CN109776767A - The conjugated polymer and its synthetic method of a kind of diketone of aphthothiophenes containing difluoro electrophilic unit and application - Google Patents
The conjugated polymer and its synthetic method of a kind of diketone of aphthothiophenes containing difluoro electrophilic unit and application Download PDFInfo
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Abstract
The invention discloses a kind of conjugated polymer of the diketone of aphthothiophenes containing difluoro electrophilic unit and its synthetic method and applications, belong to polymer applied to photoelectron material and devices field.Conjugated polymer prepared by the present invention forms non-binding effect using containing double fluorine-substituted benzheterocycle structures, fluorine atom and electron unit, enhances carrier and transmits in plane, rigid backbone structure, help to obtain high mobility.And such conjugated polymer has wider optical band gap, it is suitble to realize the complementary of absorption spectrum with the collocation of the small molecule receptor of narrow band gap, therefore it can be used for making polymer LED device, the active layer of polymer field effect transistor and polymer solar battery.
Description
Technical field
The present invention relates to polymer to be applied to photoelectron material and devices field, and in particular to a kind of aphthothiophenes containing difluoro
The conjugated polymer of diketone electrophilic unit.
Background technique
With the development of human society, the tradition non-renewable energy resources reserves such as coal, oil and natural gas are increasingly reduced, and are sought
The new energy of sustainable development is very urgent.Solar energy is inexhaustible as a kind of green regenerative energy sources.
Organic photovoltaic cell there is material to be easy to get, the preparation of lightweight, flexibility and large area as one of the important means of energy problem is solved
The advantages that thin-film device, has obtained the extensive concern of scientists.Organic solar batteries active layer material it is many kinds of simultaneously
And chemical structure is easy modification, preparation purification is easy, has significant advantage in terms of material source and cost.And it is organic too
It is positive can battery can large area prepare roll-to-roll fexible film device, thus with huge commercial application prospect.Currently, in spite of
Machine conjugated polymer material huge number, but have the material of wide absorption and high carrier mobility fewer, in order to realize
More efficient photoelectric conversion efficiency, the donor polymer material for developing novel high-performance have a very important significance.
Summary of the invention
It is an object of the invention to the deficiency for novel conjugated molecular material exploitation at present, design synthesis energy conversion effects
The conjugated polymer donor of the higher -4,9- diketone electrophilic unit Han 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene of rate
Material.
Another object of the present invention is to provide described one kind to contain 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene-
The synthetic method and application of the conjugated polymer of 4,9- diketone electrophilic unit.
The invention is realized by the following technical scheme.
A kind of conjugated polymer of the diketone of aphthothiophenes containing difluoro electrophilic unit contains bis- R-6,7- difluoro naphtho- of 1,3-
The conjugated polymer of [2,3-c] thiophene -4,9- diketone electrophilic unit, structural formula are as follows:
In formula, R is hydrogen atom or alkyl chain；Ar1, Ar2 are aromatic group；D is electron donor unit；The electron donor
Cells D and the fluoro- 5,8-Ar1 of bis- R-6,7- of 1,3- bis-, Ar2 naphtho- [2,3-c] thiophene -4,9- diketone electrophilic unit is with the side of conjugation
Formula is connected, and n is the degree of polymerization of the conjugated polymer, the natural number that the n is 1~10000.
Preferably, the alkyl chain be carbon atom number be 1~24 straight chain, branch, cyclic alkyl chain or the straight chain,
In branch, cyclic alkyl chain one or more carbon atoms by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl,
Ester group, cyano or nitro replace, and hydrogen atom is by halogen atom, oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxylic
Base, amino cation, ester group, cyano, nitro replace.
Preferably, at least one that the Ar1 or Ar2 are comprised the following structure:
R1It is one or more carbon atoms in hydrogen atom or alkyl chain or the alkyl chain by oxygen atom, alkenyl, alkynes
Base, aryl, hydroxyl, amino, carbonyl, carboxyl, nitro, phenyl or one or more of thienyl substitution or the alkyl chain
Hydrogen atom is substituted with halogen atoms.
Preferably, at least one that the electron donor cells D comprises the following structure:
Wherein, R2、R3It is former by oxygen atom, halogen for one or more carbon atoms in hydrogen atom or alkyl chain or alkyl chain
One in son, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, nitro, phenyl or thienyl substitution or alkyl chain
Or multiple hydrogen atoms are substituted with halogen atoms.
Preferably, R1、R2、R3Straight chain, branch or the cyclic alkyl chain for being 1~30 for carbon atom number.
The present invention also provides bis- R-6,7- difluoro naphtho- [2,3-c] thiophene -4,9- two containing 1,3- described in more than one
The synthetic method of the conjugated polymer of ketone electrophilic unit, includes the following steps:
(1) the fluoro- 5,8-Ar of bis- R-6,7- of 1,3- bis- is synthesized1,Ar2Naphtho- [2,3-c] thiophene -4,9- diketone electrophilic unit.
(2) under the protection of inert gas, by electron donor cells D and 1,3-, bis- R-6, fluoro- 5,8-Ar1, the Ar2 naphthalene of 7- bis-
And [2,3-c] thiophene -4,9- dione unit, catalyst tetra-triphenylphosphine palladium are dissolved in organic solvent, heated sealed is cooled to
It by reaction solution precipitating in methyl alcohol after room temperature, is successively purified, is removed with methanol, acetone, n-hexane, methylene chloride and chloroform
Chloroform component is concentrated in catalyst, and precipitating, vacuum drying are obtained containing 1,3-, bis- R-6,7- difluoro naphtho- [2,3-c] in methyl alcohol again
The conjugated polymer of thiophene -4,9- diketone.
Preferably, the electron donor cells D, fluoro- 5,8-Ar1, Ar2 naphtho- [2, the 3-c] thiophene-of 1,3- bis- R-6,7- bis-
4,9- dione unit, catalyst tetra-triphenylphosphine palladium molar ratio be 20:20:1.
Preferably, the inert gas is nitrogen or argon gas；The actual conditions of the heating are 80 DEG C of microwave and continue 2 points
Clock, 120 DEG C continue 2 minutes, and 160 DEG C continue 2 minutes, and last 200 DEG C continue 45 minutes.
Preferably, the purification is to be purified by soxhlet type method.
The present invention provides a kind of -4,9- diketone electrophilic units containing 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene
Conjugated polymer prepare polymer LED device luminescent layer, preparation polymer field effect transistor in partly leading
Body active layer prepares application in the active layer of polymer solar photovoltaic cell.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) present invention has weaker containing 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene -4,9- diketone electrophilic unit
Electron attraction, cooperate weaker electron unit that can obtain the polymer of broad-band gap.And the unit contains double fluorine and replaces
Benzheterocycle structure, fluorine atom and electron unit form non-binding effect, enhance carrier in plane, the master with rigidity
It is transmitted in chain structure, conducive to high mobility is obtained.
(2) present invention contains contains on 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene -4,9- diketone electrophilic unit thiophene
There is alkyl side chain, this is beneficial to the dissolubility for adjusting copolymer.Due to its good solution processability energy, excellent photo electric
Can, in the work of the luminescent layer of production polymer LED, polymer field effect transistor and polymer solar battery
Property layer field have good application.
Detailed description of the invention
Fig. 1 is the hot weight curve of polymer P FPT-BDT prepared by embodiment 3；
Fig. 2 is the polymer P FPT-BDT of the preparation of embodiment 3 in the UV-Visible absorption light in chlorobenzene solution and film
Spectrogram；
Fig. 3 is the cyclic voltammetry curve figure of the electro-chemical test of polymer P FPT-BDT prepared by embodiment 3 and ferrocene；
Fig. 4 is polymer P FPT-BDT prepare based on embodiment 3, the PFPT-DTBDT of the preparation of embodiment 4, embodiment 5
Short-circuit current density-voltage of the organic photovoltaic cell device of the PFPT-DFDT of PFPT-DT and embodiment 6 preparation of preparation is special
Linearity curve；
Specific embodiment
Specific implementation of the invention is further described below in conjunction with example, but embodiments of the present invention are not limited to
This.
Embodiment 1
Fluoro- 5,8- bis- (thiophene -2- base) naphtho- [2,3-c] thiophene -4,9- diketone of 1,3- bis- (2- ethylhexyl) -6,7- two
Preparation:
(1) under nitrogen protection, into two mouthfuls of round-bottomed flasks of 100mL, 4,5- difluoro phthalic acid 1 is added
(4.04g, 20mmol), drop n,N-Dimethylformamide (DMF), ethanedioly chloride (10mL) add the anhydrous dichloromethane of 20mL
Alkane makees solvent, stirs 12 hours under room temperature.In the solution of stirring be added 2,5- bis- (2- ethylhexyl) thiophene 2 (6.17g,
20mmol),AlCl3(10.67g, 80mmol) is moved it under 0 DEG C of ice-water bath and is stirred 30 minutes, then place and stir at room temperature
It mixes 3 hours.Post-processing: reaction mixture diluted hydrochloric acid aqueous solution and chloroform are extracted, organic phase is obtained, is put into single port bottle simultaneously
Silica white is admixed to be rotated, then with silicagel column cross column purification (eluant, eluent selects petroleum ether: methylene chloride is 4:1 (v/v)),
Obtain yellow solid product 3 (7.20g, yield: 75%).
(2) under nitrogen protection, in the three neck round bottom flask of 250mL, diisopropylamine (3.04g, 30mmol) is dissolved in
In anhydrous tetrahydro furan (30mL), after temperature is down to -78 DEG C, it is slowly dropped into n-BuLi (12mL, 2.5mol L thereto-1, oneself
Alkane solution), reaction, which is maintained at -78 DEG C, stirs 1 hour.Then, product 3 (3.42g, 7.20mmol) is dissolved in anhydrous tetrahydro furan
It mutters in (25mL), and is added in reaction solution, continuation is stirred 40 minutes at -78 DEG C.Finally, iodine is added into reaction solution
Tetrahydrofuran (30mL) solution of (7.62g, 30mmol), reaction are stirred overnight.Post-processing: reaction solution is poured into saturation sulfurous acid
Hydrogen sodium solution removes unreacted elemental iodine.Methylene chloride extraction, anhydrous magnesium sulfate are dry.After vacuum distillation, crude product silicon
Rubber column gel column purify (eluant, eluent selects petroleum ether: methylene chloride is 3:1 (v/v)), obtain yellow solid product 4 (2.73g, yield:
60%).
(3) under nitrogen protection, product 4 (1.90g, 3mmol) is added in two mouthfuls of round-bottomed flasks of 50mL, trimethyl thiophene
Pheno 5 (3.36g, 9mmol), bis-triphenylphosphipalladium palladium dichloride (Pd (PPh3)Cl2, 45mg, 2%mmol are dissolved in toluene (30mL)
In, it is heated to 90 DEG C and flows back 48 hours.After 4 fully reacting of product, stop heating, and cool the temperature to room temperature.Post-processing: will
Reaction solution is poured into water, ethyl acetate extraction, saturated sodium-chloride water solution washing, and anhydrous magnesium sulfate is dry.After vacuum distillation, slightly
Product silicagel column purifies (eluant, eluent selects petroleum ether: methylene chloride is 8:1 (v/v)), obtains yellow solid product 6
(1.53g, yield: 80%).
Embodiment 2
Fluoro- 5,8- bis- (5- bromothiophene -2- base) naphthols of 1,3- bis- (2- ethylhexyl) -6,7- two simultaneously [2,3-c] thiophene -4,
The preparation of 9- diketone (M1):
In the single port bottle of 100mL, compound 6 (0.69g, 1mmol) is dissolved in chloroform (30mL) and acetic acid (30mL)
The volume ratio of in the mixed solvent, the chloroform and acetic acid is 1:1.Then single port bottle is placed in ice bath, works as reacting liquid temperature
It is reduced to 0 DEG C or so, N- bromo-succinimide NBS (0.38g, 2mmol) is added by batch thereto, reaction is stirred at room temperature
8 hours.Post-processing: reaction solution is poured into water, is extracted with dichloromethane, organic layer is washed with saturated sodium-chloride water solution, anhydrous
Magnesium sulfate is dry.After vacuum distillation, crude product purified by silica gel column purifies (eluant, eluent selection petroleum ether), obtains yellow solid product M1
(fluoro- 5,8- bis- (5- bromothiophene -2- base) naphthols of 1,3- bis- (2- ethylhexyl) -6,7- two simultaneously [2,3-c] thiophene -4,9- diketone)
(0.68g, yield: 85%).
Embodiment 3
The preparation of PFPT-BDT
It is automatically controlled in glove box in water oxygen, by compound M1 (fluoro- 5, the 8- bis- of 1,3- bis- (2- ethylhexyl) -6,7- bis-
(5- bromothiophene -2- base) naphthols simultaneously [2,3-c] thiophene -4,9- diketone) (79.7mg, 0.10mmol), compound M2 (4,8- bis-
(5- (2- ethylhexyl) thiophene -2- base) benzo [1,2-b:4,5-b'] Dithiophene -2,6- diyl) two (tin trimethyls)
(90.5mg, 0.10mmol) and catalyst tetra-triphenylphosphine palladium (5.86mg, 0.005mmol) are added into 10mL microwave tube, add
Enter anhydrous dimethyl benzene (2.5mL) dissolution, the sealing of silica gel lid.Microwave tube is placed in microwave reactor, set temperature program: 80 DEG C
Continue 2 minutes, 120 DEG C continue 2 minutes, and 160 DEG C continue 2 minutes, and last 200 DEG C continue 45 minutes, are cooled to room temperature wait react
By reaction solution precipitating in 200mL methanol, soxhlet type successively is carried out with methanol, acetone, n-hexane, methylene chloride and chloroform,
Then aqueous solution (225mg, 1mmol, the 100mL of sodium diethyldithiocarbamate trihydrate are added into chloroform component
Water), it stirs 8 hours at 60 DEG C, except the palladium catalyst in dereaction, chloroform component is concentrated, use methanol precipitating, vacuum again
Cyan solid PFPT-BDT (96mg, yield: 77.6%) are obtained after drying.1H NMR、13C NMR、18F NMR analysis is that target produces
Object.Chemical equation is as follows:
Embodiment 4
The preparation of PFPT-DTBDT
It is automatically controlled in glove box in water oxygen, by compound M1 (fluoro- 5, the 8- bis- of 1,3- bis- (2- ethylhexyl) -6,7- bis-
(5- bromothiophene -2- base) naphthols simultaneously [2,3-c] thiophene -4,9- diketone) (79.7mg, 0.10mmol), compound M3 (4,8- bis-
(5- (2- ethylhexyl) thiophene -2- base) benzo [1,2-b:4,5-b'] Dithiophene [3,2-b] thiophene -2,6- diyl) two (front threes
Ji Xi) (90.5mg, 0.10mmol) and catalyst tetra-triphenylphosphine palladium (5.86mg, 0.005mmol) are added to 10mL microwave tube
In, anhydrous dimethyl benzene (2.5mL) dissolution, the sealing of silica gel lid is added.Microwave tube is placed in microwave reactor, set temperature journey
Sequence: 80 DEG C continue 2 minutes, and 120 DEG C continue 2 minutes, and 160 DEG C continue 2 minutes, and last 200 DEG C continue 45 minutes, are down to wait react
After room temperature by reaction solution precipitating in 200mL methanol, Soxhlet successively is carried out with methanol, acetone, n-hexane, methylene chloride and chloroform
Extracting, then into chloroform component be added sodium diethyldithiocarbamate trihydrate aqueous solution (225mg, 1mmol,
100mL water), it stirs 8 hours at 60 DEG C, except the palladium catalyst in dereaction, chloroform component is concentrated, it is heavy with methanol again
Analysis, obtains dark green solid PFPT-DTBDT (108mg, yield: 80.1%) after vacuum drying.1H NMR、13C NMR、18F NMR
Analysis is target product.Chemical equation is as follows:
Embodiment 5
The preparation of PFPT-DT
It is automatically controlled in glove box in water oxygen, by compound M1 (fluoro- 5, the 8- bis- of 1,3- bis- (2- ethylhexyl) -6,7- bis-
(5- bromothiophene -2- base) naphthols simultaneously [2,3-c] thiophene -4,9- diketone) (79.7mg, 0.10mmol), 5,5'-, bis- (trimethyl
Tin) -2,2'- Dithiophene M4 (49.1mg, 0.10mmol) and catalyst tetra-triphenylphosphine palladium (5.86mg, 0.005mmol) be added
Into 10mL microwave tube, anhydrous dimethyl benzene (2.5mL) dissolution, the sealing of silica gel lid is added.Microwave tube is placed in microwave reactor,
Set temperature program: 80 DEG C continue 2 minutes, and 120 DEG C continue 2 minutes, and 160 DEG C continue 2 minutes, and last 200 DEG C continue 45 minutes,
It is cooled to room temperature by reaction solution precipitating in 200mL methanol wait react, successively uses methanol, acetone, n-hexane, methylene chloride and chlorine
It is imitative to carry out soxhlet type, the aqueous solution of sodium diethyldithiocarbamate trihydrate is then added into chloroform component
(225mg, 1mmol, 100mL water) stirs 8 hours at 60 DEG C, except the palladium catalyst in dereaction, chloroform component is concentrated,
Methanol precipitating is used again, and black solid PFPT-DT (62mg, yield: 74.2%) are obtained after vacuum drying.1H NMR、13C NMR
、18F NMR analysis is target product.Chemical equation is as follows:
Embodiment 6
The preparation of PFPT-DFDT
It is automatically controlled in glove box in water oxygen, by compound M1 (fluoro- 5, the 8- bis- of 1,3- bis- (2- ethylhexyl) -6,7- bis-
(5- bromothiophene -2- base) naphthols simultaneously [2,3-c] thiophene -4,9- diketone) (79.7mg, 0.10mmol), compound M5 (3,3' bis-
Fluoro- [2,2'- Dithiophene] -5,5'- diyl)-two (tin trimethyl) (52.8mg, 0.10mmol) and catalyst tetra-triphenylphosphine palladium
(5.86mg, 0.005mmol) is added into 10mL microwave tube, and anhydrous dimethyl benzene (2.5mL) dissolution, the sealing of silica gel lid is added.It will
Microwave tube is placed in microwave reactor, set temperature program: 80 DEG C continue 2 minutes, and 120 DEG C continue 2 minutes, and 160 DEG C continue 2 points
Clock, last 200 DEG C continue 45 minutes, are cooled to room temperature by reaction solution precipitating in 200mL methanol wait react, successively with methanol,
Acetone, n-hexane, methylene chloride and chloroform carry out soxhlet type, and diethyl-dithio amino first is then added into chloroform component
The aqueous solution (225mg, 1mmol, 100mL water) of sour sodium trihydrate, is stirred 8 hours at 60 DEG C, except the palladium in dereaction is urged
Chloroform component is concentrated agent, again use methanol precipitating, obtained after vacuum drying black solid PFPT-DFDT (69mg, yield:
79.2%).1H NMR、13C NMR、18F NMR analysis is target product.Chemical equation is as follows:
Carry out thermogravimetric analysis to obtained polymer P FPT-BDT, thermogravimetric analysis (TGA) are Netzsch using instrument
TG 209, heating rate are 20 DEG C/min, and atmosphere is nitrogen, and the thermogravimetric curve for obtaining polymer P FPT-BDT is as shown in Fig. 1,
By attached drawing 1 it is found that decomposition temperature of the polymer P FPT-BDT when mass loss is 5% is 455 DEG C, it is steady to show good heat
It is qualitative.
Use ultraviolet-visible light (UV-vis) absorption spectrum for Shimadzu UV-3600UV-vis-NIR spectrometer, point
Not Ce Ding polymer P FPT-BDT chlorobenzene solution and the ultraviolet-visible light for being prepared into filminess absorption, obtain it is ultraviolet-
Visible absorption spectrum figure is as shown in Fig. 2, and as shown in Figure 2, the absorption spectrum of polymer P FPT-BDT is in three peak features, wherein
The corresponding absorption peak of short wavelength range (300 to 400nm) is local π-π * transition, and long wavelength range (500 to 700nm) is corresponding
Two absorption peaks be Intramolecular electron transfer effect caused by；Notice absorption spectrum of the absorption spectrum than solution of film
Red shift 10nm or so is wanted, this is because in the film caused by aggregation.
It is respectively reference electricity with saturated calomel electrode, platinum electrode and glass-carbon electrode using CHI630E electrochemical workstation
Pole, auxiliary electrode and working electrode, tetrabutyl ammonium hexafluorophosphate (Bu4NPF6) acetonitrile solvent (0.1mol L-1) it is working solution,
Sweep speed is set as 100mV s-1, Cyclic voltamogram of the measurement polymer P FPT-BDT in filminess.Cyclic voltammetry
(CV) test obtains polymer P FPT-BDT and the cyclic voltammetry curve of ferrocene is as shown in Fig. 3, by attached drawing 3 it is found that polymerization
The oxidizing potential and reduction potential of object PFPT-BDT is respectively 0.91eV and -1.27eV, and it is 0.38eV that ferrocene, which corresponds to current potential,
The molecular orbital energy level of polymer P FPT-BDT: the occupied molecular orbital energy level (E of highest is calculated by formulaHOMO)=- e (4.80-
0.38+0.91=-5.33 (electron-volt, eV)；Lowest unoccupied molecular orbital energy level (ELUMO)=- e (4.80-0.38-1.27)
=-3.15 (electron-volt, eV).
Embodiment 7
The preparation of the organic photovoltaic cell of conjugated polymer based on embodiment 3-6 preparation
Polymer solar photovoltaic cell part uses formal dress structure I TO/PEDOT:PSS/Activelayer/PFN-Br/
Ag.For ito glass substrate as hole-collecting electrode, ito glass successively uses acetone, detergent, deionized water and isopropanol ultrasound
Washing is then placed in the drying overnight of 70 DEG C of baking oven；By on the ito substrate after drying through plasma Surface Treatment with Plasma 4 minutes
Afterwards, spin coating PEDOT:PSS is then transferred to a thickness of annealing 20 minutes at 40 nanometers, 150 DEG C full of the glove box under nitrogen
In；The polymer and ITIC (structural formula is as follows) mixed dissolution (mass ratio of the polymer and ITIC in chlorobenzene (CB)
For 1:1, polymer concentration 12mg/mL, 6 hours are stirred at 70 DEG C to after being completely dissolved, is spun on conduct on PEDOT:PSS
Then photoactive layer makes annealing treatment active layer 10 minutes with a thickness of 100 nanometers at 100 DEG C；After having annealed, in activity
One layer 5 nanometers of spin coating of PFN-Br (structural formula is as follows) is used as cathode interface on layer.Finally, in vacuum evaporation storehouse (2.0 ×
10-6Mbar), the silver that a layer thickness is 100 nanometers is deposited on active layer by mask plate as cathode, the effective area of device
For 0.04cm2。
The performance of the solar cell device of conjugated polymer based on embodiment 3-6 preparation is as shown in table 1.
The performance of solar cell device of the table 1 based on the embodiment 3-6 conjugated polymer prepared
As shown in Table 1, the conjugated polymer that prepared by embodiment 3~6 all shows good device performance, polymer
The device of PFPT-BDT preparation shows higher open-circuit voltage (0.85V), short-circuit current density (13.98mA/cm2) and filling because
Sub (60.08%), energy conversion efficiency reaches 7.14%；The device of polymer P FPT-DTBDT preparation possesses and PFPT-BDT phase
Same open-circuit voltage, higher short-circuit current density (14.50mA/cm2) and fill factor (64.40%), energy conversion efficiency
There is maximum value 7.94%, this is because DTBDT unit ratio BDT unit possesses better flatness, better molecular stacks.It compares
Device is prepared into PFPT-DT, PFPT-DFDT and shows reduced open-circuit voltage, this is because fluorine atom reduces its HOMO
Energy level value.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention should all
For equivalent substitute mode, it is included within the scope of the present invention.
Claims (10)
1. one kind bis- R-6 containing 1,3-, the conjugated polymer of 7- difluoro naphtho- [2,3-c] thiophene -4,9- diketone electrophilic unit,
It is characterized in that, structural formula are as follows:
In formula, R is hydrogen atom or alkyl chain；Ar1, Ar2 are aromatic group；D is electron donor unit；The electron donor unit
The D and fluoro- 5,8-Ar1 of bis- R-6,7- of 1,3- bis-, Ar2 naphtho- [2,3-c] thiophene -4,9- diketone electrophilic unit is with conjugated manner phase
Even；The natural number that the n is 1~10000, n are the degree of polymerization of the conjugated polymer.
2. -4,9- diketone electrophilic the unit according to claim 1 containing 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene
Conjugated polymer, which is characterized in that the alkyl chain be carbon atom number be 1~24 straight chain, branch, cyclic alkyl chain, or
The straight chain, branch, in cyclic alkyl chain one or more carbon atoms by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, amino,
Carbonyl, carboxyl, ester group, cyano or nitro replace, and hydrogen atom is by halogen atom, oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, ammonia
Base, carbonyl, carboxyl, amino cation, ester group, cyano, nitro replace.
3. -4,9- diketone electrophilic the unit according to claim 1 containing 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene
Conjugated polymer, which is characterized in that the Ar1 or Ar2 comprises the following structure at least one of formula:
In formula, R1It is one or more carbon atoms in hydrogen atom or alkyl chain or the alkyl chain by oxygen atom, alkenyl, alkynes
Base, aryl, hydroxyl, amino, carbonyl, carboxyl, nitro, phenyl or one or more of thienyl substitution or the alkyl chain
Hydrogen atom is substituted with halogen atoms.
4. -4,9- diketone electrophilic the unit according to claim 1 containing 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene
Conjugated polymer, which is characterized in that the electron donor cells D comprises the following structure at least one of formula:
In formula, R2、R3For one or more carbon atoms in hydrogen atom or alkyl chain or alkyl chain by oxygen atom, halogen atom,
One or more in alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, nitro, phenyl or thienyl substitution or alkyl chain
A hydrogen atom is substituted with halogen atoms.
5. according to claim 3 or 4 contain 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene -4,9- diketone electrophilic
The conjugated polymer of unit, which is characterized in that R1、R2、R3Straight chain, branch or the cyclic alkyl for being 1~30 for carbon atom number
Chain.
6. a kind of such as bis- R-6,7- difluoro naphtho- [2,3-c] thiophene -4,9- according to any one of claims 1 to 5 containing 1,3-
The synthetic method of the conjugated polymer of diketone electrophilic unit, which comprises the steps of:
(1) the fluoro- 5,8-Ar of bis- R-6,7- of 1,3- bis- is synthesized1,Ar2Naphtho- [2,3-c] thiophene -4,9- diketone electrophilic unit.
(2) under the protection of inert gas, by electron donor cells D and 1,3-, bis- R-6, fluoro- 5,8-Ar1, the Ar2 naphtho- of 7- bis-
[2,3-c] thiophene -4,9- dione unit, catalyst tetra-triphenylphosphine palladium are dissolved in organic solvent, and heated sealed is cooled to room
By reaction solution precipitating in methyl alcohol after temperature, successively purified with methanol, acetone, n-hexane, methylene chloride and chloroform, removal is urged
Chloroform component is concentrated in agent, and precipitating, vacuum drying are obtained containing 1,3-, bis- R-6,7- difluoro naphtho- [2,3-c] thiophene in methyl alcohol again
The conjugated polymer of pheno -4,9- diketone.
7. -4,9- diketone electrophilic the unit according to claim 6 containing 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene
Conjugated polymer synthetic method, which is characterized in that the electron donor cells D, 1,3- bis- R-6,7- bis- fluoro- 5,8-Ar1,
Ar2 naphtho- [2,3-c] thiophene -4,9- dione unit, catalyst tetra-triphenylphosphine palladium molar ratio be 20:20:1.
8. -4,9- diketone electrophilic the unit according to claim 6 containing 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene
Conjugated polymer synthetic method, which is characterized in that the inert gas be nitrogen or argon gas；The actual conditions of the heating
Continue 2 minutes for 80 DEG C of microwave, 120 DEG C continue 2 minutes, and 160 DEG C continue 2 minutes, and last 200 DEG C continue 45 minutes.
9. -4,9- diketone electrophilic the unit according to claim 6 containing 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene
Conjugated polymer synthetic method, which is characterized in that the purification is is purified by soxhlet type method.
10. one kind -4,9- diketone electrophilic list containing 1,3- bis- R-6,7- difluoro naphtho- [2,3-c] thiophene described in claim 1
The conjugated polymer of member is in the luminescent layer for preparing polymer LED device, half in preparation polymer field effect transistor
Conductor active layer prepares application in the active layer of polymer solar photovoltaic cell.
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| CN102816298A (en) * | 2012-06-26 | 2012-12-12 | 中南大学 | Naphtha[2, 3-c]thiophene-4,9-diketone polymer and its application in solar cells |
| WO2013035710A1 (en) * | 2011-09-07 | 2013-03-14 | 住友化学株式会社 | Polymer compound and organic photoelectric conversion element |
| CN106832231A (en) * | 2017-02-22 | 2017-06-13 | 华南理工大学 | Containing 1,2,3 triazol iso-indoles 5,7（2H, 6H）The conjugated polymer and its preparation method of diketone and application |
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| CN102816298A (en) * | 2012-06-26 | 2012-12-12 | 中南大学 | Naphtha[2, 3-c]thiophene-4,9-diketone polymer and its application in solar cells |
| CN106832231A (en) * | 2017-02-22 | 2017-06-13 | 华南理工大学 | Containing 1,2,3 triazol iso-indoles 5,7（2H, 6H）The conjugated polymer and its preparation method of diketone and application |
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