CN103224486B - 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 PDFInfo
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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
Technical field
The present invention relates to the polymkeric substance based on polar functionalities S, S-dioxo-dibenzothiophene unit; The invention still further relates to polymkeric substance based on polar functionalities S, S-dioxo-dibenzothiophene unit as the application of embellishing cathode interface layer in photodiode and photovoltaic cell device of water/alcohol dissolubility.
Background technology
For organic electroluminescence device (Organic Light-emitting diodes, OLEDs), for reaching better device effect, the structure that many employings multilayer film are piled up, one deck hole transmission layer is added between anode and luminescent layer, last layer electron transfer layer is added between negative electrode and luminescent layer, such as some alcohol/water miscible take polyfluorene as the polyelectrolyte of main chain and the precursor of neutrality thereof, can effectively improve from the metal of high work function (as Al, Ag, Au) to the electron injection of active coating, and the PLED device of multilayer can be prepared by solution method, performance meets or exceeds traditional with Ba/Al, the metals such as LiF/Al are the device of negative electrode.In addition, research finds to adopt the negative electrode of conjugated polyelectrolytes to body heterojunction solar cell to modify, and can reach the effect improving device performance equally.The effect that the polymkeric substance of this kind of polarity and polyelectrolyte play comprises: the pollution of metallic cathode to active coating that can prevent evaporation; Optimize the contact of active coating and metal electrode, the shunting resistance improving device reduces series resistance; Built-in potential of effective raising device etc.
" advanced function material " (Adv.Funct.Mater.) 19(2009) on the 2457 side chain amidos reporting a series of neutrality with the homopolymerization of hydroxyl and copolymerization fluorenes as alcohol/water miscible electron injection material, on amido, the existence of hydroxyl can increase the solvability of polymkeric substance in polar solvent further.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, angle in order to chemically structure inquires into the relation between material structure and performance, author by introducing the copolymerization units of electron rich respectively on the main chain of polyfluorene, the copolymerization units of electron deficiency and unconjugated copolymerization units compare the electron injection performance of the polymkeric substance of different backbone structure, find that the polymkeric substance with electron rich main chain just can show good electron injection performance, and the impact of the conjugated degree of main chain on material electronics injection efficiency is little.
" macromole " (Macromolecules) 44 (2011) 4204 report that side chain contains diethanolamine (PCP-NOH) and phosphate ester-containing (PCP-EP) poly-[(2,7-carbazole)-replace-1,4-(2,5-alkoxy benzene)] derivative, the conjugated polymers obtained can as effective electron injecting layer for the photodiode of high-work-function metal aluminium as negative electrode.When adopting PFO-DBT15 as luminescent layer, adopting PCP-NOH and PCP-EP to reach 1.01 and 0.88cd/A as the device luminous efficiency of electron injecting layer, having exceeded the level of Ba/Al device 0.58cd/A.In addition, " polymer science magazine " (J.Polym.Sci) 49 (2011) 1263 reports a series of poly-[2,7-carbazole] side chain contains neutral amido, di-alcohol amido and phosphate-based, and the polyelectrolyte derivative after its ionization, the class that finds that this birdss of the same feather flock together [2,7-carbazole] is derivative can be applied to organic photovoltaic cell as effective cathode interface layer.As employing PFO-DBT35:PC
61when BM is as photoactive layer, open circuit voltage and the short-circuit current of the polymer solar cells of preparation are improved simultaneously, make its power-conversion efficiencies than adopting aluminium and improve more than 20% as during negative electrode.
" materials chemistry magazine " (J.Mater.Chem.) 22 (2012) 4329 reports triphenylamine homopolymer (PTPA-EP and PTPA-PO that side chain contains bound phosphate groups
3na
2), the water obtained/alcohol dissolubility conjugated polymers can as interfacial layer for reverse polymerization thing solar cell.Wherein, the lowest unocccupied molecular orbital energy level (LUMO) of ITO can be brought up to-4.3eV by PTPA-EP, is in close proximity to PC
71the lumo energy of BM, thus advantageously in electron collection, adopt PCDTBT:PC
71bM can reach 5.27% as the reverse polymerization thing efficiency of solar cell of active coating, shows its great potential for cathode interface layer.
But above-mentioned report does not all relate to water/alcohol soluble polymer based on polar functionalities S, S-dioxo-dibenzothiophene unit as the relevant information of the application of embellishing cathode interface layer in photodiode and solar-energy photo-voltaic cell device.S, S-dioxo-dibenzothiophene has strong electron-withdrawing group group-SO
2-, there is higher electron affinity and electronic mobility.Chemical material (Chem.Mater.) 20 (2008) 4499, " organic electronic " (Org.Electron.) 10 (2009) 901 and Chinese patent CN101255336 is by S, S-dioxo-dibenzothiophene is introduced in main polymer chain, obtain the blue light material of electroluminescent spectrum-stable, attract attention.The present invention is by being incorporated into S by polar group, and S-dioxo-dibenzothiophene unit side chain, develops a series of water/alcohol soluble polymer based on S, S-dioxo-dibenzothiophene derivative.This base polymer not only has excellent solubility property and Electron Injection Characteristics in environmentally friendly solvent, simultaneously due to electron-withdrawing group-SO
2-introducing can reduce the highest occupied molecular orbital(HOMO) energy level of polymkeric substance further simultaneously, therefore also there is the effect of hole blocking layer, will very large application potential be had as cathode interface material in Organic Light Emitting Diode and solar cell.
Summary of the invention
The object of the invention is to overcome prior art above shortcomings, there is provided a class containing polar substitution group S, S-dioxo-dibenzothiophene monomer and based on the simple linear polymer of the water/alcohol dissolubility of polar functionalities S, S-dioxo-dibenzothiophene unit and hyperbranched polymer.
Another object of the present invention is based on polar functionalities S by described, the simple linear polymer of the water/alcohol dissolubility of S-dioxo-dibenzothiophene unit 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-dioxo-dibenzothiophene monomer, and its structural formula is:
In formula, R is hydrogen; Or-(CH
2)
nx, n=1 ~ 30, X are diethylamino group, zwitter-ion group, diethanolamine group, Trimethylamine 99 group, bound phosphate groups and derivative thereof etc., concrete structure formula such as:
Described containing polar substitution group S, the preparation method of S-dioxo-dibenzothiophene monomer, comprises the steps:
(1) first by bromine, dibenzothiophene bromination is become the bromo-dibenzothiophene of 2,8-bis-;
(2) by 2 of preparation, the bromo-S of 8-bis-, S-dioxo-dibenzothiophene is dissolved in refining anhydrous tetrahydro furan, under low temperature (as-78 DEG C), add n-Butyl Lithium react 2 hours, then trimethyl borate is added at low temperatures, rise to room temperature reaction again, obtain white crystal 2,8-hypoboric acid-dibenzothiophene;
(3) 2, the 8-hypoboric acid obtained-dibenzothiophene is placed in flask, adds excessive hydrogen peroxide, react 5 hours at 50 DEG C, after purifying, obtain white solid 2,8-dihydroxyl-dibenzothiophene;
(4) under the protection of inert atmosphere, 2,8-dihydroxyl-dibenzothiophene is added two excessive bromoalkanes and carries out alkylated reaction, obtain white solid 2,8-bis-(bromo alkoxyl group) dibenzothiophene;
(5) 2,8-bis-(bromo alkoxyl group) dibenzothiophene is dissolved in glacial acetic acid, after adding hydrogen peroxide oxidation, obtains white solid 2,8-dibromo alkoxyl group-S, S-dioxo-dibenzothiophene;
(6) by 2,8-dibromo alkoxyl group-S, S-dioxo-dibenzothiophene slowly drips bromine and carries out bromination in glacial acetic acid/trichloromethane mixed solvent, obtains white solid 3,7-bis-bromo-2,8-bis-(bromine alkoxyl group)-dibenzothiophene;
(7) the alkoxyl group bromine of bromo-for 3,7-bis-2,8-bis-(bromine alkoxyl group)-dibenzothiophene side chain terminal and corresponding polar group are reacted, obtain polar group and replace S, S-dioxo-dibenzothiophene monomer.
One class polar functionalities S, the simple linear polymer of S-dioxo-dibenzothiophene unit, its structure is:
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 the homopolymer based on polar functionalities S, S-dioxo-dibenzothiophene, and its structure is as follows:
One class polar functionalities S, the hyperbranched polymer of S-dioxo-dibenzothiophene, chemical structure is as follows:
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 formula, R is hydrogen; Or-(CH
2)
nx, n=1 ~ 30, X are 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 structure unit:
2,7-substituted fluorene;
3,6-substituted fluorene;
2,7-replaces spiral shell fluorenes;
2,7-replaces silicon fluorenes;
2,7-substituted carbazole;
3,6-substituted carbazole;
3,9-substituted indole carbazole;
2,8-substituted indole carbazole;
3,9-substituted indole fluorenes;
2,8-substituted indole fluorenes;
isosorbide-5-Nitrae-substituted benzene;
2,2 '-replace spiral shell fluorenes
3,3-disubstituted indole-2-ketone
In formula, R
2for the straight or branched alkyl that carbonatoms is 1-16.
B is conjugation or the non-conjugated structure unit with one of following chemical structural formula:
triphenylamine;
triazine;
1,3,5-trisubstituted benzene;
n-phenyl-3,6-carbazole;
3,4,5-triphenyl-1,2,4-triazole;
4,7-bis-(4 ', 4 "-two substituted diphenylamines) base-2,1,3-diazosulfide;
4,7-bis-(4 ', 4 "-two replace triphenylamines) base-2,1,3-diazosulfide;
4,7-bis-(4 ', 4 "-two substituted diphenylamines) base-3,7-dibenzothiophene-S, S-dioxy;
4,7-bis-(4 ', 4 "-two replace triphenylamines) base-3,7-dibenzothiophene-S, S-dioxy
Described based on polar functionalities S, water/the alcohol soluble polymer of S-dioxo-dibenzothiophene unit 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 polymkeric substance described in one deck; Or to bulk heterojunction solar cell device, between photovoltaic active layers and high-work-function metal electrode, insert the film of polymkeric substance described in one deck.
Described polar functionalities S, water/the alcohol soluble polymer of S-dioxo-dibenzothiophene unit can be used for the embellishing cathode interface layer preparing luminescent device, be coated on luminescent layer with its water/methyl alcohol, DMSO isopolarity solution by spin coating, spray ink Printing or printing process, prepare the embellishing cathode interface layer (thickness is 1-30 nanometer) of luminescent device.Work function can be adopted to be greater than the stable metal (as aluminium, copper, silver, indium, nickel, lead, tin, carbon, graphite and alloy thereof) of (or equaling) 3.6 electron-volts as negative electrode.Organic electroluminescent (electrophosphorescent or the electroluminescence) material interface of high work function cathodic metal and various emission wavelength is modified with embellishing cathode interface layer, its photoelectric device by the impact of metallic cathode work function, can not obtain the quantum yield same or higher with low workfunction metal negative electrode.
Described polar functionalities S, water/the alcohol soluble polymer of S-dioxo-dibenzothiophene unit can be used for the active interface decorative layer preparing organic/polymer photovoltaics, make to realize ohmic contact between active coating and cathodic metal, be conducive to the effective collection of current carrier at ate electrode, thus the short-circuit current of raising device is to improve photoelectric transformation efficiency.Simultaneously, described polar group S, water/the alcohol soluble polymer of S-dioxo-dibenzothiophene unit effectively can suppress the dark current of conjugated polymers/soccerballene bulk heterojunction solar cell device, thus improves the open circuit voltage of device, can further improve the electricity conversion of device.
Compared with prior art, tool has the following advantages in the present invention:
(1) polar functionalities S, S-dioxo-dibenzothiophene unit polymkeric substance of the present invention can realize excellent electron injection to luminescent device and polymer photovoltaics.
(2) polar functionalities S of the present invention, S-dioxo-dibenzothiophene unit polymkeric substance is compared with the existing polymkeric substance for cathode interface layer (PFN), have and lower the highlyest occupied molecular orbital(MO) (HOMO) energy level, the effect of electron injection/hole barrier can be played simultaneously.
(3) polymer being soluble solution of the present invention is in methyl alcohol, N, in dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), water polar solvent, therefore can not there is intermixing phenomenon when constructing multilayer device between electron transfer layer and active coating.
(4) polymers soln of the present invention is by rotating, the modes such as printing apply skim on organic light emission active coating or organic solar batteries active coating, without the need to long-time heating or ultraviolet lighting to change its solvability, device preparation technology is simple.
(5) because the high-work-function metals such as aluminium have excellent air and steam stability, with polar functionalities S of the present invention, the conjugated polymers of S-dioxo-dibenzothiophene unit modifies high-work-function metal cathode interface, the aerial good processing stability of composite cathode of composition, the stability of device is greatly improved, in macromolecular LED display and polymer solar battery, have potential using value.
Accompanying drawing explanation
Fig. 1 a and Fig. 1 b is respectively Current density-voltage-luminosity graph of a relation based on red-light-emitting polymer MEH-PPV photodiode and luminous efficiency-current density graph of a relation, 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 is respectively Current density-voltage-luminosity graph of a relation based on green glow polymer P-PPV photodiode 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 that device architecture is: ITO/PEDOT:PSS/PFO-DBT35:PC based on donor polymer PFO-DBT35 bulk heterojunction solar cell device current density-voltage diagram
61bM/ cathode interface layer (P1, P10 or P12)/Al.
Embodiment
Following examples are the explanation prepared monomer and the polymkeric substance of the present invention's proposition, but the present invention will be not limited to listed example.
Embodiment 1:2,8-dihydroxyl-dibenzothiophene
Taking dibenzothiophen (20 grams, 108.7 mmoles) is dissolved in trichloromethane, adds 0.31 gram of (54 mmole) reduced iron powder, lucifuge, drips bromine (14 milliliters, 271.8 mmoles) under ice bath in this solution, at room temperature reacts 20 hours.Then with in saturated aqueous solution of sodium bisulfite and removing unreacted bromine, reaction system is poured into water, with dichloromethane extraction, saturated common salt wash, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, use trichloromethane recrystallization.Obtain the bromo-dibenzothiophene of white crystal 2,8-bis-.
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.By 2, bromo-S, the S-dioxo-dibenzothiophene of 8-bis-(3.42 grams, 10 mmoles) is dissolved in refining anhydrous tetrahydro furan, n-Butyl Lithium (12 milliliters is added at-78 DEG C, 30 mmoles), react 2 hours, then at-78 DEG C, add trimethyl borate (10.41 milliliters, 50 mmoles), keep-78 DEG C to react 2 hours, then rise to room temperature, react 24 hours.Reaction solution is poured in frozen water, add sulfuric acid, react 8 hours.Then reaction system is extracted with ethyl acetate, and saturated common salt is washed, 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, 11.83.2,8-hypoboric acid-dibenzothiophene (2.72 grams, 10 mmoles) is placed in flask, adds excessive hydrogen peroxide, react 5 hours at 50 DEG C.Then pour in frozen water by reaction system, filter, filter cake acetone recrystallization, obtains 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-bis-(4,4,5,5-tetramethyl--1,3,2-dioxaborinate)-2,8-bis-octyloxy-S, S-dioxo-dibenzothiophene
2,8-dihydroxyl-dibenzothiophene (10.8 grams, 50 mmoles) is dissolved in N,N-dimethylacetamide, adds salt of wormwood (20.7 grams, 150 mmoles), be heated to backflow, stir 2 hours under argon shield, add 1-bromooctane, react 24 hours.Then system is down to room temperature, cross and filter salt of wormwood, filtrate is poured in frozen water, and with dichloromethane extraction, saturated common salt is washed, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, underpressure distillation removing N,N-dimethylacetamide.Residue post separating-purifying (with sherwood oil: ethyl acetate=10:1 is eluent).
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, 7.25.2,8-, bis-octyloxies-dibenzothiophene (1.88 grams, 4.3 mmoles) is dissolved in glacial acetic acid, is heated to backflow, adds hydrogen peroxide (4.43 milliliters, 43 mmoles), react 1 hour.Then system is down to room temperature, reaction system is poured in frozen water, with dichloromethane extraction, set oil phase saturated common salt is washed, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, underpressure distillation removing N,N-dimethylacetamide.Residue post separating-purifying (with sherwood oil: ethyl acetate=10:1 is eluent), obtains 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 2,8-bis-octyloxy-S, S-dioxo-dibenzothiophene (4.72 grams, 10 mmoles) be dissolved in glacial acetic acid: trichloromethane=1:1(volume ratio) mixed solvent in, be heated to backflow, lucifuge, in this solution, drip bromine (1 milliliter, 20 mmoles), react 24 hours.Then reaction system is down to room temperature, with in saturated aqueous solution of sodium bisulfite and the unreacted bromine of removing, reaction system be poured into water, with dichloromethane extraction, set oil phase saturated common salt is washed, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, residue post separating-purifying (with sherwood oil: ethyl acetate=40:1 is eluent), obtains white solid.
1h NMR,
13c NMR, ESI-MASS and ultimate analysis (EA) test are indicated as bromo-2, the 8-bis-octyloxy-S of target product 3,7-bis-, S-dioxo-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.By obtained 3,7-bis-bromo-2,8-bis-octyloxy-S, S-dioxo-dibenzothiophene (0.631 gram, 1 mmole), connection boric acid pinacol ester (1.02 grams, 4 mmoles), Potassium ethanoate (1.2 grams), tetra-triphenylphosphine palladium (0.1 gram) and 1,4-dioxane (20 milliliters), refluxes 24 hours under an inert atmosphere.Be poured into water by obtained mixing solutions, with dichloromethane extraction, the saturated common salt water washing of set oil phase, anhydrous magnesium sulfate drying, after adopting silica gel column chromatography to be separated, obtains white solid after concentrated.
1h NMR,
13c NMR, MS and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 3:3,7-bis-bromo-2,8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene and 3,7-bis-(4,4,5,5-tetramethyl--1,3,2-dioxaborinate)-2,8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene
Under the protection of inert atmosphere; 2, the 8-dihydroxyl-dibenzothiophene (10.8 grams, 50 mmoles) of preparation is dissolved in N; in N-N,N-DIMETHYLACETAMIDE; add salt of wormwood (20.7 grams, 150 mmoles), be heated to backflow; stir 2 hours under argon shield; add 1,6-dibromo-hexane, react 24 hours.Then system is down to room temperature, cross and filter salt of wormwood, filtrate is poured in frozen water, and with dichloromethane extraction, saturated common salt is washed, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, underpressure distillation removing N,N-dimethylacetamide.Residue post separating-purifying (with sherwood oil: ethyl acetate=10:1 is eluent) obtains 2,8-bis-(the bromo-hexyloxy of 6-) 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)。2,8-dibromo hexyloxy-dibenzothiophene (2.33 grams, 4.3 mmoles) is dissolved in glacial acetic acid, is heated to backflow, adds hydrogen peroxide (4.43 milliliters, 43 mmoles), react 1 hour.Then system is down to room temperature, reaction system is poured in frozen water, with dichloromethane extraction, set oil phase saturated common salt is washed, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, underpressure distillation removing N,N-dimethylacetamide.Residue post separating-purifying (with sherwood oil: ethyl acetate=10:1 is eluent), obtains white solid 2,8-dibromo hexyloxy-S, S-dioxo-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 2,8-bis-octyloxy-S, S-dioxo-dibenzothiophene (10.0 grams, 17.4 mmoles) be dissolved in glacial acetic acid: trichloromethane=1:1(volume ratio) mixed solvent in, be heated to backflow, lucifuge, in this solution, drip bromine (1.8 milliliters, 34.8 mmoles), react 24 hours.Then reaction system is down to room temperature, with in saturated aqueous solution of sodium bisulfite and the unreacted bromine of removing, reaction system be poured into water, with dichloromethane extraction, set oil phase saturated common salt is washed, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, residue post separating-purifying (with sherwood oil: ethyl acetate=5:1 is eluent), obtain white solid 3,7-bis-bromo-2,8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-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)。By obtained white solid 3,7-bis-bromo-2,8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (0.732 gram, 1 mmole), connection boric acid pinacol ester (1.02 grams, 4 mmoles), Potassium ethanoate (1.2 grams), tetra-triphenylphosphine palladium (0.1 gram) and 1,4-dioxane, refluxes 24 hours under an inert atmosphere.Be poured into water by obtained mixing solutions, with dichloromethane extraction, the saturated common salt water washing of set oil phase, anhydrous magnesium sulfate drying, after adopting silica gel column chromatography to be separated, obtains white solid after concentrated.
1h NMR,
13c NMR, MS and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 4:3,7-bis-(9,9-dimethyl-9H-fluorenes-2-base)-(2,8-bis-(6-bromine hexyloxy))-S, S-dioxydibenze thiophthene
By 3,7-bis-of careful purifying bromo-2,8-bis-(the bromo-hexyloxy of 6-)-S; S-dioxo-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/L, 10 milliliters); Tetrabutyl amonium bromide (0.1 gram) and toluene (30 milliliters) add in 250 milliliters of there-necked flasks, be warming up to 90 degree and react 24 hours under protection of inert gas.Poured into by mixing solutions in frozen water, with dichloromethane extraction, set oil phase saturated common salt is washed, distillation washing, anhydrous magnesium sulfate drying.After being spin-dried for by organic solvent, silica gel column chromatography obtains white solid product after being separated.
1h NMR,
13c NMR, MS, results of elemental analyses show that obtained compound is target product.
Embodiment 5:3,7-dibromo [4,7-bis-(N-(4-bromophenyl))]-S, S-dioxydibenze thiophthene
In 250 milliliters of two-mouth bottles; add pentanoic (3.40 grams); 3; bromo-S, the S-dioxo-dibenzothiophene of 7-bis-(3.74 grams) and sodium tert-butoxide (8.69 grams), then add toluene (100 milliliters); after stirring half an hour under nitrogen protection; slow dropping 3-tertiary butyl phosphine (1.12 grams), adds palladium (0.10 gram), heating reflux reaction 24 hours.Be cooled to room temperature, with dichloromethane extraction, after removing solvent under reduced pressure, obtain solid.Fill post with silica gel, petrol ether/ethyl acetate (50:1) is made eluent and is carried out column chromatography purification, obtains yellow solid powder, productive rate: 70%.Then, in 500 milliliters of two-mouth bottles, add 4,7-bis-(N-(4-phenyl))-3,7-S, S-dioxo-dibenzothiophenes (5.51 grams), tetrahydrofuran (THF) (150 milliliters), stir, after ice bath is cooled to 0 DEG C, slowly drip N-bromo-succinimide (7.5 grams), after dripping, slowly rise to room temperature reaction 24 hours, then removal of solvent under reduced pressure, obtains solid, carrier is done with silica gel, petrol ether/ethyl acetate (20:1) makees eluent, and column chromatography obtains yellow solid, productive rate after purifying: 72%.
1h NMR,
13c NMR, MS and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Two (3-(N, N-dimethyl amido) propoxy-)-S, the S-dioxo-dibenzothiophene of embodiment 6:3,7-bis-bromo-2,8-
Under nitrogen protection; 3 are added in there-necked flask (250 milliliters); 7-bis-bromo-2; 8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (0.732 gram, 1 mmole); Tetrabutyl amonium bromide (0.3 gram); aqueous sodium hydroxide solution (50%, 4 milliliters) and dimethyl sulfoxide (DMSO) (50 milliliters), stir 1 hour.Then add excessive N, the aqueous solution (2 grams, 13 mmoles) of N-dimethyl chloride propylamin hydrochloride, continue stirring and spend the night.Mixture is poured into water, with dichloromethane extraction, anhydrous magnesium sulfate drying, after concentrated, obtains white solid by after product acetone/water mixed solution recrystallization.
1h NMR,
13c NMR, MS and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Bromo-2,8-bis-(6-diethylamine hexyloxy)-S, S-dioxo-dibenzothiophene and the zwitterionic derivative of embodiment 7:3,7-bis-
Taking 3,7-bis-bromo-2,8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (7.32 grams, 10.0 mmoles) is dissolved in DMF, is heated to backflow, under argon shield, adds diethylamine.React 24 hours.Then reaction system is down to room temperature, reaction system is poured into water, with dichloromethane extraction, set oil phase saturated common salt is washed, distillation washing, anhydrous magnesium sulfate drying.Be spin-dried for, residue post separating-purifying (taking ethyl acetate as eluent), obtain white solid 3,7-bis-bromo-2,8-bis-(6-diethylamine-hexyloxy)-S, S-dioxo-dibenzothiophene.Then, in 100 milliliters of there-necked flasks, add 3,7-bis-bromo-2,8-bis-(6-diethylamine-hexyloxy)-S, S-dioxo-dibenzothiophene (0.5 gram), add tetrahydrofuran (THF) (20 milliliters), stir under nitrogen protection.Then add excessive Isosorbide-5-Nitrae-butyl sulfonic acid lactone and DMF (20 milliliters), be slowly warming up to 100 ° of C, stir 5 days under nitrogen protection.Distill away tetrahydrofuran (THF) and excessive DMF, Ionized crude product is precipitation in ethyl acetate (100 milliliters), filters, with chloroform, dry under vacuo, obtains pulverulent solids for its zwitterionic derivative.
1h NMR,
13c NMR, MS and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Two (6-(N, N-bis-(2-hydroxyethyl) amido)-hexyloxy)-S, the S-dioxo-dibenzothiophene of embodiment 8:3,7-bis-bromo-2,8-
Bromo-for 3,7-bis-2,8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (7.32 grams, 10.0 mmoles) are dissolved in DMF, add excessive diethanolamine, react 48 hours under argon shield and room temperature.Then the solvent in decompression removing reaction system, by residual solids dried overnight in atmosphere, vacuum-drying 24 hours.Obtain powdery white solid.
1h NMR,
13c NMR, MS and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 9:3,7-bis-bromo-2,8-(6,6 '-bromo two (N, N, N-trimethyl-1-ammonium))-S, S-dioxo-dibenzothiophene
By bromo-for 3,7-bis-2,8-bis-(the bromo-hexyloxy of 6-)-S; S-dioxo-dibenzothiophene (7.32 grams, 10.0 mmoles) is dissolved in DMF; add excessive aqueous trimethylamine, react 48 hours under argon shield and room temperature.Then the solvent in decompression removing reaction system, by residual solids dried overnight in atmosphere, vacuum-drying 24 hours.Obtain powdery white solid.
1h NMR,
13c NMR, MS and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Bromo-2,8-bis-(the phosphate-based hexyloxy of 6-)-S, the S-dioxo-dibenzothiophenes of embodiment 10:3,7-bis-and 3,7-bis-bromo-2,8-bis-((6-sodium phosphate base)-hexyloxy)-S, S-dioxo-dibenzothiophene
Under the protection of inert atmosphere, bromo-for 3,7-bis-2,8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (7.32 grams, 10.0 mmoles) are dissolved in triethyl-phosphite, are heated to 140 ° of C reactions and spend the night.After reaction terminates, mixing solutions is cooled to room temperature, underpressure distillation removes remaining solvent, and crude product chromatography column purification (ethyl acetate/petroleum ether=1:1 is eluent) obtains white solid 3,7-bis-bromo-2,8-bis-(the phosphate-based hexyloxy of 6-)-S, S-dioxo-dibenzothiophene.Then; by the white solid 3 obtained; bromo-2,8-bis-(the phosphate-based hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (2.0 grams) of 7-bis-are dissolved in DMF; add excessive aqueous sodium carbonate; then flow through night next time in argon shield, product is precipitated in normal hexane, filter; with n-hexane, after vacuum-drying, obtain white powdery solids.
1h NMR,
13c NMR, MS and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 11: poly-[3,7-(two-2,8-bis-(N, N dimethylamine hexyloxy)-S, S-dioxo-dibenzothiophene] (P1) and zwitterionic derivative (P2) thereof
By through 3 of careful purifying; 7-bis-bromo-2; 8-bis-(6-diethylamine-hexyloxy)-S, S-dioxo-dibenzothiophene (0.126 gram, 0.5 mmole) is dissolved in toluene and N; in the mixed solvent of dinethylformamide; then under argon shield, add two (1,5-cyclooctadiene) nickel (2.5 milligrams), 1,5-cyclooctadiene (2.5 milligrams) and dipyridyl (10 milligrams); return stirring 24 hours under an ar atmosphere, adds bromobenzene (0.3 milliliter) reaction 6 hours.Terminate reaction, reaction system is down to room temperature, pours in methyl alcohol and precipitate, filter, precipitate in acetone after filtrate is concentrated, filter, gained filter cake dried overnight in atmosphere, then vacuum-drying 24 hours, obtains white powdery solids.
1h NMR,
13c NMR and results of elemental analyses show that obtained is target product.Then, obtained white powdery solids (500 milligrams) is added in 100 milliliters of there-necked flasks, adds tetrahydrofuran (THF) (20 milliliters), stir under nitrogen protection.Then add excessive Isosorbide-5-Nitrae-butyl sulfonic acid lactone and DMF (20 milliliters), be slowly warming up to 100 ° of C, stir 5 days under nitrogen protection.Distill away tetrahydrofuran (THF) and excessive DMF, Ionized polymkeric substance is precipitation in ethyl acetate (100 milliliters), filters, with chloroform, dry under vacuo, obtains pulverulent solids for its zwitterionic derivative.
1h NMR,
13c NMR and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 12: poly-[3,7-bis-(two (the phosphate-based hexyloxy of 6-)-S, the S-dioxo-dibenzothiophene of 2,8-)-alt-2,2 '-(9,9 '-two spiral shell fluorenes)] (P3) and ionization derivative (P4) thereof
By through 3 of careful purifying, 7-bis-bromo-2, 8-bis-(the phosphate-based hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (0.8465 gram, 1 mmole), 2, 2 '-bis-(4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate-2-base)-9, 9 '-spiro-bisfluorene (0.5683 gram, 1 mmole), be dissolved in toluene, then under argon shield, add palladium (10 milligrams), tricyclohexyl phosphine (20 milligrams) and the tetraethyl ammonium hydroxide aqueous solution (5 milliliters), under an argon after return stirring 24h, add phenylo boric acid (20 milligrams), react 6 hours, add bromobenzene (0.3 milliliter) reaction 6 hours again.Terminate reaction, reaction system is down to room temperature, pours in methyl alcohol and precipitate, filter, then with washing with acetone 24 hours to remove oligopolymer and catalyst residue, products therefrom air-dried overnight, then vacuum-drying 24 hours, obtains yellow powdery solid.Then, the white solid obtained (100 milligrams) is dissolved in DMF; add excessive aqueous sodium carbonate, then flow through night next time in argon shield, product is precipitated in normal hexane; filter, with n-hexane, after vacuum-drying, obtain white powdery solids.
1h NMR,
13c NMR and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 13: poly-[3,7-(2,8-bis-(6-octyloxy-S, S-dioxo-dibenzothiophene))]-alt-[3, the 7-bis-(two (3-(N of 2,8-, N-dimethyl propyl amine))-S, S-dioxo-dibenzothiophene)] (P5)
By through 3 of careful purifying, 7-bis-(4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate)-2, 8-bis-octyloxy-S, S-dioxo-dibenzothiophene (0.7244 gram, 1 mmole), 3, 7-bis-bromo-2, two (3-(the N of 8-, N-dimethyl amido) propoxy-)-S, S-dioxo-dibenzothiophene (0.606 gram, 1 mmole) be dissolved in toluene (15 milliliters), then under argon shield, add palladium (15 milligrams), tricyclohexyl phosphine (25 milligrams) and the tetraethyl ammonium hydroxide aqueous solution (5 milliliters), return stirring is after 48 hours under an ar atmosphere, add phenylo boric acid (20 milligrams), react 6 hours, add bromobenzene (0.5 milliliter) reaction 6 hours again.Terminate reaction, reaction system is down to room temperature, pours in methyl alcohol and precipitate, filter, then with washing with acetone 24 hours to remove oligopolymer and catalyst residue, products therefrom air-dried overnight, vacuum-drying 24 hours.
1h NMR,
13c NMR and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 14: poly-[3,7-(2,8-bis-(6-(N, N-di-alcohol amido)-hexyloxy)-S, S-dioxo-dibenzothiophene)-alt-2,8-(6,6,12,12-tetra-octyl group-6,12-indoline [1,2-b] fluorenes)] (P7)
By through 3 of careful purifying, 7-bis-(4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate)-2, 8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (0.8263 gram, 1 mmole), 3, 7-bis-bromo-2, 8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (0.6589 gram, 0.9 mmole) and 2, 8-bis-bromo-6, 6, 12, 12-tetra-octyl group-6, 12-indoline [1, 2-b] fluorenes (0.0861g, 0.1 mmole, purchased from American Sigma-Aldrich company), be dissolved in toluene, then under argon shield, add palladium (10 milligrams), tricyclohexyl phosphine (20 milligrams) and the tetraethyl ammonium hydroxide aqueous solution (5 milliliters), return stirring is after 24 hours under an ar atmosphere, add phenylo boric acid (20 milligrams), react 6 hours, add bromobenzene (0.3 milliliter) reaction 6 hours again.Terminate reaction, reaction system is down to room temperature, pours in methyl alcohol and precipitate, filter, then with washing with acetone 24 hours to remove oligopolymer and catalyst residue, products therefrom air-dried overnight, then vacuum-drying 24 hours, obtains yellow powdery solid.Further the product that obtains is dissolved and DMF mixed solvent in, add diethanolamine (0.5 gram), reaction 48 hours under argon shield and room temperature.Then reaction system is poured into water precipitation, filters, filter cake air-dried overnight, then vacuum-drying 24 hours.
1h NMR,
13c NMR and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 15: polar functionalities S, S-dioxo-dibenzothiophene unit water/alcohol dissolubility non-conjugated polymeric thing (P10)
By 1-methylisatin (1 mmole) and 2; two ((the 6-bromine hexyloxy)-3 of 8-; 7-bis-(9; 9-dimethyl-9H-fluorenes-2-base)-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 is poured in methyl alcohol after at room temperature stirring 12 hours and is precipitated, and filters, and will obtain white flock precipitate methyl alcohol and washing with acetone complete, then drying 24 hours under vacuo, obtains white fibrous polymer.Being dissolved in by the polymkeric substance obtained (100 milligrams) is further dissolved in triethyl-phosphite, is heated to 140 ° of C reactions and spends the night.After reaction terminates, mixing solutions is cooled to room temperature, underpressure distillation removes remaining solvent, obtains white solid powder.Then; further the white solid obtained (100 milligrams) is dissolved in N; in dinethylformamide; add excessive aqueous sodium carbonate; then flow through night next time in argon shield, product is precipitated in normal hexane, filter; with n-hexane, after vacuum-drying, obtain white powdery solids.
1h NMR,
13c NMR and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 16: poly-[2,7-(9,9-dioctyl) fluorenes]-co-[3,7-bis-(2,8-two (3-(N, N-dimethyl propyl amine)-S, S-dioxo-dibenzothiophene)] (P11)
By through 2 of careful purifying, 7-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate-two base)-9, 9-bis--octyl group fluorenes (0.3208 gram, 0.5 mmole), 2, 7-bis-bromo-9, 9-dioctyl fluorene (0.2194 gram, 0.40 mmole) and 3, 7-bis-bromo-2, two (3-(the N of 8-, N-dimethyl amido) propoxy-)-S, S-dioxo-dibenzothiophene (0.0606 gram, 0.10 mmole) be dissolved in toluene, then under argon shield, add palladium (2.5 milligrams), tricyclohexyl phosphine (2.5 milligrams) and the tetraethyl ammonium hydroxide aqueous solution (1 milliliter), return stirring is after 48 hours under an ar atmosphere, add phenylo boric acid (20 milligrams), react 6 hours, add bromobenzene (0.3 milliliter) reaction 6 hours again.Terminate reaction, reaction system is down to room temperature, pours in methyl alcohol and precipitate, filter, then with washing with acetone 24 hours to remove oligopolymer and catalyst residue, products therefrom air-dried overnight, then vacuum-drying 24 hours.H NMR,
13cNMR and results of elemental analyses show that obtained is target product.In addition, by regulate several compound molar ratio 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-9,9-bis--octyl group fluorenes: 2, bromo-9, the 9-dioctyl fluorene of 7-bis-: 3,7-bis-bromo-2, two (3-(N, N-dimethyl amido) propoxy-)-S, the S-dioxo-dibenzothiophene of 8-, preparation repeats above process, can obtain the derivative of the multipolymer of a series of different ratios.
1h NMR,
13c NMR and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 17: the water/alcohol dissolubility hyperbranched polymer (P12) of polar functionalities S, S-dioxo-dibenzothiophene unit
By through 2 of careful purifying, 7-two-(4, 4, 5, 5-dimethyl-1, 3, 2-dioxaborinate-two base)-bis-[9, 9 '-dioctyl)] fluorenes (0.6426 gram, 1 mmole), three (4-bromobenzene) amine (24.1 milligrams, 0.05 mmole), 3, 7-bis-bromo-2, two (3-(the N of 8-, N-dimethyl amido) propoxy-)-S, S-dioxo-dibenzothiophene (0.5475 gram, 0.95 mmole), be dissolved in toluene, then under argon shield, add palladium (10 milligrams), tricyclohexyl phosphine (20 milligrams) and the tetraethyl ammonium hydroxide aqueous solution (5 milliliters), return stirring is after 24 hours under an ar atmosphere, add phenylo boric acid (20 milligrams), react 6 hours, add bromobenzene (0.3 milliliter) reaction 6 hours again.Terminate reaction, reaction system is down to room temperature, pours in methyl alcohol and precipitate, filter, then with washing with acetone 24 hours to remove oligopolymer and catalyst residue, products therefrom air-dried overnight, then vacuum-drying 24 hours, obtaining yellow powdery solid is hyperbranched polymer presoma.Then, obtained hyperbranched polymer presoma is dissolved in THF, adds aqueous trimethylamine, at room temperature stir 5 days, solvent under reduced pressure is removed, obtains white powdery solids.
1hNMR,
13c NMR and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
Embodiment 18: the water/alcohol dissolubility hyperbranched polymer (P14) of polar functionalities S, S-dioxo-dibenzothiophene unit
3 are added in 50 milliliters of there-necked flasks, 7-bis-(4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate)-2, 8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (0.8263 gram, 1 mmole), 3, 7-dibromo [4, 7-bis-(N-(4-bromophenyl))]-S, S-dioxydibenze thiophthene (8.7 milligrams, 0.01 mmole) and 3, 7-bis-bromo-2, 8-bis-(the bromo-hexyloxy of 6-)-S, S-dioxo-dibenzothiophene (0.7248 gram, 0.99 mmole), toluene (15 milliliters) and aqueous sodium carbonate (2 mol/L, 5 milliliters) in, then under argon shield, add tetra-triphenylphosphine palladium (10 milligrams), return stirring is after 48 hours under argon gas, add phenylo boric acid (20 milligrams), react 6 hours, add bromobenzene (0.3 milliliter) reaction 6 hours again.Terminate reaction, reaction system is down to room temperature, pours in methyl alcohol and precipitate, filter, then with washing with acetone 24 hours to remove oligopolymer and catalyst residue, products therefrom air-dried overnight, then vacuum-drying 24 hours.Further the product that obtains is dissolved and DMF mixed solvent in, add diethanolamine (0.5 gram), reaction 48 hours under argon shield and room temperature.Then reaction system is poured into water precipitation, filter, filter cake air-dried overnight, then vacuum-drying 24 hours, obtains white powdery solids product.
1hNMR,
13c NMR and results of elemental analyses show that obtained is target product.Its chemical equation is as follows:
The physical chemistry of table 1 polymkeric substance and electrochemical properties
Below with the water/alcohol soluble polymer (P1, P10 and P12) of several polar functionalities S, S-dioxo-dibenzothiophene unit for example illustrates polymkeric substance of the present invention is as the application of cathode interface layer in photodiode and photovoltaic device.
Embodiment 19
By ITO conductive glass, square resistance ~ 20 Ω/, is precut into 15 millimeters × 15 millimeters square pieces.Use acetone, micron order semi-conductor special purpose detergent, deionized water, Virahol ultrasonic cleaning successively, it is for subsequent use that nitrogen purging is placed on constant temperature oven.Before using, the clean sheet of ITO in oxygen plasma etch instrument with plasma bombardment 10 minutes.Select PVK available from Aldrich Co, with tetrachloroethane obtain solution.PEDOT:PSS aqueous dispersions (about 1%) is purchased from Bayer company, and buffer layer is with the spin coating of sol evenning machine (KW-4A) high speed, and thickness is determined by strength of solution and rotating speed, with surface profiler (Tritek company Alpha-Tencor500 type) actual measurement monitoring.After film forming, in constant-temperature vacuum baking oven, drive away solvent residues, post bake.
After red light conjugated polymer MEH-PPV is weighed in white vase, proceed to nitrogen protection film forming special gloves case (VAC company), dissolve in toluene, filter with 0.45 micron membrane filter.Polymer light-emitting layer optimum thickness is 70 ~ 90 nanometers.Thickness TENCOR ALFA-STEP-500 surface profiler measures.P1 is dissolved in methyl alcohol (adding a small amount of acetic acid), is mixed with the solution of 2 mg/ml concentration, filter with 0.45 micron membrane filter.With sol evenning machine spin coating skim P1 on the substrate of ITO/PEDOT:PSS/MEH-PPV, its thickness about 5 nanometer.Aluminium electrode evaporation vacuum tightness in vacuum plating unit reaches 3 × 10
-4complete during below Pa.The thickness of plated film speed and each layer electrode is monitored in real time by quartz resonator film thickness monitor (STM-100 type, Sycon company).The region that the light-emitting zone of device is covered alternately by mask and ITO is defined as 0.15 square centimeter.All preparation process are all carried out in the glove box providing nitrogen inert atmosphere.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.Water/alcohol soluble polymer (P1) respectively on ITO/PEDOT:PSS/MEH-PPV described in spin coating skim is as interfacial layer, and then vacuum evaporation Al is as negative electrode, makes polymer LED.For showing the effect of cathode interface layer of the present invention, with adopt directly on luminescent layer vacuum evaporation Al as negative electrode device compared with.The same with the device fabrication processes of P1, P10, P12 and PFN interfacial layer, result is as shown in table 1.With or without P1(P10, P12 or PFN) Current density-voltage-luminosity of the device of layer and luminous efficiency-current density are as shown in Figure 1 a, 1 b.
Table 2 based on MEH-PPV red-light-emitting polymer, the luminescent properties of P1, P10, P12 or PFN electron transfer layer/aluminium cathode device
Example is visible thus, for MEH-PPV red light conjugated polymer conventional device, P1 is added between luminescent layer and high-work-function metal aluminium, after P10 or P12 layer, the performance of device all far away higher than the performance of AM aluminum metallization device direct on luminescent layer, and is better than adopting PFN to do device performance as cathode interface layer.
Embodiment 20
Repeat embodiment 10, with P1, P10, P12 or PFN as electron transfer layer, adopt P-PPV green glow conjugated polymers as luminescent layer, adopt high-work-function metal gold as negative electrode, other condition is constant, and measuring result is as shown in table 2.With or without the Current density-voltage-luminosity of the device of P1, P10, P12 and PFN layer and luminous efficiency-current density as shown in Fig. 2 a, Fig. 2 b.
Table 3 based on P-PPV green glow polymkeric substance, the luminescent properties of P1, P10, P12 or PFN electron transfer layer/au cathode device
Example is visible thus, for P-PPV green glow conjugated polymers conventional device, P1 is added between luminescent layer and high-work-function metal gold, after P10 or P12 layer, the performance of device all far away higher than the performance of gold evaporation device direct on luminescent layer, and is better than adopting PFN to do device performance as cathode interface layer.
Embodiment 21
By ITO conductive glass, square resistance ~ 20 Ω/, is precut into 15 millimeters × 15 millimeters square pieces.Use acetone, micron order semi-conductor special purpose detergent, deionized water, Virahol ultrasonic cleaning successively, it is for subsequent use that nitrogen purging is placed on constant temperature oven.Before using, the clean sheet of ITO in oxygen plasma etch instrument with plasma bombardment 10 minutes.Select PVK available from Aldrich Co, with tetrachloroethane obtain solution.PEDOT:PSS aqueous dispersions (about 1%) is purchased from Bayer company, buffer layer is with the spin coating of sol evenning machine (KW-4A) high speed, thickness is about 40 nanometers, is determined by strength of solution and rotating speed, with surface profiler (Tritek company Alpha-Tencor500 type) actual measurement monitoring.After film forming, in constant-temperature vacuum baking oven, drive away solvent residues, post bake.
Using polymer solar cells material (PCBM as acceptor, PFO-DBT35:PC
61bM=1:2) be placed in clean sample bottle and weigh, proceed to subsequently in the glove box of nitrogen protection, for high pure nitrogen protection is with the state maintaining hypoxemia low humidity in glove box.With suitable solvent (as toluene, chlorobenzene, dichlorobenzene etc.) by for the preparation of active coating polymer dissolution and be placed in and mixing platform carry out stirring material is dissolved completely.The ITO substrate scribbling anode buffer layer good for vacuum-drying is moved into the spin coating carrying out polymer active layers in glove box, and the process of spin coating is identical with anode buffer layer.Scraping by sharp instrument the side dialling diaphragm makes ITO layer exposed, as the anode of device after electrode evaporation.The organic solvent that dry removing is residual.Polymer solar battery active coating optimum thickness is 70 ~ 90 nanometers.Thickness TENCOR ALFA-STEP-500 surface profiler measures.P1 is dissolved in methyl alcohol (adding a small amount of acetic acid), is mixed with the solution of 0.2 mg/ml concentration, filter with 0.45 micron membrane filter.On the ITO substrate getting rid of polymer solar battery material and PEDOT:PSS layer, skim P1 polymkeric substance is generated respectively, its thickness about 5 nanometer with sol evenning machine.Aluminium electrode evaporation vacuum tightness in vacuum plating unit reaches 3 × 10
-4complete during below Pa.The thickness of plated film speed and each layer electrode is monitored in real time by quartz resonator film thickness monitor (STM-100 type, Sycon company).The region that the light-emitting zone of device is covered alternately by mask and ITO is defined as 0.15 square centimeter.All preparation process are all carried out in the glove box providing nitrogen inert atmosphere.Solar cell performance is at simulated solar irradiation (AM1.5G73.2mW/cm
2) under measure.For showing the effect of electron transfer layer of the present invention, adopt on the ITO substrate getting rid of PEDOT:PSS direct spin on polymers solar cell material PFO-DBT35:PC60BM conjugated polymers as reference, vacuum evaporation metal A l(100 nanometer on active coating) as negative electrode, make polymer solar cells device as reference device.Measuring result is as shown in table 3.With PFO-DBT35:PC
61bM conjugated polymers is compared, with or without the current density of the solar cell device of the device of P1, P10 or P12 layer and voltage relationship as shown in Figure 3.
Table 4, based on donor polymer PFO-DBT35:PC60BM, is the Photovoltaic Device Performance of electron transfer layer with P1, P10 or P12
Example is visible thus, for employing PFO-DBT35:PC
61bM is the conventional device of photoabsorption active coating, respectively spin coating skim P1 between device photoabsorption active coating and Al, and after P10 or P12, the open circuit voltage of device, short-circuit current and power conversion efficiency are all higher than the device of evaporating Al direct on photoabsorption active coating.
Claims (4)
1. a class is containing polar substitution group S, and S-dioxo-dibenzothiophene monomer, is characterized in that chemical structural formula is
In formula, R is-(CH
2)
nx, n=1 ~ 30; X concrete structure formula is as follows:
2. contain polar substitution group S described in claim 1, the preparation method of S-dioxo-dibenzothiophene monomer, comprises the steps:
(1) first by bromine, dibenzothiophene bromination is become the bromo-dibenzothiophene of 2,8-bis-; (2) 2,8-bis-bromo-dibenzothiophene of preparation are dissolved in refining anhydrous tetrahydro furan, add n-Butyl Lithium at low temperatures, react after 2 hours, add trimethyl borate, then rise to room temperature reaction, obtain white crystal 2,8-hypoboric acid-dibenzothiophene; (3) 2, the 8-hypoboric acid obtained-dibenzothiophene is placed in flask, adds excessive hydrogen peroxide, react 5 hours at 50 DEG C, after purifying, obtain white solid 2,8-dihydroxyl-dibenzothiophene; (4) under the protection of inert atmosphere, 2,8-dihydroxyl-dibenzothiophene is added two excessive bromoalkanes and carries out alkylated reaction, obtain white solid 2,8-bis-(bromo alkoxyl group) dibenzothiophene; (5) 2,8-bis-(bromo alkoxyl group) dibenzothiophene is dissolved in glacial acetic acid, after adding hydrogen peroxide oxidation, obtains white solid 2,8-dibromo alkoxyl group-S, S-dioxo-dibenzothiophene; (6) by 2,8-dibromo alkoxyl group-S, S-dioxo-dibenzothiophene slowly drips bromine and carries out bromination in glacial acetic acid/trichloromethane mixed solvent, obtain white solid 3,7-bis-bromo-2,8-bis-(bromine alkoxyl group)-S, S-dioxo-dibenzothiophene; (7) by 3, alkoxyl group bromine and the corresponding polar group of 7-bis-bromo-2,8-bis-(bromine alkoxyl group)-S, S-dioxo-dibenzothiophene side chain terminal react, obtain the S containing polar substitution group of described chemical structural formula 1 correspondence, S-dioxo-dibenzothiophene monomer.
3. contain polar substitution group S based on described in claim 1, the water/alcohol soluble polymer of S-dioxo-dibenzothiophene unit, is characterized in that structure is:
(1) simple linear polymer
X, y are molar fraction, 0≤x≤0.7,0.3≤y≤1, and x+y=1, and polymerization degree n: 1 ~ 300, works as x=0, and during y=1, described polymkeric substance is that its structure is as follows based on containing polar substitution group S, the homopolymer of S-dioxo-dibenzothiophene unit:
(2) hyperbranched polymer
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 formula, R is-(CH
2)
nx, n=1 ~ 30, X concrete structures are:
In formula, structural unit A is one of following conjugation or non-conjugated structure unit:
2,7-substituted fluorene;
3,6-substituted fluorene;
2,7-replaces spiral shell fluorenes;
2,7-replaces silicon fluorenes;
2,7-substituted carbazole;
3,6-substituted carbazole;
3,9-substituted indole carbazole;
2,8-substituted indole carbazole;
3,9-substituted indole fluorenes;
2,8-substituted indole fluorenes;
isosorbide-5-Nitrae-substituted benzene;
2,2 '-replace spiral shell fluorenes
3,3-disubstituted indole-2-ketone
R
1for the straight or branched alkyl that carbonatoms is 1-16;
In formula, B is conjugation or non-conjugated structure unit, has one of following chemical structural formula:
triphenylamine;
triazine;
1,3,5-trisubstituted benzene;
n-phenyl-3,6-carbazole;
3,4,5-triphenyl-1,2,4-triazole;
4,7-bis-(4 ', 4 "-two substituted diphenylamines) base-2,1,3-diazosulfide;
4,7-bis-(4 ', 4 "-two replace triphenylamines) base-2,1,3-diazosulfide;
4,7-bis-(4 ', 4 "-two substituted diphenylamines) base-3,7-dibenzothiophene-S, S-dioxy;
4,7-bis-(4 ', 4 "-two replace triphenylamines) base-3,7-dibenzothiophene-S, S-dioxy.
4. according to claim 3 containing polar substitution group S, water/the alcohol soluble polymer of S-dioxo-dibenzothiophene unit is as the purposes of cathode interface materials application in Organic Light Emitting Diode or solar cell, it is characterized in that the polymer LED to multilayered structure, between luminescent layer and high-work-function metal electrode, insert the film of polymkeric substance described in one deck; Or to bulk heterojunction solar cell device, between photovoltaic active layers and high-work-function metal electrode, insert the film of polymkeric substance described in one deck.
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| CN109180912A (en) * | 2018-09-21 | 2019-01-11 | 台州学院 | Conjugation microporous polymer and preparation method thereof based on Cyanuric Chloride and dibenzothiophenes |
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| CN113061141B (en) * | 2019-12-31 | 2022-03-29 | 华南理工大学 | Water-soluble conjugated polymer for photothermal therapy, polymerized monomer thereof, preparation method and application |
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