CN108084408A - A kind of polymer active layer material containing alkylthio group thiophene-fluoro diazosulfide and preparation method thereof - Google Patents
A kind of polymer active layer material containing alkylthio group thiophene-fluoro diazosulfide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polymer active layer materials containing alkylthio group thiophene fluoro diazosulfide and preparation method thereof.The characteristics of polymer active layer material belongs to D A type structures, has thermostabilization, and raw material is commonly easy to get, solution processable, production cost is relatively low.This kind of polymer active layer material is used to prepare polymer solar battery, and the advantageous effect that energy conversion efficiency is 4.4~7.5% can be obtained under conditions of optimised devices, has certain actual application value.
Description
Technical field
The present invention relates to polymer active layer materials for polymer solar battery and preparation method thereof, and in particular to
A kind of polymer active layer material containing alkylthio group thiophene-fluoro diazosulfide and preparation method thereof.
Background technology
The consumption of traditional energy and with serious environment and ecological problem, therefore there is an urgent need for research and develop novel energy
To be alleviated.In recent years, since polymer solar (Polymer Solar cells, PSCs) is inexpensive, light with manufacture
Matter, flexibility and the potentiality of convenient solar panel can be printed by high-throughput, thus receive people's concern.However, in order to
Realize the target of application, the development of novel active layer material plays an important role to improving device performance.
Although the electron donation of sulphur atom is weaker than oxygen atom, due to the overlapping of p π (C)-d π (S) track, pi-electron can
The empty 3d tracks of bivalent sulfur atom are entered from the p tracks of carbon-carbon double bond, therefore sulphur atom has certain energy for receiving pi-electron
Power.This causes alkylthio group side chain to play an important role in the photoelectric properties for adjusting polymer.Wherein, taken based on thiophene alkylthio group
The diazosulfide-four in generation connects the photoelectric conversion efficiency that thiophene alternating conjugated polymer achieves 7.76%
(Org.Electron.,2017,40,36-41)。
Fluorine atom size itself is small, and van der Waals radius is, after introducing polymer backbone, this causes polymer backbone
There are one better flatness, so as to which charge be promoted effectively to transmit.In addition, compared with other atoms, fluorine atom
Pauling electronegativity is 4.0, is that electronegativity is most strong in all elements.This shows that fluorine atom can effectively reduce conjugated system
The cloud density of system.So as to so that highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are more stablized, can be not
In the case of the steric hindrance for increasing polymer chain, open-circuit voltage (V is improvedoc).Furthermore the high electronegativity of fluorine atom usually can change
The dipole moment of conjugated polymer generates very strong intermolecular interaction between polymer chain.And then influence nanotopography
It is formed, crystallization or orientation such as polymeric, the charge transmission of these and polymer solar battery (PSC) and compound close
Cut phase is closed.
The present invention passes through the number for adjusting fluorine atom by introducing alkyl sulfide thiophene in diazosulfide system, if
Meter has synthesized a kind of polymer donor material containing alkylthio group thiophene-fluoro diazosulfide, is acceptor material in fullerene
Bulk heterojunction solar cells in, achieve preferable photoelectric conversion efficiency, have good application potential.
The content of the invention
It is an object of the invention to provide a kind of polymer active layers materials containing alkylthio group thiophene-fluoro diazosulfide
Material and preparation method thereof.
The technical scheme is that：
A kind of polymer active layer material containing alkylthio group thiophene-fluoro diazosulfide has below general formula (I)：
In formula (I), R is C6-C24Straight or branched alkyl, shown in the structural formula such as formula (II) of E：
In formula (II), X is H or F, Y are the structural formula of H or F, G as shown in any structure in formula (III)：
In formula (III), R1It is H or F, R2It is H or F, R3It is H or F, R4It is H or F.
The preparation method of the above-mentioned polymer active layer material containing alkylthio group thiophene-fluoro diazosulfide, including
Following steps：
(1) 3- mercapto-thiophenes are reacted with bromoalkane, obtain intermediate compound a：
The structural formula of the 3- mercapto-thiophenes is
The structural formula of the intermediate compound a is
R is C6-C24Straight or branched alkyl；
(2) intermediate compound a and the reaction of N- bromo-succinimides, obtain intermediate compound b：
The structural formula of the intermediate compound b is
(3) intermediate compound b passes through bromine transport reaction, obtains intermediate compound c：
The structural formula of the intermediate compound c is
(4) intermediate compound c is reacted with tributyltin chloride, obtains intermediate compound d：
The structural formula of the intermediate compound d is
(5) the dibromide coupling reaction of intermediate compound d and E, obtains intermediate compound e：
The structural formula of the dibromide of the E is
X is H or F, Y are H or F,
The structural formula of the intermediate compound e is
(6) intermediate compound e is reacted with N- bromo-succinimides, obtains intermediate compound f：
(7) intermediate compound f is polymerize with the bilateral tin reagent of G, obtains final product (I),
The structural formula of the bilateral tin reagent of the G is one kind of following structures：
R1It is H or F, R2It is H or F, R3It is H or F, R4It is H or F.
Preferably, step (1) carries out as follows：In reaction bulb, by potassium tert-butoxide and absolute ethyl alcohol 10-70mmol：
The proportioning of 20-40mL is separately added into potassium tert-butoxide and absolute ethyl alcohol, under conditions of ice bath, instills 3- mercapto-thiophenes, 3- dropwise
The molar ratio of mercapto-thiophene and potassium tert-butoxide is 3-43：10-70 is stirred 30~40 minutes, is vacuumized, nitrogen protection；It again will be anti-
Bottle is answered to be placed in 60~90 DEG C of oil bath pan, 20~30 minutes is kept the temperature, bromoalkane, bromoalkane is then added dropwise into reaction bulb
Molar ratio with 3- mercapto-thiophenes is 3-43：3-43 when 60~90 DEG C of reaction 3-4 are small, stand cooling, water quenching is added to go out, use
Ether extracts, anhydrous magnesium sulfate drying, and funnel filtering is spin-dried for solvent, petroleum ether crosses column, obtains colorless oil using Rotary Evaporators
Liquid is intermediate compound a.
Preferably, step (2) carries out as follows：Solvent is done with dichloromethane, intermediate compound a is added to reaction bulb
In, in ice bath and under the conditions of being protected from light, be added dropwise into reaction bulb be dissolved in n,N-Dimethylformamide N- bromos succinyl it is sub-
The molar ratio of amine, N- bromo-succinimides and intermediate compound a are 10-38：10-38, reaction overnight, are extracted using dichloromethane
It takes, anhydrous magnesium sulfate drying, funnel filtering is spin-dried for solvent using Rotary Evaporators, column is crossed using petroleum ether, obtains colorless oil liquid
Body is intermediate compound b.
Preferably, step (3) carries out as follows：By intermediate compound b and tetrahydrofuran 10-32mmol：10-30ml's
Intermediate compound b and tetrahydrofuran are added sequentially in reaction bulb by proportioning, vacuumize, logical nitrogen, 20 are kept the temperature at -60~70 DEG C
~30 minutes, then by intermediate compound b and lithium diisopropylamine 10-32：The molar ratio of 10-32 is added dropwise into reaction bulb
Lithium diisopropylamine, after dripping off, -60~70 DEG C be stirred to react 1~2 it is small when, then by mass concentration be 5~10% it is dilute
Hydrochloric acid is added in reaction bulb, and reaction is quenched, and is stirred 30~40 minutes, is then extracted using dichloromethane, anhydrous magnesium sulfate is done
Dry, funnel filtering is spin-dried for solvent using Rotary Evaporators, and petroleum ether crosses column, obtains colourless oil liquid, is intermediate compound c.
Preferably, step (4) carries out as follows：By intermediate compound c and tetrahydrofuran 10-15mmol：10-20mL's
Intermediate compound c, anhydrous tetrahydro furan are added sequentially in reaction bulb by proportioning, are vacuumized, logical nitrogen, in -78~80 DEG C of guarantors
Temperature 20~30 minutes, then by intermediate compound c and n-BuLi 10-15：The molar ratio of 10-15 is added dropwise just into reaction bulb
Butyl lithium, after dripping off, -78~80 DEG C be stirred to react 2~3 it is small when, then by intermediate compound c and tributyltin chloride 10-
15：The molar ratio of 10-15 adds in tributyltin chloride, -78~80 DEG C be stirred to react 0.5-1 it is small when, move to room temperature, reacted
Night is added water quenching, is extracted using dichloromethane, anhydrous magnesium sulfate drying, and funnel filtering is spin-dried for molten using Rotary Evaporators
Agent obtains colourless oil liquid, is intermediate compound d.
Preferably, step (5) carries out as follows：Using toluene as solvent, by the dibromide of intermediate compound d, E, four
Triphenylphosphine palladium 5-10：1.5-3.5：The molar ratio of 0.1-0.2 is added sequentially in reaction bulb, and toluene is with intermediate compound d's
It matches as 20-30mL：5-10mmol when reaction 36~48 is small under the conditions of 100~110 DEG C of oil bath, uses petroleum ether and two
(volume ratio of petroleum ether-dichloromethane is 10 to chloromethanes:1) column is crossed, obtains peony thick liquid, is intermediate compound e.
Preferably, step (6) carries out as follows：Intermediate compound e is dissolved in chloroform, is added to reaction bulb
In, under conditions of ice bath, then by intermediate compound e and N- bromo-succinimides 1-1.5：2.5-3.8 molar ratio add in
N- bromo-succinimides, reaction 2~3 it is small when after, be warmed to room temperature, be further continued for reaction 2~3 it is small when, water is added to quench, uses dichloro
Methane extracts, anhydrous magnesium sulfate drying, and funnel filtering is spin-dried for solvent using Rotary Evaporators, uses petroleum ether and dichloromethane
(volume ratio of petroleum ether and dichloromethane is 5:1) column is crossed, obtains peony thick liquid, is intermediate compound f.
Preferably, step (7) carries out as follows：By 0.1-0.2mmol：0.1-0.2mmol：The proportioning of 3-4mL is dry
The dry bilateral tin reagent of intermediate compound f, G and chromatographically pure chlorobenzene are sequentially added in dry reaction unit, puts up reaction dress
It postpones, liquid nitrogen frozen, defrosting deoxygenation, vacuum pump vacuumize, 2~5 times repeatedly, after solution freezes, rapidly join and intermediate chemical combination
Object f molar ratios are 1.5~2% Pd2(dba)3And with intermediate compound f molar ratios be 6~8% P (o-tol)3, remove again
Oxygen vacuumizes, logical nitrogen, is protected from light, is put into 100~110 DEG C of oil bath pan and reacts 2~3 days, treats that reaction mixture cools down, move
It to room temperature, using chromatographically pure chloroform, ultra-pure water, is extracted, is spin-dried for the 1/10~1/8 of total volume, by solution dropwise
Sedimentation in Chromatographic Pure Methanol, filtering are added in, Chromatographic Pure Methanol, acetone, petroleum ether, dichloromethane, chloroform is reused and carries out
Extracting is spin-dried for chloroform to the 1/10~1/8 of total volume, reuses Chromatographic Pure Methanol sedimentation, filters, be dried in vacuo deep
Green solid is final subject polymer (I).
The beneficial effects of the present invention are：
(1) product of the invention is the polymer active layer material for belonging to D-A type structure, and thermal stability is good, and raw material is common
It is easy to get, solution processable, production cost is low.
(2) polymer active layer material of the invention is used to prepare polymer solar battery, in the condition of optimised devices
The advantageous effect that energy conversion efficiency is 4.4~7.5% can be obtained down, and there is certain actual application value.
Description of the drawings
Fig. 1 is the polymer solar battery for the polymer active layers material preparation that the present invention has chemical structural formula 1-3
Current density-voltage (J-V) curve.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
A kind of chemical constitution is 1 polymer active layer material, and synthetic route is as follows：
(1) chemical structural formula is the synthesis of the intermediate of a：
In 500mL two-mouth bottles, potassium tert-butoxide (7.2g, 64.5mmol), absolute ethyl alcohol (40mL) are added in.In the item of ice bath
Under part, compound 3- mercapto-thiophenes (5.0g, 43.0mmol) are instilled dropwise, are stirred 30 minutes.It vacuumizes, nitrogen protection.Anti-
Bottle is answered to keep the temperature 20 minutes as in 80 DEG C of oil bath pans.Instilled dropwise into reaction bulb the bromo- 2- octyl groups-dodecanes of 1- (15.6g,
43.2mmol), when 80 DEG C of reactions 3 are small.Cooling is stood, water quenching is added to go out.It is extracted using ether, anhydrous magnesium sulfate drying, funnel
Filtering, solvent is spin-dried for using Rotary Evaporators.Column is crossed using petroleum ether, obtains colourless oil liquid 15.3g, yield 90%.1H
NMR(400MHz,CDCl3,TMS/ppm):δ7.31(d,1H),δ7.07(s,1H),δ7.00(d,1H),δ2.83(d,2H),δ
1.59-1.57(m,1H),δ1.39-1.25(m,32H),δ0.89-0.86(m,6H).
(2) chemical structural formula is the synthesis of the intermediate of b：
Intermediate compound a (15.0g, 37.85mmol) obtained by step (1) is added in 100mL there-necked flasks, uses two
Chloromethanes makees solvent.Under conditions of ice bath, a small amount of n,N-Dimethylformamide dissolving N- bromo fourths Asia acid imide is used
(6.7g, 37.85mmol), is added to constant pressure funnel, is protected from light, and is added dropwise in reaction bulb.Reaction overnight, uses dichloromethane
Alkane extracts, anhydrous magnesium sulfate drying, and funnel filtering is spin-dried for solvent using Rotary Evaporators.Column is crossed using petroleum ether, obtains colorless oil
Shape liquid 17.6g, yield 98%.1H NMR(400MHz,CDCl3,TMS/ppm):δ7.25(d,1H),δ6.93(d,1H),δ
2.83(d,2H),δ1.59-1.57(m,1H),δ1.39-1.25(m,32H),δ0.89-0.86(m,6H).
(3) chemical structural formula is the synthesis of the intermediate of c：
Intermediate compound b (15.0g, 31.65mmol) obtained by step (2) is added in 500mL two-mouth bottles, adds in four
Hydrogen furans 30mL.It vacuumizes, logical nitrogen.20 minutes are kept the temperature at -70 DEG C, instills lithium diisopropylamine dropwise into reaction bulb
(15.8mL,31.65mmol).After dripping off, -70 DEG C be stirred to react 1 it is small when.The dilute hydrochloric acid that mass concentration is 10% is added to
In reaction bulb, reaction is quenched, stirs 30 minutes.It is extracted using dichloromethane, anhydrous magnesium sulfate drying, funnel filtering uses rotation
Turn evaporimeter and be spin-dried for solvent.Column is crossed using petroleum ether, obtains colourless oil liquid 7.5g, yield 50%.1H NMR(400MHz,
CDCl3,TMS/ppm):δ6.98(d,1H),δ6.96(d,1H),δ2.81(d,2H),δ1.59-1.57(m,1H),δ1.39-
1.25(m,32H),δ0.89-0.86(m,6H).
(4) chemical structural formula is the synthesis of the intermediate of d：
Intermediate compound c (7.0g, 14.77mmol) obtained by step (3) is added in 100mL two-mouth bottles, adds in nothing
Water tetrahydrofuran 20mL.It vacuumizes, logical nitrogen.20 minutes are kept the temperature at -78 DEG C, instills n-BuLi dropwise into reaction bulb
(5.9mL,14.77mmol).After dripping off, -78 DEG C be stirred to react 2 it is small when, rapidly join tributyltin chloride (4.0mL,
14.77mmol).- 78 DEG C be stirred to react 0.5 it is small when, move to room temperature, reaction is overnight.Water is added to quench, is extracted using dichloromethane
It takes, anhydrous magnesium sulfate drying, funnel filtering is spin-dried for solvent using Rotary Evaporators.Colourless oil liquid 8.6g is obtained, yield is
85%.It need not be further purified and can be used in next step.
(5) chemical structural formula is the synthesis of the intermediate of e：
By intermediate compound d (7.0g, 10.21mmol), the bis- bromo- 2,1,3- diazosulfides of 4,7- obtained by step (4)
(1g, 3.4mmol), tetra-triphenylphosphine palladium (0.2g, 0.17mmol) are added in 100mL two-mouth bottles, add toluene (30mL) conduct
Solvent.When 110 DEG C of reactions 48 of oil bath pan are small.Using petroleum ether and dichloromethane, (volume ratio of the two is 10:1) silica gel is crossed
Column obtains peony thick liquid 1.89g.Yield is 60%.1H NMR(400MHz,CDCl3,TMS/ppm):δ 8.05 (d, J=
1.2Hz, 2H), δ 7.83 (s, 2H), δ 7.19 (d, J=1.27Hz, 2H), δ 2.92 (d, J=6.2Hz, 4H), δ 1.67-1.64
(m,2H),δ1.45-1.25(m,64H),δ0.88-0.84(m,12H).
(6) chemical structural formula is the synthesis of the intermediate of f：
In 250mL two-mouth bottles, compound e (1.5g, 1.62mmol) is dissolved in chloroform, under conditions of ice bath,
It is disposable to add in N- bromo-succinimides (0.6g, 3.57mmol).React 2 it is small when after, be warmed to room temperature, still further react 2 small
When.Water is added to quench, is extracted using dichloromethane, anhydrous magnesium sulfate drying, funnel filtering is spin-dried for solvent using Rotary Evaporators.
Use petroleum ether and dichloromethane (volume ratio 5:1) column is crossed, obtains peony thick liquid 1.57g.Yield is 90%.1H NMR
(400MHz,CDCl3,TMS/ppm):δ 7.91 (s, 2H), δ 7.76 (s, 2H), δ 2.93 (d, J=6.1Hz, 4H), δ 1.62-
1.59(m,2H),δ1.44-1.21(m,64H),δ0.87-0.84(m,12H).13C NMR(100MHz,CDCl3,TMS/ppm):δ
152.09,138.86,134.99,129.79,125.13,124.89,115.88,77.28,77.02,76.77,40.05,
38.06,33.00,31.93,31.92,29.95,29.69,29.66,29.65,29.36,26.61,22.70,22.69,
14.13.
(7) chemical constitution is the synthesis of 1 polymer active layer material：
Reactant and reaction unit are dried, added in Kolle flask obtained by step (6) intermediate compound f (201mg,
0.18mmol), (3,3 '-two fluoro- [2,2 '-bithiophene] -5,5 '-diyl) double tin trimethyls (99mg, 0.18mmol), 3mL colors
Compose pure chlorobenzene.Reaction unit, liquid nitrogen frozen, defrosting deoxygenation are put up, vacuum pump vacuumizes, repeatedly for three times.After solution freezes, quickly
Add in Pd2(dba)3(3mg),P(o-tol)3(5mg).Again deoxygenation, vacuumize, logical nitrogen, be protected from light, be put into 110 DEG C of oil bath pans
Middle reaction three days.It treats that reaction mixture cools down, moves to room temperature.Using chromatographically pure chloroform, ultra-pure water, extracted.It is spin-dried for
To 30mL or so, solution is added dropwise in Chromatographic Pure Methanol and settles, filter.Again using Chromatographic Pure Methanol, acetone, oil
Ether, dichloromethane, chloroform are stripped, and are spin-dried for chloroform to 30mL or so, are reused Chromatographic Pure Methanol sedimentation, are taken out
Filter, is dried in vacuo to obtain dark green solid 143mg, yield 68%.
(8) chemical constitution is that the polymer solar battery of 1 polymer active layers material preparation and its photovoltaic performance are surveyed
Examination：
The device architecture of polymer solar battery is ITO/PEDOT:PSS/D:PC71BM/PFN-Br/Al.In ultrasonic wave
In bath, ITO coated glass (10 Ω/sq.) is cleaned respectively with deionized water, acetone and isopropanol.10 are cleaned in oxygen plasma
After minute, the PEDOT of 30nm thickness:PSS anode buffer layers are spun onto on ITO matrixes, are then dried among 150 DEG C of baking oven
15 minutes.Active layer material is by chlorobenzene-dichloro-benzenes mixed solvent (volume ratio 1:1) concentration of dissolving is the polymerization of 10mg/mL
Object and PC71The mixture composition of BM, polymer and PC71The mass ratio of BM is 1:1, it is then spin coated onto PEDOT:At the top of PSS.
Before device detection, 2.5% chloronaphthalene of addition chlorobenzene-dichloro-benzenes mixed solvent volume is handled as additive.
Under the speed conditions of 3000rpm, concentration be 0.5mg/mL PFN-Br methanol solution on active layer spin coating 30 seconds.Active layer
Thickness controlled by KLA Tencor D-100 instrument by adjusting the speed of spin coating.Finally, it is about 4 × 10 in pressure- 4Under the vacuum condition of Pa, the Al successive sedimentations of 100nm are on photosensitive layer.After being assembled into polymer solar cell device structure,
The test of photovoltaic performance is carried out, effective work area of battery is 0.1cm2.Battery short circuit electric current JscFor 10.42mA/cm2,
Open-circuit voltage VocFor 0.69V, fill factor, curve factor FF is 0.62, and the energy conversion efficiency for thus calculating battery is 4.48%.
Embodiment 2
A kind of chemical constitution is 2 polymer active layer material, and synthetic route is as follows：
(1) chemical structural formula is the synthesis of the intermediate of a with embodiment 1
(2) chemical structural formula is the synthesis of the intermediate of b with embodiment 1
(3) chemical structural formula is the synthesis of the intermediate of c with embodiment 1
(4) chemical structural formula is the synthesis of the intermediate of d with embodiment 1
(5) chemical structural formula is the synthesis of the intermediate of g：
By intermediate compound d (6.6g, 9.6mmol), fluoro- 2,1, the 3- benzo thiophenes two of 4,7-, bis- bromo- 5- obtained by step (4)
Azoles (1g, 3.2mmol), tetra-triphenylphosphine palladium (0.2g, 0.17mmol) are added in 100mL two-mouth bottles, add 30mL toluene conducts
Solvent.When 110 DEG C of reactions 48 of oil bath pan are small.Use petroleum ether and dichloromethane (volume ratio 10:1) silicagel column is crossed, is obtained dark red
Color thick liquid 2.3g, yield 75%.1H NMR(400MHz,CDCl3,TMS/ppm):δ8.21(s,1H),δ8.07(s,
1H), δ 7.75 (d, J=1.6Hz, 1H), δ 7.31 (s, 1H), δ 7.23 (s, 1H), δ 2.93 (d, J=6.0Hz, 4H), δ 1.69-
1.62(m,2H),δ1.45-1.23(m,64H),δ0.88-0.84(m,12H).
(6) chemical structural formula is the synthesis of the intermediate of h：
In 250mL two-mouth bottles, the intermediate compound e (1.5g, 1.59mmol) obtained by step (5) will be dissolved in three chloromethanes
It is disposable to add in N- bromo-succinimides (0.62g, 3.50mmol) under conditions of ice bath in alkane.React 2 it is small when after, rise
To room temperature, be further continued for reaction 2 it is small when.Water is added to quench, is extracted using dichloromethane, anhydrous magnesium sulfate drying, funnel filtering uses
Rotary Evaporators are spin-dried for solvent.Use petroleum ether and dichloromethane (volume ratio 5:1) column is crossed, obtains peony thick liquid
1.6g.Yield is 90%.1H NMR(400MHz,CDCl3,TMS/ppm):δ8.12(s,1H),δ7.90(s,1H),δ7.68(d,J
=12.8Hz, 1H), δ 2.95-2.92 (m, 4H), δ 1.64-1.60 (m, 2H), δ 1.48-1.21 (m, 64H), δ 0.88-0.83
(m,12H).13C NMR(100MHz,CDCl3,TMS/ppm):δ149.57,138.19,134.70,130.65,124.49,
116.68,111.05,40.14,40.05,37.74,33.11,31.94,29.96,29.71,29.68,29.64,29.38,
26.59,22.71,22.70,14.15.
(7) chemical constitution is the synthesis of 2 polymer active layer material：
Reactant and reaction unit are dried, added in Kolle flask obtained by step (6) intermediate compound h (202mg,
0.18mmol), (3,3 '-two fluoro- [2,2 '-bithiophene] -5,5 '-diyl) double tin trimethyls (97mg, 0.18mmol), 3mL colors
Compose pure chlorobenzene.Reaction unit, liquid nitrogen frozen, defrosting deoxygenation are put up, vacuum pump vacuumizes, repeatedly for three times.After solution freezes, quickly
Add in Pd2(dba)3(3mg),P(o-tol)3(4mg).Again deoxygenation, vacuumize, logical nitrogen, be protected from light, be put into 110 DEG C of oil bath pans
Middle reaction three days.It treats that reaction mixture cools down, moves to room temperature.Using chromatographically pure chloroform, ultra-pure water, extracted.It is spin-dried for
To 30mL or so, solution is added dropwise in Chromatographic Pure Methanol and settles, filter.Again using Chromatographic Pure Methanol, acetone, oil
Ether, dichloromethane, chloroform are stripped, and are spin-dried for chloroform to 30mL or so, are reused Chromatographic Pure Methanol sedimentation, are taken out
Filter, is dried in vacuo to obtain dark green solid 143mg, yield 68%.
(8) chemical constitution is that the polymer solar battery of 2 polymer active layers material preparation and its photovoltaic performance are surveyed
Examination：
With the method and condition described in embodiment 1, prepare and test based on the polymer solar electricity that chemical structural formula is 2
Pond, battery short circuit electric current JscFor 13.56mA/cm2, open-circuit voltage VocFor 0.74V, fill factor, curve factor FF is 0.69, is thus calculated
The energy conversion efficiency for going out battery is 6.94%.
Embodiment 3
A kind of chemical constitution is the polymer active layer material for 3, and synthetic route is as follows：
Step (1) to (4) is the same as embodiment 1；
(5) chemical structural formula is the synthesis of the intermediate of I：
By compound d (6.3g, 9.15mmol), bis- bromo- bis- fluoro- diazosulfides (1g, 3.05mmol) of 5,6- of 4,7-, four
Triphenylphosphine palladium (0.2g, 0.17mmol) is added in 100ml two-mouth bottles, adds toluene as solvent.In 110 DEG C of reactions of oil bath pan
48 it is small when.Use petroleum ether and dichloromethane (volume ratio 10:1) silicagel column is crossed, obtains kermesinus thick liquid 2.3g, yield is
80%.1H NMR(400MHz,CDCl3,TMS/ppm):δ8.23(s,2H),δ7.34(s,2H),δ2.92(d,4H),δ1.66-
1.63(m,2H),δ1.42-1.23(m,64H),δ0.88-0.85(m,12H).
(6) chemical structural formula is the synthesis of the intermediate of J：
In 250mL two-mouth bottles, the compound I (1.5g, 1.56mmol) obtained by step (5) is dissolved in chloroform,
It is disposable to add in N- bromo-succinimides (0.6g, 3.43mmol) under conditions of ice bath.React 2 it is small when after, rise to room
Temperature, be further continued for reaction 2 it is small when.Water is added to quench, is extracted using dichloromethane, anhydrous magnesium sulfate drying, funnel filtering uses rotation
Evaporimeter is spin-dried for solvent.Use petroleum ether and dichloromethane (volume ratio 5:1) column is crossed, obtains peony thick liquid 1.6g.Production
Rate is 90%.1H NMR(400MHz,CDCl3,TMS/ppm):δ8.08(s,2H),δ2.92(d,4H),δ1.60-1.57(m,
2H),δ1.42-1.21(m,64H),δ0.87-0.83(m,12H).13C NMR(100MHz,CDCl3,TMS/ppm):δ152.09,
138.86,134.99,129.79,125.13,124.89,115.88,77.28,77.02,76.77,40.05,38.06,
33.00,31.93,31.92,29.95,29.69,29.66,29.65,29.36,26.61,22.70,22.69,14.13.
(7) chemical constitution is the synthesis of 3 polymer active layer material：
Reactant and reaction unit are dried, added in Kolle flask obtained by step (6) compound J (200mg,
0.17mmol), (3,3 '-two fluoro- [2,2 '-bithiophene] -5,5 '-diyl) double tin trimethyls (90mg, 0.17mmol), 3mL colors
Compose pure chlorobenzene.Reaction unit, liquid nitrogen frozen, defrosting deoxygenation are put up, vacuum pump vacuumizes, repeatedly for three times.After solution freezes, quickly
Add in Pd2(dba)3(3mg),P(o-tol)3(4mg).Again deoxygenation, vacuumize, logical nitrogen, be protected from light, be put into 110 DEG C of oil bath pans
Middle reaction three days.It treats that reaction mixture cools down, moves to room temperature.Using chromatographically pure chloroform, ultra-pure water, extracted.It is spin-dried for
To 30mL or so, solution is added dropwise in Chromatographic Pure Methanol and settles, filter.Again using Chromatographic Pure Methanol, acetone, oil
Ether, dichloromethane, chloroform are stripped, and are spin-dried for chloroform to 30mL or so, are reused Chromatographic Pure Methanol sedimentation, are taken out
Filter, is dried in vacuo to obtain dark green solid 120mg, yield 72%.
(8) chemical constitution is that the polymer solar battery of 3 polymer active layers material preparation and its photovoltaic performance are surveyed
Examination：
With the method and condition described in embodiment 1, prepare and test based on the polymer solar electricity that chemical structural formula is 3
Pond, battery short circuit electric current JscFor 13.72mA/cm2, open-circuit voltage VocFor 0.80V, fill factor, curve factor FF is 0.69, is thus calculated
The energy conversion efficiency for going out battery is 7.50%.
Claims (9)
1. a kind of polymer active layer material containing alkylthio group thiophene-fluoro diazosulfide, which is characterized in that there is formula
(I) structure shown in：
In formula (I), R is C6-C24Straight or branched alkyl, shown in the structural formula such as formula (II) of E：
In formula (II), X is H or F, Y are the structural formula of H or F, G as shown in any structure in formula (III)：
In formula (III), R1It is H or F, R2It is H or F, R3It is H or F, R4It is H or F.
2. the preparation side of the polymer active layer material described in claim 1 containing alkylthio group thiophene-fluoro diazosulfide
Method, which is characterized in that include the following steps：
(1) 3- mercapto-thiophenes are reacted with bromoalkane, obtain intermediate compound a：
The structural formula of the 3- mercapto-thiophenes is
The structural formula of the intermediate compound a is
R is C6-C24Straight or branched alkyl
(2) intermediate compound a and the reaction of N- bromo-succinimides, obtain intermediate compound b：
The structural formula of the intermediate compound b is
(3) intermediate compound b passes through bromine transport reaction, obtains intermediate compound c：
The structural formula of the intermediate compound c is
(4) intermediate compound c is reacted with tributyltin chloride, obtains intermediate compound d：
The structural formula of the intermediate compound d is
(5) the dibromide coupling reaction of intermediate compound d and E, obtains intermediate compound e：
The structural formula of the dibromide of the E is
X is H or F, Y are H or F,
The structural formula of the intermediate compound e is
(6) intermediate compound e is reacted with N- bromo-succinimides, obtains intermediate compound f：
(7) intermediate compound f is polymerize with the bilateral tin reagent of G, obtains final product (I),
The structural formula of the bilateral tin reagent of the G is one kind of following structures
R1It is H or F, R2It is H or F, R3It is H or F, R4It is H or F.
3. the system of the polymer active layer material according to claim 2 containing alkylthio group thiophene-fluoro diazosulfide
Preparation Method, which is characterized in that the concrete operations of step (1) are：
In reaction bulb, by potassium tert-butoxide and absolute ethyl alcohol 10-70mmol：The proportioning of 20-40mL be separately added into potassium tert-butoxide and
Absolute ethyl alcohol under conditions of ice bath, instills 3- mercapto-thiophenes, the molar ratio of 3- mercapto-thiophenes and potassium tert-butoxide is 3- dropwise
43：10-70 is stirred 30~40 minutes, is vacuumized, nitrogen protection；Reaction bulb is placed in 60~90 DEG C of oil bath pan, kept the temperature again
20~30 minutes, then it is added dropwise bromoalkane into reaction bulb, the molar ratio of bromoalkane and 3- mercapto-thiophenes is 3-43：3-
43, when 60~90 DEG C of reaction 3-4 are small, cooling is stood, water quenching is added to go out, is extracted using ether, anhydrous magnesium sulfate drying, funnel mistake
Filter, solvent is spin-dried for using Rotary Evaporators, and petroleum ether crosses column, obtains colourless oil liquid, is intermediate compound a.
4. the polymer active layers material containing alkylthio group thiophene-fluoro diazosulfide according to claim 2
The preparation method of material, which is characterized in that the concrete operations of step (2) are：
Solvent is done with dichloromethane, intermediate compound a is added in reaction bulb, in ice bath and under the conditions of being protected from light, to reaction bulb
In the N- bromo-succinimides for being dissolved in n,N-Dimethylformamide, N- bromo-succinimides and intermediate compound is added dropwise
The molar ratio of a is 10-38：10-38, reaction overnight, are extracted using dichloromethane, anhydrous magnesium sulfate drying, and funnel filtering uses
Rotary Evaporators are spin-dried for solvent.Column is crossed using petroleum ether, obtains colourless oil liquid, is intermediate compound b.
5. the system of the polymer active layer material according to claim 2 containing alkylthio group thiophene-fluoro diazosulfide
Preparation Method, which is characterized in that the concrete operations of step (3) are：
By intermediate compound b and tetrahydrofuran 10-32mmol：The proportioning of 10-30ml by intermediate compound b and tetrahydrofuran successively
It is added in reaction bulb, vacuumizes, logical nitrogen, 20~30 minutes are kept the temperature at -60~70 DEG C, then it is different by intermediate compound b and two
Propylcarbamic lithium 10-32：Lithium diisopropylamine is added dropwise into reaction bulb for the molar ratio of 10-32, after dripping off, -60~
70 DEG C be stirred to react 1~2 it is small when, then by mass concentration be 5~10% dilute hydrochloric acid be added in reaction bulb, reaction is quenched,
Stirring 30~40 minutes, is then extracted using dichloromethane, anhydrous magnesium sulfate drying, and funnel filtering is revolved using Rotary Evaporators
Dry solvent, petroleum ether cross column, obtain colourless oil liquid, are intermediate compound c.
6. the system of the polymer active layer material according to claim 2 containing alkylthio group thiophene-fluoro diazosulfide
Preparation Method, which is characterized in that the concrete operations of step (4) are：
By intermediate compound c and tetrahydrofuran 10-15mmol：The proportioning of 10-20mL is by intermediate compound c, anhydrous tetrahydro furan
Be added sequentially in reaction bulb, vacuumize, logical nitrogen, 20~30 minutes are kept the temperature at -78~80 DEG C, then by intermediate compound c with
N-BuLi 10-15：N-BuLi is added dropwise into reaction bulb for the molar ratio of 10-15, after dripping off, in -78~80 DEG C of stirrings
When reaction 2~3 is small, then by intermediate compound c and tributyltin chloride 10-15：The molar ratio of 10-15 adds in tributyl chlorination
Tin, -78~80 DEG C be stirred to react 0.5-1 it is small when, move to room temperature, reaction overnight, is added water quenching, extracted using dichloromethane
It takes, anhydrous magnesium sulfate drying, funnel filtering is spin-dried for solvent using Rotary Evaporators, obtains colourless oil liquid, is centreization
Close object d.
7. the system of the polymer active layer material according to claim 2 containing alkylthio group thiophene-fluoro diazosulfide
Preparation Method, which is characterized in that the concrete operations of step (5) are：
Using toluene as solvent, by the dibromide of intermediate compound d, E, tetra-triphenylphosphine palladium 5-10：1.5-3.5：0.1-0.2's
Molar ratio is added sequentially in reaction bulb, and the proportioning of toluene and intermediate compound d are 20-30mL：5-10mmol, 100~110
DEG C oil bath under the conditions of reaction 36~48 it is small when, cross column using petroleum ether and dichloromethane, obtain peony thick liquid, be in
Between compound e.
8. the system of the polymer active layer material according to claim 2 containing alkylthio group thiophene-fluoro diazosulfide
Preparation Method, which is characterized in that the concrete operations of step (6) are：
Intermediate compound e is dissolved in chloroform, is added in reaction bulb, under conditions of ice bath, then by intermediate compound e
With N- bromo-succinimides 1-1.5：The molar ratio of 2.5-3.8 adds in N- bromo-succinimides, when reaction 2~3 is small after, rise
To room temperature, be further continued for reaction 2~3 it is small when, water is added to quench, is extracted using dichloromethane, anhydrous magnesium sulfate drying, funnel filtering,
Solvent is spin-dried for using Rotary Evaporators, column is crossed using petroleum ether and dichloromethane, obtains peony thick liquid, is intermediate chemical combination
Object f.
9. the system of the polymer active layer material according to claim 2 containing alkylthio group thiophene-fluoro diazosulfide
Preparation Method, which is characterized in that the concrete operations of step (7) are：
By 0.1-0.2mmol：0.1-0.2mmol：The proportioning of 3-4mL sequentially adds dry centre in dry reaction unit
The bilateral tin reagent of compound f, G and chromatographically pure chlorobenzene, after putting up reaction unit, liquid nitrogen frozen, defrosting deoxygenation, vacuum pumping is true
Sky, 2~5 times repeatedly, after solution freezes, rapidly join with intermediate compound f molar ratios be 1.5~2% Pd2(dba)3And with
Intermediate compound f molar ratios are 6~8% P (o-tol)3, again deoxygenation, vacuumize, logical nitrogen, be protected from light, be put into 100~110
DEG C oil bath pan in react 2~3 days, treat that reaction mixture cools down, move to room temperature, using chromatographically pure chloroform, ultra-pure water, into
Row extraction, is spin-dried for the 1/10~1/8 of total volume, and solution is added dropwise in Chromatographic Pure Methanol and settles, filter, reuses chromatography
Pure methanol, acetone, petroleum ether, dichloromethane, chloroform are stripped, and are spin-dried for chloroform to the 1/10~1/8 of total volume,
It reuses Chromatographic Pure Methanol sedimentation, filter, be dried in vacuo to obtain dark green solid, be final subject polymer (I).
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