoltaic device below.
Embodiment 19
With the ITO conductive glass, square resistance～20 Ω/, precut become 15 millimeters * 15 millimeters square sheets.Use acetone, micron order semi-conductor special purpose detergent, deionized water, Virahol ultrasonic cleaning successively, it is standby that nitrogen purging is placed on constant temperature oven.Before the use, the clean sheet of ITO in the oxygen plasma etch instrument with plasma bombardment 10 minutes.Select for use PVK available from Aldrich company, with the tetrachloroethane obtain solution.PEDOT:PSS aqueous dispersions (about 1%) is available from Bayer company, and buffer layer is with the spin coating of sol evenning machine (KW-4A) high speed, and thickness is by strength of solution and rotating speed decision, with surface profiler (Alpha-Tencor500 of Tritek company type) actual measurement monitoring.After the film forming, in the constant temperature vacuum drying oven, drive away solvent residues, post bake.
In white vase, after the weighing, change red light conjugated polymer MEH-PPV over to nitrogen protection film forming special gloves case (VAC company), in toluene, dissolve, with 0.45 micron membrane filtration.Polymer light-emitting layer optimum thickness is 70～90 nanometers.Thickness is measured with TENCOR ALFA-STEP-500 surface profiler.P1 is dissolved in methyl alcohol (adding little acetic acid), be mixed with the solution of 2 mg/ml concentration, with 0.45 micron membrane filtration.With sol evenning machine spin coating skim P1 on the substrate of ITO/PEDOT:PSS/MEH-PPV, about 5 nanometers of its thickness.Aluminium electrode evaporation vacuum tightness in vacuum plating unit reaches 3 * 10 -4Finish when Pa is following.The thickness of plated film speed and each layer electrode is by quartz resonator film thickness monitor (STM-100 type, Sycon company) monitoring in real time.The light-emitting zone of device is defined as 0.15 square centimeter by mask and the mutual zone that covers of ITO.All preparation process are all carried out in the glove box of nitrogen inert atmosphere is provided.The I-E characteristic of device, luminous intensity and external quantum efficiency are recorded by Keithley236 current/voltage source-measuring system and a calibrated silicon photo diode.Described water/the alcohol soluble polymer of spin coating skim (P1) is as interfacial layer on ITO/PEDOT:PSS/MEH-PPV respectively, and vacuum evaporation Al makes polymer LED as negative electrode then.For showing the effect of cathode interface layer of the present invention, and adopt directly that vacuum evaporation Al compares as the device of negative electrode on luminescent layer.With P1, P10, the device fabrication processes of P12 and PFN interfacial layer is the same, and the result is as shown in table 1.Having or not P1(P10, P12 or PFN) current density-voltage-luminosity of device of layer and luminous efficiency-current density be shown in Fig. 1 a, Fig. 1 b.
Table 2 is based on the MEH-PPV red-light-emitting polymer, P1, P10, the luminescent properties of P12 or PFN electron transfer layer/aluminium cathode device
Figure BDA00003010959200251
Example as seen thus, for MEH-PPV red light conjugated polymer conventional device, between luminescent layer and high-work-function metal aluminium, add P1, behind P10 or the P12 layer, the performance of device all is higher than on luminescent layer the directly performance of AM aluminum metallization device far away, and is better than adopting PFN to do device performance as the cathode interface layer.
Embodiment 20
Repeat embodiment 10, use P1, P10, P12 or PFN adopt P-PPV green glow conjugated polymers as luminescent layer as electron transfer layer, adopt the high-work-function metal gold as negative electrode, and other condition is constant, and measuring result is as shown in table 2.Have or not P1, P10, the current density-voltage-luminosity of the device of P12 and PFN layer and luminous efficiency-current density are shown in Fig. 2 a, Fig. 2 b.
Table 3 is based on P-PPV green glow polymkeric substance, P1, P10, the luminescent properties of P12 or PFN electron transfer layer/au cathode device
Figure BDA00003010959200252
Example as seen thus, for P-PPV green glow conjugated polymers conventional device, between luminescent layer and high-work-function metal gold, add P1, behind P10 or the P12 layer, the performance of device all is higher than on luminescent layer the directly performance of gold evaporation device far away, and is better than adopting PFN to do device performance as the cathode interface layer.
Embodiment 21
With the ITO conductive glass, square resistance～20 Ω/, precut become 15 millimeters * 15 millimeters square sheets.Use acetone, micron order semi-conductor special purpose detergent, deionized water, Virahol ultrasonic cleaning successively, it is standby that nitrogen purging is placed on constant temperature oven.Before the use, the clean sheet of ITO in the oxygen plasma etch instrument with plasma bombardment 10 minutes.Select for use PVK available from Aldrich company, with the tetrachloroethane obtain solution.PEDOT:PSS aqueous dispersions (about 1%) is available from Bayer company, buffer layer is with the spin coating of sol evenning machine (KW-4A) high speed, thickness is about 40 nanometers, by strength of solution and rotating speed decision, with surface profiler (Alpha-Tencor500 of Tritek company type) actual measurement monitoring.After the film forming, in the constant temperature vacuum drying oven, drive away solvent residues, post bake.
(PCBM is as acceptor, PFO-DBT35:PC with the polymkeric substance solar cell material 61BM=1:2) place weighing in the clean sample bottle, change over to subsequently in the glove box of nitrogen protection, protect to keep the state of hypoxemia low humidity for high pure nitrogen in the glove box.To be used to prepare the polymer dissolution of active coating and place to stir on the mixing platform with appropriate solvent (as toluene, chlorobenzene, dichlorobenzene etc.) material is dissolved fully.The ITO substrate that scribbles anode buffer layer that vacuum-drying is good moves into the spin coating of carrying out the polymer active layer in the glove box, and the process of spin coating is identical with anode buffer layer.Scrape with sharp device and to dial side of diaphragm-operated and make the ITO layer exposed, behind the electrode evaporation as the anode of device.Drying is removed residual organic solvent.Polymer solar battery active coating optimum thickness is 70～90 nanometers.Thickness is measured with TENCOR ALFA-STEP-500 surface profiler.P1 is dissolved in methyl alcohol (adding little acetic acid), be mixed with the solution of 0.2 mg/ml concentration, with 0.45 micron membrane filtration.On the ITO substrate that gets rid of polymer solar battery material and PEDOT:PSS layer, generate skim P1 polymkeric substance, about 5 nanometers of its thickness respectively with sol evenning machine.Aluminium electrode evaporation vacuum tightness in vacuum plating unit reaches 3 * 10 -4Finish when Pa is following.The thickness of plated film speed and each layer electrode is by quartz resonator film thickness monitor (STM-100 type, Sycon company) monitoring in real time.The light-emitting zone of device is defined as 0.15 square centimeter by mask and the mutual zone that covers of ITO.All preparation process are all carried out in the glove box of nitrogen inert atmosphere is provided.The solar cell performance is at simulated solar irradiation (AM1.5G73.2mW/cm 2) measure down.For showing the effect of electron transfer layer of the present invention, employing is being got rid of on the ITO substrate of PEDOT:PSS directly spin on polymers solar cell material PFO-DBT35:PC60BM conjugated polymers as reference, vacuum evaporation metal A l(100 nanometer on active coating), makes polymkeric substance solar cell device as the reference device as negative electrode.Measuring result is as shown in table 3.With PFO-DBT35:PC 61The BM conjugated polymers is compared, and has or not P1, and the current density of the solar cell device of the device of P10 or P12 layer and voltage relationship are as shown in Figure 3.
Table 4 is based on giving body polymer P FO-DBT35:PC60BM, and with P1, P10 or P12 are the Photovoltaic Device Performance of electron transfer layer
Figure BDA00003010959200261
Thus the example as seen, for the employing PFO-DBT35:PC 61BM is the conventional device of photoabsorption active coating, difference spin coating skim P1 between device photoabsorption active coating and Al, and behind P10 or the P12, the open circuit voltage of device, short-circuit current and power conversion efficiency all are higher than the device of direct evaporating Al on the photoabsorption active coating.

Claims (4)

1. a class contains polar substitution group S, and S-dioxy-dibenzothiophene monomer is characterized in that chemical structural formula is
In the formula, R is a hydrogen; Or-(CH 2) nX, n=1～30; X is diethylamino group, zwitter-ion group, diethanolamine group, Trimethylamine 99 group or bound phosphate groups and derivative thereof, and the concrete structure formula is as follows:
Figure FDA00003010959100012
2. the described polar substitution group S that contains of claim 1, the preparation method of S-dioxy-dibenzothiophene monomer comprises the steps:
(1) with the liquid bromine dibenzothiophene bromination is become 2,8-two bromo-dibenzothiophene earlier; (2) will prepare 2,8-two bromo-S, S-dioxy-dibenzothiophene are dissolved in the refining anhydrous tetrahydro furan, add n-Butyl Lithium at low temperatures, react after 2 hours, add trimethyl borate, rise to room temperature reaction then, obtain white crystal 2,8-hypoboric acid-dibenzothiophene; (3) will obtain 2,8-hypoboric acid-dibenzothiophene places flask, adds excessive hydrogen peroxide, 50 ℃ of down reactions 5 hours, behind the purifying white solid 2,8-dihydroxyl-dibenzothiophene; (4) under the protection of inert atmosphere, with 2,8-dihydroxyl-dibenzothiophene adds two excessive bromoalkanes and carries out alkylated reaction, obtains white solid 2,8-two (bromo alkoxyl group) dibenzothiophene; (5) with 2,8-two (bromo alkoxyl group) dibenzothiophene is dissolved in the glacial acetic acid, behind the adding hydrogen peroxide oxidation, obtains white solid 2,8-dibromo alkoxyl group-S, S-dioxy-dibenzothiophene; (6) with 2,8-dibromo alkoxyl group-S, S-dioxy-dibenzothiophene slow dropping liquid bromine in glacial acetic acid/trichloromethane mixed solvent carries out bromination, obtains white solid 3,7-two bromo-2,8-two (bromine alkoxyl group)-dibenzothiophene; (7) with 3,7-two bromo-2, the alkoxyl group bromine of 8-two (bromine alkoxyl group)-dibenzothiophene side chain terminal reacts with corresponding polar group, obtains the S that contains the polar substitution group of described chemical structural formula 1 correspondence, S-dioxy-dibenzothiophene monomer.
3. based on the described polar substitution group S that contains of claim 1, the unitary water/alcohol soluble polymer of S-dioxy-dibenzothiophene is characterized in that structure is:
(1) simple linear polymer
Figure FDA00003010959100021
X, y are molar fraction, 0≤x≤0.7,0.3≤y≤1, and x+y=1, and polymerization degree n: 1～300, work as x=0, during y=1, described polymkeric substance is for based on containing polar substitution group S, the unitary homopolymer of S-dioxy-dibenzothiophene, its structure is as follows:
(2) hyperbranched polymer
Figure FDA00003010959100023
X, y are molar fraction, 0≤x≤0.65,0.3≤y≤0.95, and x+y=0.95; Polymerization degree n 1, n 2, n 3Scope be 1～300;
In the formula, R is a hydrogen; Or-(CH 2) nX, n=1～30, X is diethylamino group, zwitter-ion group, diethanolamine group, Trimethylamine 99 group, bound phosphate groups and derivative thereof, concrete structure is:
In the formula, structural unit A is one of following conjugation or non-conjugated structural unit:
Figure FDA00003010959100032
2, the 7-substituted fluorene;
Figure FDA00003010959100033
3, the 6-substituted fluorene;
Figure FDA00003010959100034
2,7-replaces the spiral shell fluorenes;
2,7-replaces the silicon fluorenes;
Figure FDA00003010959100036
2, the 7-substituted carbazole;
Figure FDA00003010959100037
3, the 6-substituted carbazole;
3,9-substituted indole carbazole;
Figure FDA00003010959100042
2,8-substituted indole carbazole;
Figure FDA00003010959100043
3,9-substituted indole fluorenes;
Figure FDA00003010959100044
2,8-substituted indole fluorenes;
Figure FDA00003010959100045
1, the 4-substituted benzene;
Figure FDA00003010959100046
2,2 '-replacement spiral shell fluorenes
Figure FDA00003010959100047
3,3-disubstituted indole-2-ketone
R 2For carbonatoms is the straight or branched alkyl of 1-16;
In the formula, B is conjugation or non-conjugated structural unit, has one of following chemical structural formula:
Figure FDA00003010959100051
Triphenylamine;
Figure FDA00003010959100052
Triazine;
Figure FDA00003010959100053
1,3, the 5-trisubstituted benzene;
N-phenyl-3, the 6-carbazole;
Figure FDA00003010959100055
3,4,5-triphenyl-1,2,4-triazole;
Figure FDA00003010959100056
4, and 7-two (4 ', 4 "-two substituted diphenylamines) base-2,1, the 3-diazosulfide;
Figure FDA00003010959100057
4, and 7-two (4 ', 4 "-two replacement triphenylamines) base-2,1, the 3-diazosulfide;
Figure FDA00003010959100058
4, and 7-two (4 ', 4 "-two substituted diphenylamines) base-3,7-dibenzothiophene-S, S-dioxy;
Figure FDA00003010959100061
4, and 7-two (4 ', 4 "-two replacement triphenylamines) base-3,7-dibenzothiophene-S, S-dioxy.
4. claim 3 is described based on polar functionalities S, unitary water/the alcohol soluble polymer of S-dioxy-dibenzothiophene is as the application of cathode interface material at Organic Light Emitting Diode or solar cell, it is characterized in that polymer LED, between luminescent layer and high-work-function metal electrode, insert the film of the described polymkeric substance of one deck multilayered structure; Or, between photovoltaic active coating and high-work-function metal electrode, insert the film of the described polymkeric substance of one deck to bulk heterojunction solar cell device.
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