CN102827356A - Conjugated polymer of 9-heptadecyl carbazole and chloroquinoxaline - Google Patents
Conjugated polymer of 9-heptadecyl carbazole and chloroquinoxaline Download PDFInfo
- Publication number
- CN102827356A CN102827356A CN2012103169188A CN201210316918A CN102827356A CN 102827356 A CN102827356 A CN 102827356A CN 2012103169188 A CN2012103169188 A CN 2012103169188A CN 201210316918 A CN201210316918 A CN 201210316918A CN 102827356 A CN102827356 A CN 102827356A
- Authority
- CN
- China
- Prior art keywords
- polymer
- conjugated polymers
- heptadecyl
- carbazole
- fluoro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 Cc1ccc(-c2nc(c(-c([s]3)ccc3Br)cc(F)c3-c([s]4)ccc4Br=C)c3nc2-c2ccc(*)[s]2)[s]1 Chemical compound Cc1ccc(-c2nc(c(-c([s]3)ccc3Br)cc(F)c3-c([s]4)ccc4Br=C)c3nc2-c2ccc(*)[s]2)[s]1 0.000 description 4
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention belongs to the organic polymer functional material field, and concreatly relates to a conjugated polymer of 9-heptadecyl carbazole and chloroquinoxaline, a structural general formula of the conjugated polymer is shown as the following formula:. The conjugated polymer takes 9-heptadecyl-2,7-carbazole as a power supply unit, and a dibromo chloroquinoxaline monomer is taken as an electron-deficient unit, the conjugated polymer is prepared by a Suzuki coupling reaction, and is used for a donor material of a heterojunction solar energy cell. The polymer introduces a strong electron-withdrawing group fluorine atom on an electron-deficient unit, thereby the HOMO energy level of the material can be effectively reduced, thereby the open-circuit voltage of the polymer photovoltaic cell can be enhanced. By using cyclic voltammetry determination, non-chloroquinoxaline-9-heptadecyl substituted carbazole polymer is compared with the conjugated polymer, the HOMO energy level of a single fluoropolymer is lower by 0.02-0.2eV than that of the non-chloroquinoxaline, and the HOMO energy level of the double fluoro polymer is lower by 0.05-0.3eV than that of the non-chloroquinoxaline. The fluoro material and PCBM is blended and used in a photolytic activity layer of the heterojunction polymer solar energy battery, and the open-circuit voltage of the device is 0.6-1.0V.
Description
Technical field
The invention belongs to functional high polymer material field, be specifically related to the conjugated polymers of a kind of 9-heptadecyl carbazole and fluoro quinoxaline.
Background technology
The intensification day by day of the environmental pollution that causes along with energy dilemma and combustion of fossil fuels has received more concern to the exploitation of renewable energy source.Polymer solar battery because its preparation process is simple, cost is low, in light weight and can be prepared into outstanding advantage such as flexible device; Become domestic and international research focus in recent years, the focus of current polymer solar battery research is to develop efficiently conjugated polymers to improve its photovoltaic energy conversion efficient for body and acceptor material.For the polymer materials that serves as electron donor(ED), the absorption spectrum of material has determined the short-circuit current of device, and the HOMO energy level of material has determined the open circuit voltage of device, and the structure of material and carrier mobility have determined the packing factor of device.For obtained performance good give the body polymer materials, electron rich unit (D) and electron deficiency unit (A) giving of introducing alternately that the main chain of conjugated polymers forms-acceptor (D-A-D) type polymkeric substance is become the emphasis of giving the research of body polymkeric substance at present.
Quinoxaline and verivate thereof be as one type of novel short of electricity unit, receives much concern in recent years and obtain good performance, for example synthetic PECz-DTQX such as Cao Yong; With the PCBM blend, electricity conversion is for reaching 6.07%, [advanced material Adv.Mater.2011; 23 (27), 3086-3089].
In order further to improve the photoelectric transformation efficiency of polymer solar battery, under the prerequisite that guarantees big short-circuit current, the selection that is inevitable of the open circuit voltage of enhance device.Research in recent years shows, will have the body unit that receives that the fluorine atom of haling electrical property introduces to the body polymkeric substance and can effectively reduce the highest occupied molecular orbital energy (HOMO can) of material, and then can promote the open circuit voltage of battery.As 2009; People such as Hou Jianhui are through receiving on the body unit to introduce and draw electric group F atom to obtain polymer P BDTTT-CF at PBDTTT-C; The HOMO of material can be reduced to-5.22eV by-5.12eV; Open circuit voltage has been brought up to 0.76V [Nat.Photon.2009,3,649-653] by 0.7V.2010; People such as Luping Yu the donor material PTBF0 of its research and development receive introduce fluorine atom on the body unit; Obtain polymer P TBF1, the HOMO of material can be reduced to-5.15eV by-4.94eV, and open circuit voltage has been brought up to 0.74V [J.Am.Chem.Soc.2011 by 0.58V; 133,1885-1894].
Fluorine atom is to effect of material performance in view of the above; On this electron deficiency of quinoxaline unit, introduce fluorine atom prepare novel fluorine-containing D-A-D type be expected to further reduce HOMO for the body polymkeric substance can; Promote open circuit voltage; Thereby improve the device photovoltaic performance, but also do not see structure, the preparation method of relevant this type of material so far and be applied to the report in the photovoltaic cell.
Summary of the invention
Deficiency to prior art; The objective of the invention is to, the conjugated polymers of a kind of 9-heptadecyl carbazole and fluoro quinoxaline is provided, this conjugated polymers is by 9-heptadecyl-2; The 7-carbazole is as giving electric unit; Two bromines replace fluoro quinoxaline monomer as the short of electricity unit, make through the Suzuki linked reaction, can be used in the donor material of body heterojunction solar cell.This polymkeric substance can effectively reduce material HOMO energy level owing on electron deficiency unit quinoxaline, introduced strong electron-withdrawing group fluorine atom, thereby promotes the open circuit voltage of polymer photovoltaic cell.
To achieve these goals, the present invention adopts following technical solution:
The conjugated polymers of a kind of 9-heptadecyl carbazole and fluoro quinoxaline, the general structure of said conjugated polymers is suc as formula shown in the I:
In the formula, R
1: H or F atom;
R
2: a position or para-position carbon atomicity are the alkoxyl phenyl of 4 to 20 straight or branched, and perhaps carbonatoms is the 2-alkylthrophene base or 2 of 4 to 20 straight or branched, 3-dialkyl group thienyl;
R
3: H or carbonatoms are 1 to 20 straight or branched alkyl.
Preferred polymer A in the conjugated polymers of described 9-heptadecyl carbazole and fluoro quinoxaline, its structure is suc as formula shown in the II:
Preferred polymer B in the conjugated polymers of described 9-heptadecyl carbazole and fluoro quinoxaline, its structure is suc as formula shown in the III:
Preferred polymkeric substance C in the conjugated polymers of described 9-heptadecyl carbazole and fluoro quinoxaline, its structure is suc as formula shown in the IV:
Preferred polymkeric substance D in the conjugated polymers of described 9-heptadecyl carbazole and fluoro quinoxaline, its structure is suc as formula shown in the V:
Preferred polymkeric substance E in the conjugated polymers of described 9-heptadecyl carbazole and fluoro quinoxaline, its structure is suc as formula shown in the VI:
The preferred polymkeric substance F of the conjugated polymers of described 9-heptadecyl carbazole and fluoro quinoxaline, its structure is suc as formula shown in the VII:
Preferred polymkeric substance G in the conjugated polymers of described 9-heptadecyl carbazole and fluoro quinoxaline, its structure is suc as formula shown in the VIII:
Preferred polymkeric substance H in the conjugated polymers of described 9-heptadecyl carbazole and fluoro quinoxaline, its structure is suc as formula shown in the IX:
The conjugated polymers of described 9-heptadecyl carbazole and fluoro quinoxaline derivatives, its polyreaction adopt the reaction equation shown in Scheme 1 to carry out.
Concrete synthesis step is following:
(1) receives the preparation of fluorine-containing quinoxaline of body unit and verivate thereof
With 5 or 5,6 fluorine-containing 4,7-two bromo-2,1; The 3-diazosulfide is dissolved in the absolute ethyl alcohol, adds Peng Qinghuana under 0 ℃ in batches, reacts 20h under the room temperature then, and reaction finishes the back and concentrates and removes ethanol; Add suitable quantity of water, ethyl acetate extraction, organic phase is used anhydrous magnesium sulfate drying, and bullion is selected purification by silica gel column chromatography for use; Obtain fluorinated diamine, then with 1,2-two R
2Base second diketone is a solvent reaction with acetic acid, make 6 or 6,7 fluorine-containing 5,8-two bromo-2,3-two R
2The base quinoxaline.
With above-mentioned 6 or 6,7 fluorine-containing 5,8-two bromo-2,3-two R
2Base quinoxaline and 4-R
3Base-2-tributyl tin thiophene is through the Stille linked reaction, and products therefrom is solvent with DMF/THF, carries out bromo with NBS, and it is fluorine-containing 5 to obtain 6 or 6,7,8-two (5-bromo-4-R
3The base thiophene)-2, the disubstituted quinoxaline of 3-.
(2) give body unit 9-heptadecyl-2, the preparation of 7-carbazole boric acid ester
With 2,7-dibromo carbazole is dissolved among the DMSO, and under alkaline condition, reaction obtains 9-heptadecyl-2,7-dibromo carbazole.With 9-heptadecyl-2,7-dibromo carbazole is dissolved among the THF, cools to below-78 ℃, adds n-BuLi, behind reaction 1h under-78 ℃; Directly add 2-isopropoxy-4,4,5,5-tetramethyl-1,3; 2-two dislikes, and reaction obtains 9-heptadecyl-2,7-carbazole borate after accomplishing.
(3) preparation of polymkeric substance
This is reflected under the nitrogen protection and carries out, and gets that a certain amount of replaced by 6 of body units fluorine-containing 5,8-two (5-bromo-4-R
3The base thiophene)-2, the disubstituted quinoxaline of 3-or 6, the two fluoro-5 of 7-, 8-two (5-bromo-4-R
3The base thiophene)-2, the disubstituted quinoxaline of 3-, with the 9-heptadecyl-2 of equimolar amount, 7-carbazole boric acid ester and tetraethyl ammonium hydroxide join in two mouthfuls of flasks of exsiccant; The toluene dissolving, fluoro quinoxaline monomer concentration is controlled at about 0.03mol/L, adds catalyzer three (diphenylmethylene acetone) two palladiums of 0.02 times of molar weight and the part tri-o-tolyl phosphorus of 0.08 times of molar weight behind the ventilation 0.5h, continues ventilation 0.5h; Begin heating then, behind the back flow reaction 60h, add bromobenzene, add phenylo boric acid behind the 1h; Back flow reaction 12h again, stopped reaction, system is cooled to room temperature; Reaction solution is splashed into sedimentation in the methyl alcohol, filter, 50 ° of C bakings of the polymkeric substance vacuum drying oven of collection 12h; Carry out cable-styled extraction with methyl alcohol, normal hexane, chloroform successively, concentrate chloroform extracted solution, with methyl alcohol sedimentation once more; Filter, obtain shown in I, containing fluoro quinoxaline and 9-heptadecyl-2, the conjugated polymers of 7-carbazole.The beneficial effect of the conjugated polymers of 9-heptadecyl carbazole of the present invention and fluoro quinoxaline is following:
Adopt 9-heptadecyl-2, the 7-carbazole is as giving electric unit, and two bromo fluoro quinoxaline derivativess prepare the conjugated polymers of 9-heptadecyl substituted carbazole and fluoro quinoxaline derivatives as the short of electricity unit through the Suzuki linked reaction.Utilize cyclic voltammetric to measure; Compare with fluoro quinoxaline-9-heptadecyl substituted carbazole polymkeric substance (structural formula A ' ~ D ') (seeing table 1) not; The HOMO energy level of single fluorinated polymer is the low 0.02-0.2eV of fluoric more not, and the HOMO of two fluorinated polymers is the low 0.05～0.3eV of fluoric more not.Above-mentioned fluoro material and PCBM blended applications are in the body heterojunction optical activity layer of polymer solar cell, and the open circuit voltage of device is at 0.6～1.0V.
Another object of the present invention is; Through on electron deficiency unit quinoxaline, introducing strong electron-withdrawing group group; The HOMO that reduces polymer materials can; Thereby improve the open circuit voltage of photovoltaic cell, propose the application of conjugated polymers in the preparation polymer photovoltaic cell of described 9-heptadecyl carbazole and fluoro quinoxaline.
Description of drawings
Fig. 1 is a polymer A ' C-V figure;
Fig. 2 is the C-V figure of polymer A;
Below in conjunction with accompanying drawing and embodiment the present invention is done further and to explain.
Embodiment
In order to understand the present invention better, to set forth in detail with performance this polymkeric substance is synthetic respectively below, the example of being lifted does not limit protection scope of the present invention.
Embodiment 1: receive body unit 6-fluoro-5,8-two (5-bromothiophene)-2,3-two (3-octyloxyphenyl) quinoxaline synthetic
Synthetic route is following:
(1) the 4-fluoro-3,6-two bromo-1,2-phenylenediamine (compound 1) synthetic
5-fluoro-4,7-two bromo-2,1, (5g 16mmol) is dissolved in the absolute ethyl alcohol (150ml) the 3-diazosulfide, adds NaBH under 0 ℃ in batches
4(11.1g 290mol), at room temperature reacts 20h then.After reaction finishes, concentrate and remove ethanol, add 160ml water, ethyl acetate extraction, saturated common salt water washing organic phase, anhydrous MgSO
4Drying concentrates and obtains bullion, and (25:1, v/v) silica gel column chromatography obtain 3.5g product (compound 1), and yield is 78% with n-hexane/ethyl acetate.
Synthesizing of (2) 1,2-two (3-octyloxyphenyl) second diketone (compound 2)
To cuprous bromide (4.33g, add in THF 30.2mmol) (40ml) solution LiBr (5.25g, 60.4mmol), stirring and dissolving under the room temperature; Ice bath is cooled to 0 ℃, and the Grignard reagent of bromobenzene octyl ether between dropping [a bromobenzene octyl ether (8.6g, 30.2mmol), Mg (1g; 41.7mmol), THF (30ml)], behind the reaction 20min, begin to drip oxalyl chloride (1.71g under 0 ℃; 13.5mmol), dropwise, continue reaction 30min.In system, add saturated NH
4Cl solution cancellation reaction, ethyl acetate extraction, saturated common salt water washing organic phase, anhydrous MgSO
4Drying concentrates, and obtains bullion, with n-hexane/ethyl acetate (200:1, v/v) silica gel column chromatography obtain 1,2-two (3-octyloxyphenyl) second diketone 3.46g (compound 2), yield is 55%.
(3) the 6-fluoro-5,8-two bromo-2,3-two (3-octyloxyphenyl) quinoxaline (compound 3) synthetic
(0.59g, 1.9mmol) (0.88g 1.9mmol) is dissolved among the 40ml HAc compound 1, is warming up to 60 ℃, closes heating, reacts 2h under the room temperature with compound 2.Suction filtration, the washing with alcohol filter cake gets 6-fluoro-5,8-two bromo-2,3-two (3-octyloxyphenyl) quinoxaline 1.31g (compound 3), yield is 97%.
(4) the 6-fluoro-5,8-two thiophene-2,3-two (3-octyloxyphenyl) quinoxaline (compound 4) synthetic
With compound 3 (0.821g, 1.15mmol), 2-tributyl tin thiophene (0.918g, 2.46mmol) and Pd (PPh
3) Cl
2(32mg 0.046mmol) is dissolved in the 20ml toluene N
2The reaction of protection refluxed is spent the night.Concentrate toluene, bullion is used the normal hexane recrystallization, gets safran solid 6-fluoro-5,8-two thiophene-2, and 3-two (3-octyloxyphenyl) quinoxaline 0.66g (compound 4), yield is 80%.
(5) the 6-fluoro-5,8-two (5-bromothiophene)-2,3-two (3-octyloxyphenyl) quinoxaline (compound 5) synthetic
With compound 4 (0.5g, 0.7mmol) and NBS (0.261g 1.47mmol) is dissolved among the DMF (20ml), be heated to 40 ℃ after; Insulation reaction 7h, the methanol wash filter cake is filtered in cooling; Obtain 6-fluoro-5,8-two (5-bromothiophene)-2,3-two (3-octyloxyphenyl) quinoxaline bullion; The normal hexane recrystallization obtains pure article 0.43g (compound 5), and yield is 70%.
The nuclear-magnetism characterization data:
1H NMR (500MHz, CDCl
3, ppm): δ=7.89 (d, 1H), 7.77 (d, 1H), 7.53 (dd, 3H), 7.22 (ddd, 2H), 7.14 (dd, 2H), 7.09 (d, 2H), 6.98 (d, 2H), 4.04 (q, 4H), 1.80 (m, 4H), 1.49 (m, 4H), 1.33 (m, 16), 0.89 (t, 6H).
Embodiment 2: give body unit 9-heptadecyl-2,7-carbazole boric acid ester synthetic
Synthetic route is following:
(1) 9-heptadecyl-2,7-dibromo carbazole (compound 6) synthetic
With 2,7-dibromo carbazole (20.3g, 62.5mmol), Pottasium Hydroxide (20.3g, 362.5mmol) and DMSO (160mL) add in the reaction flask of 500mL, feed N
2, heat to 40 ℃ after, (time 2h drips off the back at 40 ℃ of reaction 6h for 38.6g, the DMSO solution of 200ml 94.1mmol) to drip 9-heptadecyl-p-toluenesulfonic esters.Then reaction solution is poured in the 700mL water, normal hexane extraction merges organic phase, and to neutral, anhydrous magnesium sulfate drying spends the night with the saturated common salt rinsing agent.Filter, concentrate, obtain bullion, the industrial alcohol recrystallization obtains white solid 18.2g (compound 6), and yield is 51.8%.
(2) 9-heptadecyl-2,7-carbazole boric acid ester (compound 7) synthetic
With compound 9 (8.2g, 14.6mmol) and THF (150ml) add in the 250mL reaction bulb, liquid nitrogen cooling adds n-BuLi (19.7ml to below-78 ℃ with syringe; 2.2mol/L), add the back and react 1h down at-78 ℃, add 2-isopropoxy-4,4 then; 5,5-tetramethyl-1,3,2-two dislikes (8.5g; 43.9mmol), add the back and react 1h down at-78 ℃, be warmed up to room temperature reaction 12h subsequently.Add 100ml water, tell organic phase, water extracts with anhydrous diethyl ether, merges organic phase, and is extremely neutral with the saturated common salt rinsing agent, anhydrous magnesium sulfate drying.Filter, concentrate, obtain bullion 12.5g.Silica gel column chromatography, eluent are selected n-hexane/ethyl acetate for use, and (200:1 v/v), obtains pure article 4.7g (compound 7), and yield is 49%.
The nuclear-magnetism characterization data:
1HNMR (500MHz, CDCl3, ppm): δ=8.122 (m, 2H), 8.02 (s, 1H), 7.88 (s; 1H), 7.66,7.65 (d, 2H), 4.67 ~ 4.71 (m, 1H), 2.31 ~ 2.33 (m; 2H), 1.92 ~ 1.96 (m, 2H), 1.39 (s, 24H), 1.19 ~ 1.22 (m, 10H); 1.12 (m, 12H), 0.96,0.98 (m, 2H), 0.80 ~ 0.83 (t, 6H).
Embodiment 3: polymer A
This is reflected under the nitrogen protection and carries out, the acceptor blocking compound 5 that embodiment 1 is obtained (175.8mg, 0.2mmol), embodiment 2 obtains give body unit compound 7 (131.5mg, 0.2mmol); Tetraethyl ammonium hydroxide (20%, 1.5ml) and toluene (15ml) join in two mouthfuls of flasks of exsiccant, ventilation 0.5h adds catalyzer three (diphenylmethylene acetone) two palladiums (3.7mg) and part tri-o-tolyl phosphorus (6.5mg); Continue ventilation 0.5h, begin heating then, behind the back flow reaction 60h, add the 2.2ul bromobenzene; Add the 2.4mg phenylo boric acid behind the 1h, react 12h again, stopped reaction, system is cooled to room temperature; Reaction solution is used the methyl alcohol sedimentation, filter, obtain polymkeric substance, 50 ℃ of dry 12h of following vacuum drying oven; Carry out cable-styled extraction with methyl alcohol, normal hexane, chloroform successively, concentrate chloroform extracted solution,, filter with methyl alcohol sedimentation once more; Obtain conjugated polymers A (seeing table 1), yield is 59.3%, number-average molecular weight 22134, distribution coefficient 1.86.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag
+Electrode is a reference electrode, Bu
4NPF
6Make ionogen, in acetonitrile solvent, through the initial oxidation current potential of cyclic voltammetry polymer A
Be 0.59V, and polymer A ' the initial oxidation current potential
Be 0.50V, according to HOMO can calculation formula-(eV of 4.72+ initial oxidation current potential/V), the HOMO that obtains polymer A can be-5.31eV, than fluoric respective material A ' not-5.22eV, low 0.09eV sees table 1 and Fig. 1, Fig. 2.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61The sandwich battery structure of BM/LiF/Al, with polymer A according to weight ratio 1:5 and acceptor material PC
61BM processes photovoltaic cell, useful area 0.0314cm
2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.82V, short-circuit current density 9.0mA/cm
2, packing factor 0.45, photoelectric transformation efficiency is 3.31%.
Embodiment 4: polymer B
The unitary compound method of acceptor is distinguished the 5-fluoro-4 that only is wherein, 7-two bromo-2,1 with embodiment 1; The 3-diazosulfide changes 5 into, 6-two fluoro-4,7-two bromo-2; 1, the 3-diazosulfide synthesizes 6; 7-two fluoro-5,8-two (5-bromothiophene)-2,3-two (3-octyloxyphenyl) quinoxaline (compound 8); Adopt 9-heptadecyl-2 to body unit, 7-carbazole boric acid ester (compound 7) then, adopts embodiment 3 described methods to obtain the polymkeric substance that structural formula is B, productive rate 61.4%, number-average molecular weight 24120, distribution coefficient 2.14.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag
+Electrode is a reference electrode, Bu
4NPF
6Make ionogen, in acetonitrile solvent, can be-5.36eV through the HOMO of cyclic voltammetry polymer B film, than fluoric respective material A ' not-5.22eV, low 0.14eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61The sandwich battery structure of BM/LiF/Al, with polymer B according to certain weight ratio and acceptor material PC
61BM processes photovoltaic cell, useful area 0.0314cm
2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.85V, photoelectric transformation efficiency is 3.58%.
Embodiment 5: polymkeric substance C
The unitary compound method of acceptor is with embodiment 1; Distinguish the 2-tributyl tin thiophene that is wherein and change 4-hexyl-2-tributyl tin thiophene into; Compound method according to synthetic compound 5; Synthesize 6-fluoro-5,8-two (5-bromo-4-hexyl thiophene)-2,3-two (3-octyloxyphenyl) quinoxaline (compound 9); Adopt 9-heptadecyl-2 to body unit, 7-carbazole boric acid ester (compound 7) then, adopts embodiment 3 described methods to obtain the polymkeric substance that structural formula is C, productive rate 71.6%, number-average molecular weight 15687, distribution coefficient 1.86.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag
+Electrode is a reference electrode, Bu
4NPF
6Make ionogen, in acetonitrile solvent, can be-5.23eV through the HOMO of cyclic voltammetry polymkeric substance C film, than fluoric respective material B ' not-5.15eV, low 0.08eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61The sandwich battery structure of BM/LiF/Al, with polymkeric substance C according to certain weight ratio and acceptor material PC
61BM processes photovoltaic cell, useful area 0.0314cm
2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.74V, photoelectric transformation efficiency is 2.85%.
Embodiment 6: polymkeric substance D
With embodiment 5, difference is with 6-fluoro-5 8-two (5-bromo-4-hexyl thiophene)-2; 3-two (3-octyloxyphenyl) quinoxaline (compound 9) changes 6 into, 7-two fluoro-5,8-two (5-bromo-4-hexyl thiophene)-2; 3-two (3-octyloxyphenyl) quinoxaline (compound 10) adopts embodiment 5 described methods to obtain the polymkeric substance that structural formula is D, productive rate 69.7%; Number-average molecular weight 25312, distribution coefficient 1.91.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag
+Electrode is a reference electrode, Bu
4NPF
6Make ionogen, in acetonitrile/solvent, can be-5.29eV through the HOMO of cyclic voltammetry polymkeric substance D film, than fluoric respective material B ' not-5.15eV, low 0.14eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61The sandwich battery structure of BM/LiF/Al, with polymkeric substance D according to certain weight ratio and acceptor material PC
61BM processes photovoltaic cell, useful area 0.0314cm
2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.81V, photoelectric transformation efficiency is 3.23%.
Implement 7: polymkeric substance E
With embodiment 1; The difference be with wherein 1,2-two (3-octyloxyphenyl) second diketone (compound 2) changes 1 into, 2-two (5-octyl group thiophene) second diketone; Compound method according to compound 5; Synthesize 6-fluoro-5,8-two (5-bromothiophene)-2,3-two (5-octyl group thienyl) quinoxaline (compound 11); Adopt 9-heptadecyl-2 to body unit, 7-carbazole boric acid ester (compound 7) then, adopts embodiment 3 described methods to obtain the polymkeric substance that structural formula is E, productive rate 70.6%, number-average molecular weight 28453, distribution coefficient 2.17.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag
+Electrode is a reference electrode, Bu
4NPF
6Make ionogen, in acetonitrile solvent, can be-5.26eV through the HOMO of cyclic voltammetry polymkeric substance E film, than fluoric respective material C ' not-5.20eV, low 0.06eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61The sandwich battery structure of BM/LiF/Al, with polymkeric substance E according to certain weight ratio and acceptor material PC
61BM processes photovoltaic cell, useful area 0.0314cm
2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.82V, photoelectric transformation efficiency is 3.45%.
Embodiment 8: polymkeric substance F
With embodiment 7, difference is with 6-fluoro-5 8-two (5-bromothiophene)-2; 3-two (5-octyl group thienyl) quinoxaline (compound 11) changes 6 into; 7-two fluoro-5,8-two (5-bromothiophene)-2,3-two (5-octyl group thienyl) quinoxaline (compound 12); Adopt embodiment 7 described methods to obtain the polymkeric substance that structural formula is F, productive rate 73.8%.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag
+Electrode is a reference electrode, Bu
4NPF
6Make ionogen, in acetonitrile solvent, can be-5.35eV through the HOMO of cyclic voltammetry polymkeric substance F film, than fluoric respective material C ' not-5.20eV, low 0.15eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61The sandwich battery structure of BM/LiF/Al, with polymkeric substance F according to certain weight ratio and acceptor material PC
61BM processes photovoltaic cell, useful area 0.0314cm
2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.86V, photoelectric transformation efficiency is 3.95%.
Embodiment 9: polymkeric substance G
With embodiment 1, the difference be with wherein 1,2-two (3-octyloxyphenyl) second diketone (compound 2) changes 1 into; 2-two (5-octyl group thiophene) second diketone; 2-tributyl tin thiophene changes 4-hexyl-2-tributyl tin thiophene into, according to the compound method of synthetic compound 5, synthesizes 6-fluoro-5 fully; 8-two (5-bromo-4-hexyl thiophene)-2,3-two (5-octyl group thiophene) quinoxaline (compound 13); Adopt 9-heptadecyl-2 to body unit, 7-carbazole boric acid ester (compound 7) then, adopts embodiment 3 described methods to obtain the polymkeric substance that structural formula is G, productive rate 67.3%, number-average molecular weight 33127, distribution coefficient 2.08.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag
+Electrode is a reference electrode, Bu
4NPF
6Make ionogen, in the solvent of acetonitrile/orthodichlorobenzene=1:5, can be-5.26eV through the HOMO of cyclic voltammetry polymkeric substance G film, than fluoric respective material D ' not-5.17eV, low 0.09eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61The sandwich battery structure of BM/LiF/Al, with polymkeric substance G according to certain weight ratio and acceptor material PC
61BM processes photovoltaic cell, useful area 0.0314cm
2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.77V, photoelectric transformation efficiency is 3.14%.
Embodiment 10: polymkeric substance H
With embodiment 9, difference is with 6-fluoro-5 8-two (5-bromo-4-hexyl thiophene)-2; 3-two (5-octyl group thienyl) quinoxaline (compound 13) changes 6 into, 7-two fluoro-5,8-two (5-bromo-4-hexyl thiophene)-2; 3-two (5-octyl group thienyl) quinoxaline (compound 14) adopts embodiment 9 described methods to obtain the polymkeric substance that structural formula is H, productive rate 77.1%; Number-average molecular weight 21407, distribution coefficient 2.10.
Electro-chemical test: with CHI660D type electrochemical workstation, the employing glass-carbon electrode is a working electrode, and platinum wire electrode is a counter electrode, Ag/Ag
+Electrode is a reference electrode, Bu
4NPF
6Make ionogen, in the solvent of acetonitrile/orthodichlorobenzene=1:5, can be-5.32eV through the HOMO of cyclic voltammetry polymkeric substance H film, than fluoric respective material D ' not-5.17eV, low 0.15eV sees table 1.
Photovoltaic performance research: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
61The sandwich battery structure of BM/LiF/Al, with polymkeric substance H according to certain weight ratio and acceptor material PC
61BM processes photovoltaic cell, useful area 0.0314cm
2, under Newport Thermal Oriel 69911 simulated solar light sources, carry out the current-voltage test, utilize Keithley 2611 sources table to gather, open circuit voltage is 0.82V, photoelectric transformation efficiency is 4.31%.
The HOMO energy level of table 1 polymkeric substance
Claims (10)
1. the conjugated polymers of 9-heptadecyl carbazole and fluoro quinoxaline is characterized in that the general structure of this conjugated polymers is suc as formula shown in the I:
In the formula, R
1: H or F atom;
R
2: a position or para-position carbon atomicity are the alkoxyl phenyl of 4 to 20 straight or branched, and perhaps carbonatoms is the 2-alkylthrophene base or 2 of 4 to 20 straight or branched, 3-dialkyl group thienyl;
R
3: H or carbonatoms are 1 to 20 straight or branched alkyl.
2. the conjugated polymers of 9-heptadecyl carbazole as claimed in claim 1 and fluoro quinoxaline is characterized in that, the structure of this conjugated polymers is suc as formula shown in the II:
3. the conjugated polymers of 9-heptadecyl carbazole as claimed in claim 1 and fluoro quinoxaline is characterized in that, the structure of this conjugated polymers is suc as formula shown in the III:
4. the conjugated polymers of 9-heptadecyl carbazole as claimed in claim 1 and fluoro quinoxaline is characterized in that, the structure of this conjugated polymers is suc as formula shown in the IV:
5. the conjugated polymers of 9-heptadecyl carbazole as claimed in claim 1 and fluoro quinoxaline is characterized in that, the structure of this conjugated polymers is suc as formula shown in the V:
6. the conjugated polymers of 9-heptadecyl carbazole as claimed in claim 1 and fluoro quinoxaline is characterized in that, the structure of this conjugated polymers is suc as formula shown in the VI:
7. the conjugated polymers of 9-heptadecyl carbazole as claimed in claim 1 and fluoro quinoxaline is characterized in that, the structure of this conjugated polymers is suc as formula shown in the VII:
8. the conjugated polymers of 9-heptadecyl carbazole as claimed in claim 1 and fluoro quinoxaline is characterized in that, the structure of this conjugated polymers is suc as formula shown in the VIII:
9. the conjugated polymers of 9-heptadecyl carbazole as claimed in claim 1 and fluoro quinoxaline is characterized in that, the structure of this conjugated polymers is suc as formula shown in the IX:
10. the application of the conjugated polymers of arbitrary described 9-heptadecyl carbazole and fluoro quinoxaline in the preparation polymer photovoltaic cell among the claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210316918.8A CN102827356B (en) | 2012-08-30 | 2012-08-30 | The conjugated polymers of 9-heptadecyl carbazole and fluoroquinoxaline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210316918.8A CN102827356B (en) | 2012-08-30 | 2012-08-30 | The conjugated polymers of 9-heptadecyl carbazole and fluoroquinoxaline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102827356A true CN102827356A (en) | 2012-12-19 |
| CN102827356B CN102827356B (en) | 2015-08-12 |
Family
ID=47330687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210316918.8A Expired - Fee Related CN102827356B (en) | 2012-08-30 | 2012-08-30 | The conjugated polymers of 9-heptadecyl carbazole and fluoroquinoxaline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102827356B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108831997A (en) * | 2018-06-26 | 2018-11-16 | 东莞理工学院 | A kind of sandwich structure memory device and preparation method thereof |
| CN111675802A (en) * | 2020-06-24 | 2020-09-18 | 西安近代化学研究所 | Wide-band-gap conjugated polymer based on monofluoroquinoxaline-furan as electricity-deficient unit and application |
| CN114874418A (en) * | 2022-04-24 | 2022-08-09 | 广东聚石科技研究有限公司 | Conjugated polymer based on trifluoromethyl substituted quinoxaline and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928382A (en) * | 2009-06-25 | 2010-12-29 | 中国科学院化学研究所 | Block conjugated polymer, and preparation method and use thereof |
| WO2011143825A1 (en) * | 2010-05-21 | 2011-11-24 | 海洋王照明科技股份有限公司 | Conjugated polymer containing dithienopyrrole-quinoxaline, preparation method and uses thereof |
| CN102292838A (en) * | 2009-01-20 | 2011-12-21 | 东丽株式会社 | Material for photovoltaic element, and photovoltaic element |
-
2012
- 2012-08-30 CN CN201210316918.8A patent/CN102827356B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102292838A (en) * | 2009-01-20 | 2011-12-21 | 东丽株式会社 | Material for photovoltaic element, and photovoltaic element |
| CN101928382A (en) * | 2009-06-25 | 2010-12-29 | 中国科学院化学研究所 | Block conjugated polymer, and preparation method and use thereof |
| WO2011143825A1 (en) * | 2010-05-21 | 2011-11-24 | 海洋王照明科技股份有限公司 | Conjugated polymer containing dithienopyrrole-quinoxaline, preparation method and uses thereof |
Non-Patent Citations (4)
| Title |
|---|
| 《Journal of the American Chemical Society》 20110304 Samuel C. Price，et al "Fluorine Substituted Conjugated Polymer of Medium Band Gap Yields 7% Efficiency in Polymer-Fullerene Solar Cells" 第4625-4631页 1-10 第133卷, * |
| 《Solar Energy Materials & Solar Cells》 20120713 Renee Kroon，et al "New quinoxaline and pyridopyrazine-based polymers for solution-processable photovoltaics" 第280-286页 1-10 第105卷, * |
| RENEE KROON，ET AL: ""New quinoxaline and pyridopyrazine-based polymers for solution-processable photovoltaics"", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》, vol. 105, 13 July 2012 (2012-07-13), pages 280 - 286, XP028933097, DOI: doi:10.1016/j.solmat.2012.06.029 * |
| SAMUEL C. PRICE，ET AL: ""Fluorine Substituted Conjugated Polymer of Medium Band Gap Yields 7% Efficiency in Polymer-Fullerene Solar Cells"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 133, 4 March 2011 (2011-03-04), pages 4625 - 4631 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108831997A (en) * | 2018-06-26 | 2018-11-16 | 东莞理工学院 | A kind of sandwich structure memory device and preparation method thereof |
| CN111675802A (en) * | 2020-06-24 | 2020-09-18 | 西安近代化学研究所 | Wide-band-gap conjugated polymer based on monofluoroquinoxaline-furan as electricity-deficient unit and application |
| CN111675802B (en) * | 2020-06-24 | 2022-12-13 | 西安近代化学研究所 | Wide-band-gap conjugated polymer based on monofluoroquinoxaline-furan as electricity-deficient unit and application |
| CN114874418A (en) * | 2022-04-24 | 2022-08-09 | 广东聚石科技研究有限公司 | Conjugated polymer based on trifluoromethyl substituted quinoxaline and preparation method and application thereof |
| CN114874418B (en) * | 2022-04-24 | 2023-12-19 | 广东聚石科技研究有限公司 | Conjugated polymer based on trifluoromethyl substituted quinoxaline, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102827356B (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103087083A (en) | Diketopyrrolopyrrole derivative and preparation method and application thereof | |
| CN102816302B (en) | Dithiophene pentalene-fluoroquinoxaline conjugated polymer | |
| CN102827358B (en) | Conjugated polymer of 4,8-di(5-isooctyl thiophene)phenyl [1,2-b; 3,4-b]bithiophene and chloroquinoxaline | |
| CN102816299B (en) | Conjugated polymer of 4, 8-diisooctyl alkoxy phenyl [1, 2-b; 3, 4-b] bithiophene and fluoro-quinoxaline | |
| CN102617835A (en) | Conjugated polymer of polyacenaphthylene and quinoxaline, as well as preparation method and application of conjugated polymer | |
| CN102827356B (en) | The conjugated polymers of 9-heptadecyl carbazole and fluoroquinoxaline | |
| CN102838733B (en) | Conjugated polymer of 9,9-dioctyl fluorene and fluorinated quinoxaline | |
| CN102827357B (en) | Two thieno-cyclopentadiene-fluoroquinoxaline conjugated polymers | |
| CN102838732B (en) | Conjugated polymer of 4,8-diisooctane alkoxy phenyl [1,2-b;3,4-b] bithiophene and fluorinated quinoxaline | |
| CN105061730A (en) | Fluorine-containing phenanthrene quinoxaline and thiophene conjugated polymer | |
| CN102816301B (en) | Dithiophene ring-fused germanium pentadiene-fluoroquinoxaline conjugated polymer | |
| CN102816306B (en) | Fluoroquinoxaline-thiophene conjugated polymer | |
| CN102816304B (en) | 9-octylcarbazole-fluoroquinoxaline conjugated polymer | |
| CN102816303B (en) | Bithiophene silicon pentalene-fluoroquinoxaline conjugated polymer | |
| CN103865044B (en) | Containing the multipolymer and its preparation method and application of cyclopentadienedithiderivatives and benzo two (selenole) unit | |
| CN102827088B (en) | Chloroquinoxaline compound | |
| CN102816307B (en) | Dithiophene ring-fused germanium pentadiene-fluoroquinoxaline conjugated polymer | |
| CN102827359B (en) | The conjugated polymers of 9,9-dioctyl silicon fluorenes and fluoroquinoxaline | |
| CN102850529B (en) | Conjugated polymer of 4,8-di(5-isooctylthiophene)phenyl[1,2-b;3,4-b]bisthiophene and fluoroquinoxaline | |
| CN102816300B (en) | The conjugated polymers of fluoroquinoxaline and furans | |
| CN102816305B (en) | Bithiophene silicon pentalene-fluoroquinoxaline conjugated polymer | |
| CN103833979A (en) | Bitriselenophen-benzodi(benzoselendiazole) copolymer, preparation method and application thereof | |
| CN103833981A (en) | Benzo[3,4-b]dithiophene-benzo-di(benzoselenadiazole) copolymer as well as preparation method and application thereof | |
| CN111675802B (en) | Wide-band-gap conjugated polymer based on monofluoroquinoxaline-furan as electricity-deficient unit and application | |
| CN103626972A (en) | Copolymer containing siliconfluorene-benzobis(benzothiadiazole), preparation method thereof and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150812 Termination date: 20200830 |