CN110343235A - A kind of naphtho- Dithiophene conjugated polymer and the preparation method and application thereof - Google Patents
A kind of naphtho- Dithiophene conjugated polymer and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of naphtho- Dithiophene conjugated polymer and preparation method thereof, which has following molecular formula:R represents hydrogen atom or the alkyl with 1-30 carbon atom in formula；The repetitive unit number of n representation polymer, the natural number between 5-1000.The available excellent performance parameter of device based on naphtho- Dithiophene conjugated polymer of the invention, open-circuit voltage, short circuit current and fill factor are 0.953V, 13.92mA cm respectively‑2, 0.566, final energy transformation efficiency reaches 7.51%.
Description
Technical field
The present invention relates to a kind of naphtho- Dithiophene conjugated polymers and preparation method thereof, and in particular to a kind of PNDT-3T is poly-
Close application of the object in electrooptical device.
Background technique
It in recent years, is donor based on copolymer and non-fullerene small molecule is the non-fullerene polymer solar-electricity of receptor
Pool technology makes remarkable progress.Due to booming, the solar battery of polymeric donor and non-fullerene small molecule receptor
Energy conversion efficiency have reached 14% or more.In numerous non-fullerene small molecules, due to ITIC, IDIC, ITCPTC is easy
In synthesis, there is strong absorption in visible light region, can easily be accommodated energy level, and there is excellent stable appearance in blend film
Property, it is proved to be very effective acceptor material.The absorption region of above-mentioned material all in 700-1000nm, in order to these by
For body match materials to obtain better device performance, designing and preparing Wideband gap polymer donor material is to improve energy to turn
Change the effective way of efficiency.
It recent studies have shown that, based on the wide band gap polymer of benzo [1,2-b:4,5-b'] Dithiophene (BDT) in non-fowler
Excellent photovoltaic property is shown in alkene solar battery.By adding thiophene unit in BDT side chain positions, conjugation can be increased
Degree and the coplanarity for improving polymer chain, help to improve the transformation efficiency of energy.Thiophene unit has stronger electron
Property, the HOMO energy level of the wide band gap polymer based on BDT is relatively high.Therefore, suitable electrophilic unit can be introduced to reduce
HOMO energy level obtains wider band gap simultaneously.Hydrogen on ester group substituted thiophene can introduce a weak electron-withdrawing group effectively to drop
The HOMO energy level of low polymer.Jen et al. devises a kind of weak electrophilic unit, bis- (the 5- bromines of bis- (2- ethylhexyls) 2,5-
Thiophene -2- base) thieno [3,2-b] thiophene -3,6- dicarboxylic ester (TT-Th), and using the BDT unit of the side chain containing thiophene as donor
A kind of novel wide band gap polymer PBDT-TT is synthesized.The band gap of the polymer is 1.88eV, and HOMO energy level is -5.23eV,
By the optimization and characterization of device, energy conversion efficiency has reached 11.38%.The alkyl chain of Hou Jianhui et al. selection different length
Having designed and synthesized three kinds of band gap is 1.93eV, and HOMO energy level is the Wideband gap polymer of -5.5eV.Wherein it is based on PDBT-
The device energy conversion efficiency of EF-T:IT-4F has reached 14.2%, and fill factor has also reached 0.76.
In the report of numerous wide band gap polymers based on BDT, the BDT unit containing side chain is in the majority, and based on BDT's
Polymer is seldom, in addition, a phenyl ring is added in BDT unit constitutes naphtho- Dithiophene NDT, the conjugation journey of main chain can be improved
The flatness of degree and molecule, to reinforce its crystallinity and carrier mobility.The NDT of linear structure compared with BDT Conjugate extended and
High mobility degree is higher, so the Polymer photovoltaic materials for developing the NDT based on linear structure have very important significance.
Summary of the invention
It is an object of the invention to a kind of use naphtho- Dithiophene as donor monomer, ester in view of the above-mentioned problems, having invented
The new polymers that the terthienyl that base replaces is synthesized as receptor unit.In order to achieve the above object, this invention takes such as
Lower technical solution:
A kind of naphtho- Dithiophene conjugated polymer PNDT-3T, which is characterized in that polymer molecule formula is as follows:
Wherein, R represents hydrogen atom or the alkyl with 1-30 carbon atom；The repetitive unit number of n representation polymer is
Natural number between 5-1000, segment end group are R or H.
Preferably, R is 2- hexyl decyl, and polymer molecule formula is as follows:
A kind of preparation method of naphtho- Dithiophene conjugated polymer PNDT-3T, which comprises the steps of:
(1) thiophene -3- formic acid is dissolved in tetrahydrofuran and reacts to obtain with carbon tetrabromide under diisopropylamino lithium catalysis
- 3 carboxylic acid of 2- bromothiophene；
(2) -3 carboxylic acid of 2- bromothiophene and 2- hexyl decyl alcohol are made in dicyclohexylcarbodiimide and 4-dimethylaminopyridine catalysis
2- hexyl decyl 2- bromothiophene -3- carboxylate is obtained with lower reaction；
(3) 2- hexyl decyl 2- bromothiophene -3- carboxylate is urged with bis- (tin trimethyl) thiophene of 2,5- in tetra-triphenylphosphine palladium
The lower reaction of change effect obtains bis- (2- hexyl decyls) [2,2':5', 2 "-three thiophene] -3,3 "-dicarboxylic ester；
(4) bis- (2- hexyl decyls) [2,2':5', 2 "-three thiophene] -3,3 "-dicarboxylic esters and N-bromosuccinimide
It is dissolved in haloform reaction and obtains bis- (2- hexyl decyls) 5,5 "-two bromo- [2,2':5', 2 "-three thiophene] -3,3 "-dicarboxylic acids；
(5) naphthols bromine reaction under acetic acid and ferric trichloride catalytic effect obtains 1,3,5,7- tetrabromobisphenol, 6- dihydroxy
Naphthalene；
(6) 1,3,5,7- tetrabromobisphenol, 6- dihydroxy naphthlene react to obtain 3,7- bis- bromo- 2 under acetic acid and glass putty catalytic action,
6- dihydroxy naphthlene；
(7) the bromo- 2,6- dihydroxy naphthlene of 3,7- bis- and trifluoromethanesulfanhydride anhydride react under methylene chloride and pyridine catalytic action
Obtain bis- (fluoroform sulphonyl) naphthalenes of the bromo- 2,6- of 3,7- bis-；
(8) bis- (fluoroform sulphonyl) naphthalenes of the bromo- 2,6- of 3,7- bis- and trimethyl silicane ethyl-acetylene are in diisopropylamine, four triphenyls
Reaction obtains bis- (trimethylsilyl acetylene) naphthalenes of the bromo- 3,7- of 2,6- bis- under phosphine palladium and cuprous iodide catalytic action；
(9) bis- (trimethylsilyl acetylene) naphthalenes of the bromo- 3,7- of 2,6- bis- and nine water vulcanized sodium are catalyzed in N-methyl pyrrolidones makees
Bis- (trimethylstannyl) naphtho- [2,3-b:6,7-b'] Dithiophenes of 2,7- are obtained with lower reaction；
(10) naphtho- [2,3-b:6,7-b'] Dithiophene is reacted under diisopropylamino lithium effect with trimethyltin chloride
To bis- (trimethylstannyl) naphtho- [2,3-b:6,7-b'] Dithiophenes of 2,7-；
(11) bis- (2- hexyl decyls) 5,5 "-two bromo- [2,2':5', 2 "-three thiophene] -3,3 "-dicarboxylic acids and 2,7- is bis-
(trimethylstannyl) naphtho- [2,3-b:6,7-b'] Dithiophene is reacted under tetra-triphenylphosphine palladium catalytic action obtains polymer
PNDT-3T。
Specific reaction molecular formula is as follows:
A kind of application of naphtho- Dithiophene conjugated polymer PNDT-3T, is used to prepare solar battery electron donor material
Material.
Naphtho- Dithiophene conjugated polymer provided by the invention and preparation method thereof, has the advantages that
(1) present invention is using naphtho- Dithiophene as donor monomer, and the terthienyl that ester group replaces is as receptor unit, synthesis
The polymer of novel broad-band gap, this linear NDT structure have more compared to the BDT structure of leading position
Conjugate extended and high mobility.
(2) 2- hexyl decyl is introduced into three league matches point and forms weak electron-withdrawing group, the HOMO energy of polymer can be reduced
Grade.
(3) PNDT-3T polymer of the invention can be used for the preparation of solar battery electron donor material, can solve device
The problem of part low efficiency.
Detailed description of the invention
Fig. 1 is the thermogravimetric analysis figure of polymer P NDT-3T of the invention.
Fig. 2 is the uv-visible absorption spectra of polymer P NDT-3T of the invention.
Fig. 3 is the Cyclic voltamogram curve graph of polymer P NDT-3T of the invention.
Fig. 4 is the J-V curve graph of photovoltaic device made of polymer P NDT-3T and ITCPIC of the invention.
Fig. 5 is the EQE curve graph of photovoltaic device made of polymer P NDT-3T and ITCPIC of the invention.
Specific embodiment
Below by example, the present invention is further elaborated, it is therefore intended that more fully understands the contents of the present invention, is lifted
Example be not intended to limit protection scope of the present invention.
(1) synthesis of polymer
2- bromothiophene -3- carboxylic acid (2)
Chemicals 1 (4g, 31.3mmol) is added in the flask of 100mL, after the dissolution of 60mL tetrahydrofuran, air-blowing 15 divides
Clock.Diisopropylamino lithium (2M, 62.5mmol) is slowly added into reaction solution at -78 DEG C and at -78 DEG C reaction 0.5 it is small
When.Then it in -78 DEG C of upper disposable additions carbon tetrabromide (10.36g, 31.3mmol), is reacted 1 hour after slowly restoring room temperature.
After reaction, 10mL water and 10mL hydrochloric acid are added into solution, three times with ether extraction mixture.After solvent is spin-dried for, use
Ethanol/water (4:1) recrystallization, finally obtained product are white solid (5g, yield 78%).1H NMR(CDCl3,400MHz),
d(ppm):d 7.44(d,1H),7.26(d,1H).13C NMR(CDCl3,100MHz),d(ppm):d 166.99,130.40,
130.12,126.66,122.36.
2- hexyl decyl 2- bromothiophene -3- carboxylate (3)
By compound 2 (5g, 24.4mmol), dicyclohexylcarbodiimide (6.1g, 29.3mmol) and 4- dimethylamino pyrrole
Pyridine (0.89g, 7.32mmol) is dissolved in 100mL methylene chloride.2- hexyl decyl alcohol (5.6g, 24.4mmol) is added into reaction solution
Reaction is stayed overnight at room temperature afterwards.After reaction, it is purified after mixed liquor suction filtration being spin-dried for by silica gel column chromatography, uses petroleum
Ether/methylene chloride (5:1) is used as eluant, eluent, and finally obtaining product is colourless liquid.(9.5g, 91% yield)1H NMR(CDCl3,
400MHz),d(ppm):d 7.36(d,1H),7.21(d,1H),4.19(d,2H),1.73(m,1H),1.27(m,24H),0.85
(m,6H).13C NMR(CDCl3,100MHz),d(ppm):d 162.03,132.61,129.65,125.55,119.45,
67.64,37.37,31.92,31.83,31.38,29.33,26.75,26.73,22.70,22.67,14.14,14.12.
Bis- (2- hexyl decyls) [2,2':5', 2 "-three thiophene] -3,3 "-dicarboxylic esters (4)
By compound 3 (1.32g, 25.1mmol) and 2, the mixture of bis- (tin trimethyl) thiophene (0.5g, 1.2mmol) of 5-
It is added in the flask of 100mL, and is dissolved with 30mL toluene.Solution is being added in tetra-triphenylphosphine palladium (138mg, 0.12mmol)
In after, be refluxed overnight with nitrogen air-blowing 10 minutes, and under conditions of 110 DEG C of anhydrous and oxygen-frees.It is cooled to room temperature after reaction,
Solvent is evaporated, crude product is purified by silica gel column chromatography, is used petroleum ether/methylene chloride (5:1) as eluant, eluent, is obtained Huang
Color oily liquids (0.67g, 70% yield).1H NMR(CDCl3,400MHz),d(ppm):d 7.29(d,2H),7.19(s,
2H),6.96(d,2H),4.03(d,4H),1.97(m,2H),1.14(m,48H),0.78(m,12H).13C NMR(CDCl3,
400MHz),d(ppm):d 163.25,142.50,135.98,130.54,129.17,128.31,124.11,67.66,
37.32,35.59,31.92,31.84,31.31,29.65,29.59,29.34,26.77,22.70,22.67,14.14,
14.12.
Bis- (2- hexyl decyls) 5,5 "-two bromo- [2,2':5', 2 "-three thiophene] -3,3 "-dicarboxylic acids (5)
Compound 4 (0.5g, 0.6mmol) is added in the flask of 100mL and uses the chloroform of 20mL as solvent, in room temperature
Under be slowly added to N-bromosuccinimide (0.24g, 1.3mmol).It is reacted 2 hours under conditions of being protected from light.After reaction,
10mL water is added in mixture, mixture is extracted with dichloromethane three times and with anhydrous MgSO4It is dry.Solvent is spin-dried for
Afterwards, crude product purified by silica gel column further purifies, and uses petroleum ether/methylene chloride (3:1) as eluant, eluent, obtains yellow oil
(0.42g, 70% yield).1H NMR(CDCl3,400MHz),d(ppm):d 7.42(s,2H),7.34(s,2H),4.12(d,
4H),1.67(m,2H),1.25(m,48H),0.85(m,12H).13C NMR(CDCl3,400MHz),d(ppm):d 162.01,
143.54,135.33,132.77,129.46,128.62,111.10,67.99,37.29,31.93,31.85,31.28,
29.63,29.60,26.73,22.11,22.08,14.15.
1,3,5,7- tetrabromobisphenol, 6- dihydroxy naphthlene (7)
Chemicals 6 (10g, 31.3mmol) is added in 250mL flask and uses 100mL acetic acid as solvent.13mL is added
After bromine at 120 DEG C back flow reaction 12 hours, then add ferric trichloride (0.75g, 4.6mmol) and 13mL bromine, 120
Back flow reaction 12 hours at DEG C.After reaction, it is cooled to room temperature and is added the ice water of 100mL, after product is filtered drying
Light green solid is recrystallized to give with 1,4- dioxane.(21g, yield 71%)1H NMR(400MHz,THF)δ5.58(s,
2H),7.25(s,2H),7.89(s,2H)
The bromo- 2,6- dihydroxy naphthlene (8) of 3,7- bis-
Chemicals 7 (5g, 10.5mmol) is added in 250mL flask and uses 100mL acetic acid as solvent.Into reaction solution
It is added glass putty (2.5g, 21mmol), back flow reaction 75 hours at 120 DEG C.After being cooled to room temperature after reaction, to mixture
Middle addition 100mL water.Product is filtered and is washed with water, chemicals 8 are obtained after drying, is white solid.(2.5g, 75%)1H
NMR(400MHz,DMSO)δ7.93(s,2H),7.36(s,2H),5.92(s,2H).
Bis- (fluoroform sulphonyl) naphthalenes (9) of the bromo- 2,6- of 3,7- bis-
Compound 8 (2g, 6.3mmol) is added in 100mL flask and uses 40mL methylene chloride as solvent.To reaction
After 3mL pyridine is added in liquid, it is slowly added to trifluoromethanesulfanhydride anhydride (2.2mL, 14mmol).After reacting 15 hours at room temperature, add
Enter 10mL water and 10mL hydrochloric acid.It is three times and dry with anhydrous magnesium sulfate that mixture is extracted with dichloromethane, after solvent is spin-dried for, slightly
Product is purified with silica gel column chromatography, is used methylene chloride as eluant, eluent, is obtained white solid.(2.27g, 62%)1H NMR
(400MHz,CDCl3)δ8.16(s,2H),7.05(s,2H).
Bis- (trimethylsilyl acetylene) naphthalenes (10) of the bromo- 3,7- of 2,6- bis-
By compound 9 (1g, 1.7mmol), 12mL diisopropylamine, tetra-triphenylphosphine palladium (150mg, 0.13mmol) and iodate
Cuprous (120mg, 0.63mmol) is added in 100mL flask, is dissolved with 30mL dimethylformamide.Air-blowing ten minutes later, is delayed
It is slow that trimethyl silicane ethyl-acetylene (0.35g, 3.5mmol) is added and reacts 1 hour at room temperature.After reaction be added 5mL water and
5mL hydrochloric acid, mixture are extracted with dichloromethane dry with anhydrous magnesium sulfate afterwards three times.After being spin-dried for solvent, crude product passes through silicon
Rubber column gel column purification, uses petroleum ether as eluant, eluent, obtains white solid.(0.73g, 65% yield)1H NMR(400MHz,CDCl3)δ
7.90(s,2H),7.79(s,2H),0.45(s,18H).
Naphtho- [2,3-b:6,7-b'] Dithiophene (11)
(400mg, 0.93mmol) the He Jiushui vulcanized sodium of compound 10 (800mg, 3.33mmol) is added to the burning of 100mL
In bottle, and use 20mL N-methyl pyrrolidones as solvent.After reaction flows back 12 hours at 185 DEG C, stop heating and cooling
To room temperature.It feeds the mixture into 20mL saturated aqueous ammonium chloride.Gained sediment is collected by filtration and with water, methanol and hexane
Washing.Obtain light yellow solid.(0.42g, 75%)1H NMR(400MHz,CDCl3)δ8.61(s,2H),8.50(s,2H),
7.58(d,2H),7.46(d,2H).
Bis- (trimethylstannyl) naphtho- [2,3-b:6,7-b'] Dithiophenes (12) of 2,7-
Compound 11 (200mg, 0.83mmol) is added in 50mL flask and is dissolved in 20mL tetrahydrofuran.Air-blowing
After 15 minutes, diisopropylamino lithium (2M, 1.66mmol) is slowly added into reaction solution at -78 DEG C, restore room temperature after
Back flow reaction 2 hours at 65 DEG C.Then in -78 DEG C of upper disposable additions trimethyltin chloride (1M, 3.8mL), slow recovery room
It is reacted 20 hours after temperature.10mL water is added after reaction terminating into mixed liquor, with ether extraction mixture three times and with anhydrous sulphur
Sour magnesium is dry.After being spin-dried for solvent, using ethyl alcohol recrystallization, finally obtaining product is yellow solid (0.42g, yield 90%).1H NMR(400MHZ,CDCl3):8.53(s,2H),7.81(s,2H),7.54(s,2H),0.53(s,18H).
Bis- (trimethylstannyl) benzo [1,2-b:4,5-b'] Dithiophenes (13) of 2,6-
Benzo [1,2-b:4,5-b'] Dithiophene (0.6g, 3.2mmol) is added in 50mL flask and is dissolved in 20mL
In tetrahydrofuran.After air-blowing 15 minutes, diisopropylamino lithium (2M, 4mL) is slowly added into reaction solution at -78 DEG C, -
It is reacted 2 hours at 78 DEG C.Then slowly anti-after recovery room temperature in -78 DEG C of upper disposable additions trimethyltin chloride (1M, 10mL)
It should stay overnight.10mL water is added after reaction terminating into mixed liquor, it is three times and dry with anhydrous magnesium sulfate with ether extraction mixture.
After being spin-dried for solvent, with ethyl alcohol recrystallization, white crystalline solid (1.46g, yield 90%) is obtained.1H NMR(CDCl3,
400MHz),d(ppm):d 8.26(s,2H),7.41(s,2H),0.43(m,18H).13C NMR(CDCl3,400MHz),d
(ppm):d 141.77,141.36,138.61,130.99,115.11,8.31.
Polymer P NDT-3T
Compound 5 (141.46mg, 0.15mmol) and 12 (84.90mg, 0.15mmol) are added in 50mL flask and molten
Solution was in the toluene of 8mL, with nitrogen air-blowing 10 minutes.After flask is added in tetra-triphenylphosphine palladium (8mg), then air-blowing 10 minutes.
Reaction solution is gradually heated to 110 DEG C and is reacted 16 hours under 110 DEG C and nitrogen atmosphere.After reaction, stop heating simultaneously
It is cooled to room temperature, mixture is deposited in 60mL methanol and is filtered.In vacuum drying oven after drying, crude product passes through silicagel column
Purification, obtains product.(65% yield)
(2) heat stability testing
The thermal stability of polymer is tested by thermogravimetric analysis (TGA).The result shows that polymer P NDT-3T is in weightlessness
Decomposition temperature when 5% is 372 DEG C.
(3) ultraviolet-ray visible absorbing is tested
It can be seen that absorption peak of the PNDT-3T in solution and film is respectively in 502 and 528nm.
(4) electro-chemical test
It is tested using electrochemical properties of the electrochemical workstation to the polymer, the initial oxidation potential of PNDT-3T
It (Eox) is 1.07V relative to Ag/Ag+.The initial reduction current potential (Ered) of PNDT-3T is -1.01eV relative to Ag/Ag+.Cause
This, the HOMO and lumo energy of our available PNDT-3T is respectively -5.44eV and -3.36eV.
(5) preparation and representation of device
Device architecture is ITO/PEDOT:PSS/ polymer: ITCPTC/Ca/Al.Ito glass substrate successively use suds,
After deionized water, acetone and isopropanol ultrasonic cleaning, used ozone treatment 20 minutes after being dried in vacuum overnight at 110 DEG C.Then
PEDOT:PSS with 4000rpm spin coating 30 seconds and is annealed 10 minutes at 145 DEG C in ito glass substrate.To have different dense
It spends additive and is dissolved in 1,2- dichloro-benzenes (DCB) to the mixture of receptor weight ratio PNDT-3T and ITCPTC, then 90
It is stirred overnight at DEG C.Then, active layer was with 1500rpm spin coating 40 seconds.Finally, being sequentially completed electron transfer layer with the method for vapor deposition
With the preparation of electrode layer.Current density-voltage (J-V) curve is measured under the simulated light of AM1.5G by Keithley 2400,
In, solar simulator is corrected by the silicon solar cell of calibration.EQE value then uses QEX10 solar battery IPCE
Measuring system measures.Device open-circuit voltage, short circuit current and fill factor based on PNDT-3T, be respectively for 0.953V,
13.92mA cm-2, 0.566, final energy transformation efficiency be 7.51%.
Although for illustrative purposes, it has been described that exemplary embodiments of the present invention, those skilled in the art
Member it will be understood that, can be in form and details in the case where the scope and spirit for not departing from invention disclosed in appended claims
On the change that carry out various modifications, add and replace etc., and all these changes all should belong to appended claims of the present invention
Protection scope, and each step in the claimed each department of product and method, can in any combination
Form is combined.Therefore, to disclosed in this invention the description of embodiment be not intended to limit the scope of the invention,
But for describing the present invention.Correspondingly, the scope of the present invention is not limited by embodiment of above, but by claim or
Its equivalent is defined.
Claims (4)
1. a kind of naphtho- Dithiophene conjugated polymer PNDT-3T, which is characterized in that polymer molecule formula is as follows:
Wherein, R represents hydrogen atom or the alkyl with 1-30 carbon atom；The repetitive unit number of n representation polymer is 5-
Natural number between 1000, segment end group are R or H.
2. naphtho- Dithiophene conjugated polymer PNDT-3T according to claim 1, which is characterized in that R is the 2- hexyl last of the ten Heavenly stems
Base, polymer molecule formula are as follows:
3. the preparation method of naphtho- Dithiophene conjugated polymer PNDT-3T described in one of -2, feature exist according to claim 1
In including the following steps:
(1) thiophene -3- formic acid is dissolved in tetrahydrofuran and reacts to obtain 2- bromine with carbon tetrabromide under diisopropylamino lithium catalysis
- 3 carboxylic acid of thiophene；
(2) -3 carboxylic acid of 2- bromothiophene and 2- hexyl decyl alcohol are under dicyclohexylcarbodiimide and 4-dimethylaminopyridine catalytic action
Reaction obtains 2- hexyl decyl 2- bromothiophene -3- carboxylate；
(3) 2- hexyl decyl 2- bromothiophene -3- carboxylate and bis- (tin trimethyl) thiophene of 2,5- are catalyzed in tetra-triphenylphosphine palladium makees
Bis- (2- hexyl decyls) [2,2':5', 2 "-three thiophene] -3,3 "-dicarboxylic esters are obtained with lower reaction；
(4) bis- (2- hexyl decyls) [2,2':5', 2 "-three thiophene] -3,3 "-dicarboxylic esters are dissolved in N-bromosuccinimide
Haloform reaction obtains bis- (2- hexyl decyls) 5,5 "-two bromo- [2,2':5', 2 "-three thiophene] -3,3 "-dicarboxylic acids；
(5) naphthols bromine reaction under acetic acid and ferric trichloride catalytic effect obtains 1,3,5,7- tetrabromobisphenol, 6- dihydroxy naphthlene；
(6) 1,3,5,7- tetrabromobisphenol, 6- dihydroxy naphthlene react to obtain the bromo- 2,6- bis- of 3,7- bis- under acetic acid and glass putty catalytic action
Hydroxyl naphthalene；
(7) the bromo- 2,6- dihydroxy naphthlene of 3,7- bis- and trifluoromethanesulfanhydride anhydride react under methylene chloride and pyridine catalytic action obtains
Bis- (fluoroform sulphonyl) naphthalenes of the bromo- 2,6- of 3,7- bis-；
(8) bis- (fluoroform sulphonyl) naphthalenes of the bromo- 2,6- of 3,7- bis- and trimethyl silicane ethyl-acetylene are in diisopropylamine, tetra-triphenylphosphine palladium
Bis- (trimethylsilyl acetylene) naphthalenes of the bromo- 3,7- of 2,6- bis- are obtained with reaction under cuprous iodide catalytic action；
(9) bis- (trimethylsilyl acetylene) naphthalenes of the bromo- 3,7- of 2,6- bis- and nine water vulcanized sodium are under N-methyl pyrrolidones catalytic action
Reaction obtains bis- (trimethylstannyl) naphtho- [2,3-b:6,7-b'] Dithiophenes of 2,7-；
(10) naphtho- [2,3-b:6,7-b'] Dithiophene reacts to obtain 2 with trimethyltin chloride under diisopropylamino lithium effect,
Bis- (trimethylstannyl) naphtho- [2,3-b:6,7-b'] Dithiophenes of 7-；
(11) bis- (2- hexyl decyls) 5,5 "-two bromo- [2,2':5', 2 "-three thiophene] -3,3 "-dicarboxylic acids and 2, the bis- (front threes of 7-
Base stannane base) naphtho- [2,3-b:6,7-b'] Dithiophene reacts under tetra-triphenylphosphine palladium catalytic action and obtains polymer P NDT-
3T。
4. the application of naphtho- Dithiophene conjugated polymer PNDT-3T described in one of -3 according to claim 1, which is characterized in that
It is used to prepare solar battery electron donor material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708112A (en) * | 2019-10-24 | 2021-04-27 | 位速科技股份有限公司 | Conjugated polymer and organic photovoltaic element |
| TWI734227B (en) * | 2019-10-24 | 2021-07-21 | 位速科技股份有限公司 | Conjugated polymers and organic photovoltaic elements |
| EP4145548A4 (en) * | 2020-04-30 | 2023-11-22 | FUJIFILM Corporation | Photoelectric conversion element, imaging element, optical sensor, and compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011078246A1 (en) * | 2009-12-25 | 2011-06-30 | 住友化学株式会社 | Polymer compound, and thin film and ink composition each containing same |
| CN102224157A (en) * | 2008-11-21 | 2011-10-19 | 国立大学法人广岛大学 | Novel compound, process for producing the compound, organic semiconductor material, and organic semiconductor device |
| CN102532492A (en) * | 2011-12-29 | 2012-07-04 | 中国科学院化学研究所 | Crosslinking thiopheno[3,4-b] thiophene conjugated polymer and preparation method and application thereof |
| US20130035464A1 (en) * | 2011-08-01 | 2013-02-07 | Antonio Facchetti | Semiconducting Compounds and Devices Incorporating Same |
-
2019
- 2019-06-27 CN CN201910565435.3A patent/CN110343235A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102224157A (en) * | 2008-11-21 | 2011-10-19 | 国立大学法人广岛大学 | Novel compound, process for producing the compound, organic semiconductor material, and organic semiconductor device |
| WO2011078246A1 (en) * | 2009-12-25 | 2011-06-30 | 住友化学株式会社 | Polymer compound, and thin film and ink composition each containing same |
| US20130035464A1 (en) * | 2011-08-01 | 2013-02-07 | Antonio Facchetti | Semiconducting Compounds and Devices Incorporating Same |
| CN102532492A (en) * | 2011-12-29 | 2012-07-04 | 中国科学院化学研究所 | Crosslinking thiopheno[3,4-b] thiophene conjugated polymer and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YANAN SHI ET AL.: "A-π-D-π-A small-molecule donors with different end alkyl chains obtain different morphologies in organic solar cells", 《CHINESE CHEMICAL LETTERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708112A (en) * | 2019-10-24 | 2021-04-27 | 位速科技股份有限公司 | Conjugated polymer and organic photovoltaic element |
| TWI734227B (en) * | 2019-10-24 | 2021-07-21 | 位速科技股份有限公司 | Conjugated polymers and organic photovoltaic elements |
| CN112708112B (en) * | 2019-10-24 | 2023-12-26 | 位速科技股份有限公司 | Conjugated polymer and organic photovoltaic element |
| EP4145548A4 (en) * | 2020-04-30 | 2023-11-22 | FUJIFILM Corporation | Photoelectric conversion element, imaging element, optical sensor, and compound |
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