CN103772659A - Copolymer containing cyclopentadiene bithiophene-benzo-bis (benzothiadiazole) and preparation method and application thereof - Google Patents

Copolymer containing cyclopentadiene bithiophene-benzo-bis (benzothiadiazole) and preparation method and application thereof Download PDF

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CN103772659A
CN103772659A CN201210417333.5A CN201210417333A CN103772659A CN 103772659 A CN103772659 A CN 103772659A CN 201210417333 A CN201210417333 A CN 201210417333A CN 103772659 A CN103772659 A CN 103772659A
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thiophene
alkyl
benzo
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structural formula
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周明杰
管榕
李满园
黄佳乐
黎乃元
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

A benzo-bithiophene copolymer containing a dicyanomethylene cyclopentadiene bithiophene unit has the following structural formula: P: (shown in the Specification), wherein the R1, R2 and R4 are H, alkyls from C1 to C6 or alkoxy groups from C1 to C16; the R3 is an alkyl from C1 to C16, an alkoxy group from C1 to C16 or thiophene (R is an alkyl from C1 to C16) having a structural formula shown in the Specification; the n is an integer from 1 to 60. The benzo-bithiophene copolymer containing the dicyanomethylene cyclopentadiene bithiophene unit has a relatively narrow energy gap. The invention further provides a preparation method of the benzo-bithiophene copolymer containing the dicyanomethylene cyclopentadiene bithiophene unit, as well as solar battery devices, organic electroluminescent devices and organic field effect transistors, which adopt the benzo-bithiophene copolymer containing a dicyanomethylene cyclopentadiene bithiophene unit.

Description

Containing cyclopentadienedithiderivatives-benzo two (diazosulfide) co-polymer and its preparation method and application
Technical field
The present invention relates to a kind of benzo two thiophene-based multipolymers, its preparation method containing methylene dicyanoethyl cyclopenta two thiophene units and use this to contain solar cell device and the organic electroluminescence device of the benzo two thiophene-based multipolymers of methylene dicyanoethyl cyclopenta two thiophene units.
Background technology
Energy problem is the significant problem that countries in the world are extremely paid close attention to.Sun power is the optimal substitute energys of the following mankind, and the solar cell that is electric energy by solar energy converting is also the focus of research.The conjugated polymer thin films solar cell of rising in recent years has that cost is low, lightweight, manufacture craft is simple, can be prepared into the outstanding advantages such as flexible device.In addition, organic materials is of a great variety, designability is strong, is hopeful the design by material and optimizes the performance that improves solar cell.
Benzo two thiophene derivants, two thiophene pass through phenyl ring condensed ring in a plane, have strengthened its planarity and rigid structure, have higher light, heat and environmental stability.The phenyl ring that is positioned at center has reduced the electron rich number of both sides thiphene ring, makes it have lower HOMO energy level.Due to the large π key of the conjugation system of its expansion, π-π between π key is stacking has higher carrier mobility, and therefore, it all shows wide application prospect in fields such as organic electronics.But the band gap (energy level difference between HOMO energy level and lumo energy) of existing benzo two thiophene derivants is wider.
Summary of the invention
Based on this, be necessary the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units that provide a kind of band gap narrower.
In addition, be also necessary to provide a kind of preparation method of the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units.
In addition, be also necessary to provide a kind of solar cell device, organic electroluminescence device and organic field effect tube that uses this to contain the benzo two thiophene-based multipolymers of methylene dicyanoethyl cyclopenta two thiophene units.
Containing benzo two thiophene-based multipolymers for methylene dicyanoethyl cyclopenta two thiophene units, there is following structural formula:
P:
Figure BDA00002316997600021
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600022
r ' is C 1~ C 16alkyl.
A preparation method who contains the benzo two thiophene-based multipolymers of methylene dicyanoethyl cyclopenta two thiophene units, is characterized in that, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is: b is:
Figure BDA00002316997600024
Wherein, R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600025
r ' is C 1~ C 16alkyl;
Under nitrogen protection; the compd A that is 1:1 ~ 1.5:1 by mol ratio and compd B carry out coupling reaction in the organic solvent that contains organic palladium catalyzer, obtain the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units that following structural formula represents after separating-purifying:
P:
Figure BDA00002316997600026
Wherein, the integer that n is 1 ~ 60.
Therein in an embodiment, described organic palladium catalyzer is selected from least one in the mixture of three (dibenzalacetone) two palladiums and tri-o-tolyl phosphine, two (triphenylphosphine) palladium chloride and tetrakis triphenylphosphine palladium, and the mol ratio of described organic palladium catalyzer and described compd B is 1:10000 ~ 1:20.
In an embodiment, described coupling reaction carries out under refluxing therein, and the time of described coupling reaction is 24 ~ 72 hours.
Therein in an embodiment, described separating-purifying is as follows containing the step of the benzo two thiophene-based copolymer ps of methylene dicyanoethyl cyclopenta two thiophene units: the reaction solution carrying out after coupling reaction to described compd A and compd B adds methyl alcohol carry out precipitating and filter, by chromatographic separation after dry the solids obtaining after filtering, again obtain the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units of purifying with methyl alcohol precipitating filtration.
In an embodiment, the preparation process of described compd A comprises the steps: therein
Under nitrogen protection; the dichloromethane solution of the Compound C that following structural formula is represented drops to and contains 1; in the methylene dichloride of 3-dicyclohexylcarbodiimide and DMAP, under normal temperature, react 12 hours ~ 15 hours; wherein said Compound C, 1; the mol ratio of 3-dicyclohexylcarbodiimide and DMAP is 3:3:1 ~ 4:3.5:1; after being purified, reaction solution obtains the Compound D that following structural formula represents
C is:
Figure BDA00002316997600031
d is:
Figure BDA00002316997600032
wherein, R 1, R 2for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group;
The compd E that the Compound D that is 1:1 ~ 1.5:1 by mol ratio and following structural formula represent adds in solvent and is heated to backflow formation mixed solution at 78-100 ℃, described solvent is selected from least one in ethanol and propyl alcohol, to the alcohol saturated solution that drips potassium hydroxide or sodium hydroxide in described mixed solution, when described mixed solution become blackish green after continuation reaction 10 ~ 15 minutes, after purification, obtain the compound F 17-hydroxy-corticosterone that following structural formula represents
E is:
Figure BDA00002316997600033
f is: wherein, R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600035
r ' is C 1~ C 16alkyl, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group;
Under nitrogen protection; to the hexane solution that adds n-Butyl Lithium in the tetrahydrofuran solution of the compound F 17-hydroxy-corticosterones of-78 ℃; the mol ratio of described compound F 17-hydroxy-corticosterone and described n-Butyl Lithium is 1:2 ~ 1:2.5; at-78 ℃, stirring reaction adds trimethyltin chloride reaction to be warming up to room temperature after 0.5 ~ 1 hour after 2 ~ 2.5 hours; the mol ratio of described compound F 17-hydroxy-corticosterone and described trimethyltin chloride is 1:2 ~ 1:2.5, continues after reaction is purified for 20 ~ 24 hours to obtain described compd A.
In an embodiment, the preparation process of described compd E comprises the steps: therein
Oxalyl chloride point was added in 3～5 days to 1 of compound G that following structural formula represents for three times; in 2-dichloroethane solution; the mol ratio of described oxalyl chloride and described compound G is 1:1.5 ~ 1:1.8; under argon shield, back flow reaction obtains reaction mixture for 10～15 days; to after reaction mixture freeze overnight, filter and obtain described compd E
G is:
Figure BDA00002316997600041
wherein, R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600042
r ' is C 1~ C 16alkyl, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group;
A kind of solar cell device, comprises active coating, and the material of described active coating comprises the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units with following structural formula:
P:
Figure BDA00002316997600043
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600044
r ' is C 1~ C 16alkyl.
A kind of organic electroluminescence device, comprises luminescent layer, and the material of described luminescent layer is the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units with following structural formula:
P:
Figure BDA00002316997600051
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600052
r ' is C 1~ C 16alkyl.
A kind of organic field effect tube, comprises organic semiconductor layer, it is characterized in that, the material of described organic semiconductor layer is the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units with following structural formula:
P:
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600054
r ' is C 1~ C 16alkyl.
The above-mentioned benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units, owing to having introduced ketone structure in the ring of cyclopentadiene in structure, strengthen planeness and the conjugation degree of condensed ring system, thereby can improve the carrier mobility of the benzo two thiophene-based multipolymers of methylene dicyanoethyl cyclopenta two thiophene units; Introduce thiphene ring by the both sides at cyclopentadienone, and on thiophene 3,4 solvabilities of introducing the modifications such as alkyl and improve the benzo two thiophene-based multipolymers of methylene dicyanoethyl cyclopenta two thiophene units; Strong be subject to body unit (methylene dicyanoethyl cyclopentenes 1,4-Dithiapentalene) copolymerization by benzo two thiophene-based monomers and other, form the copolymer molecule of a kind of " weak to body-strong acceptor ", by giving the interaction of this " push away-La electronics " in acceptor, be conducive to fall low molecular band gap, its absorption band moves to infrared and near infrared low energy wave band, expand the light abstraction width of material, improve the utilization ratio of material to sunlight; The above-mentioned benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units are applied to solar cell and can increase substantially effciency of energy transfer; The above-mentioned benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units are applied to organic electroluminescence device and can increase substantially luminous efficiency; The above-mentioned benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units are applied to organic effect transistor and can increase substantially mobility.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units of an embodiment;
Fig. 2 is the structural representation of the solar cell device of an embodiment;
Fig. 3 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 4 is the structural representation of the organic field effect tube device of an embodiment.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is further illustrated.
The benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units of one embodiment, have following structural formula:
P:
Figure BDA00002316997600061
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600062
r ' is C 1~ C 16alkyl.
The above-mentioned benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units, owing to having introduced ketone structure in the ring of cyclopentadiene in structure, strengthen planeness and the conjugation degree of condensed ring system, thereby can improve the carrier mobility of the benzo two thiophene-based multipolymers of methylene dicyanoethyl cyclopenta two thiophene units; Introduce thiphene ring by the both sides at cyclopentadienone, and on thiophene 3,4 solvabilities of introducing the modifications such as alkyl and improve the benzo two thiophene-based multipolymers of methylene dicyanoethyl cyclopenta two thiophene units; Strong be subject to body unit (methylene dicyanoethyl cyclopentenes 1,4-Dithiapentalene) copolymerization by benzo two thiophene-based monomers and other, form the copolymer molecule of a kind of " weak to body-strong acceptor ", by giving the interaction of this " push away-La electronics " in acceptor, be conducive to fall low molecular band gap.
The preparation method of the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units of one embodiment, as shown in Figure 1, comprises the following steps:
Step S100, provide compd A and compd B.
A is:
Figure BDA00002316997600071
b is:
Figure BDA00002316997600072
Wherein, R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600073
r ' is C 1~ C 16alkyl
Wherein the preparation of compd A comprises the following steps:
Step S111, under nitrogen protection; the dichloromethane solution of the Compound C that following structural formula is represented drops to and contains 1; in the methylene dichloride of 3-dicyclohexylcarbodiimide (DDC) and DMAP (DMAP), under normal temperature, react 12 hours ~ 15 hours; wherein Compound C, 1; the mol ratio of 3-dicyclohexylcarbodiimide and DMAP is 3:3:1 ~ 4:3.5:1; the Compound D that following structural formula represents will be obtained after reaction solution separating-purifying
C is:
Figure BDA00002316997600074
d is:
Figure BDA00002316997600075
wherein, R 1, R 2for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group.
The reaction formula of this step is:
Figure BDA00002316997600076
Preferably, the step of separating-purifying is, will be with normal hexane recrystallization twice after reacting liquid filtering, and through column chromatographic isolation and purification.
Step S112, the Compound D that is 1:1 ~ 1.5:1 by mol ratio and the compd E that structural formula represents as follows add in solvent and are heated to backflow formation mixed solution at 78-100 ℃, solvent is selected from least one in ethanol and propyl alcohol, to the alcohol saturated solution that drips potassium hydroxide or sodium hydroxide in mixed solution, when mixed solution become blackish green after continuation reaction 10 ~ 15 minutes, after separating-purifying, obtain the compound F 17-hydroxy-corticosterone that following structural formula represents
E is:
Figure BDA00002316997600081
f is:
Figure BDA00002316997600082
wherein, R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600083
r ' is C 1~ C 16alkyl, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group;
The reaction formula of this step is:
Figure BDA00002316997600084
Preferably, the step of separating-purifying is: mixed solution is poured in ice-water bath, and the rear normal hexane by ethanol, heat of filtration obtains compound F 17-hydroxy-corticosterone after repeatedly washing the solids obtaining being dried.
Preferably, compd E is prepared by following steps:
By oxalyl chloride, (structural formula is ) in 3 ~ 5 days, point add 1 of compound G that following structural formula represents for three times; in 2-dichloroethane solution; the mol ratio of described oxalyl chloride and described compound G is 1:1.5 ~ 1.8; under argon shield, back flow reaction obtains reaction mixture for 10～15 days; to after reaction mixture freeze overnight, filter and obtain described compd E
G is:
Figure BDA00002316997600086
wherein, R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
r ' is C 1~ C 16alkyl, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group.
The reaction formula of this step is:
Figure BDA00002316997600092
In present embodiment, purify by normal hexane and washing with alcohol successively filtering the solid obtaining after reaction mixture freeze overnight.
Step S113, under nitrogen protection; to the hexane solution that adds n-Butyl Lithium in the tetrahydrofuran solution of the compound F 17-hydroxy-corticosterones of-78 ℃; the mol ratio of described compound F 17-hydroxy-corticosterone and n-Butyl Lithium (n-BuLi) is 1:2 ~ 1:2.5, and at-78 ℃, stirring reaction adds trimethyltin chloride (Me after 2 ~ 2.5 hours 3snCl) reaction was warming up to room temperature after 0.5 ~ 1 hour, and the mol ratio of compound F 17-hydroxy-corticosterone and trimethyltin chloride is 1:2 ~ 1:2.5, continued after reaction is purified for 20 ~ 24 hours to obtain compd A.
The reaction formula of this step is:
Figure BDA00002316997600093
Preferably, when separating-purifying compd A, the mixture that reaction is obtained is slowly poured in frozen water, and the organic phase that extraction obtains is used respectively 5% NaHCO 3solution, the washing of saturated NaCl solution, dry rear filtration, removes excessive trimethyltin chloride by filtrate distillation.
Preferably, in the hexane solution of n-Butyl Lithium, the volumetric molar concentration of n-Butyl Lithium is 2.5mol/L.
The synthesized reference document of compd B: Macromolecules2008,41,6664-6671.
Step S200, preparation contain the benzo two thiophene-based copolymer ps of methylene dicyanoethyl cyclopenta two thiophene units.
Under nitrogen protection; the compd A that is 1:1 ~ 1.5:1 by mol ratio and compd B carry out coupling reaction in the organic solvent that contains organic palladium catalyzer, obtain the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units that following structural formula represents after separating-purifying:
P:
Figure BDA00002316997600101
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkyl; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600102
r ' is C 1~ C 16alkyl.
The reaction formula of this step is:
In present embodiment, organic palladium catalyzer is selected from three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture, two (triphenylphosphine) palladium chloride (Pd (pph 3) 2cl 2) and tetrakis triphenylphosphine palladium (Pd (pph 3) 4) at least one.Be appreciated that organic palladium catalyzer is not limited to cited kind, as long as energy catalytic cpd A and compd B carry out Stille coupling reaction.
In present embodiment, organic solvent is selected from least one in toluene, tetrahydrofuran (THF) and DMF.Be appreciated that organic solution also can be used other solvents, as long as can make compd A and compd B react, and enough.
In present embodiment, the mol ratio of organic palladium catalyzer and compd B is 1:10000 ~ 1:20.The mol ratio that is appreciated that organic palladium catalyzer and compd B is not limited to 1: 10000 ~ 1:20, to adding the catalyzer that adds catalytic amount in the organic solvent of compd A and compd B.
In present embodiment, coupling reaction carries out under refluxing, and the time of coupling reaction is 24 ~ 72 hours.The temperature of reaction that is appreciated that coupling reaction is not limited to reflux temperature, as long as can make compd A and compd B react; Reaction times is also not limited to 24 ~ 72 hours, as long as can make compd A and compd B react completely as far as possible.
In present embodiment, separating-purifying is as follows containing the step of the benzo two thiophene-based copolymer ps of methylene dicyanoethyl cyclopenta two thiophene units: carry out reaction solution after coupling reaction to compd A and compd B and add and in methyl alcohol, carry out precipitating and filter, by chromatographic separation after dry the solids obtaining after filtering, again obtain the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units of purifying with methyl alcohol precipitating filtration.
Benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units prepared by the preparation method of the above-mentioned benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units have lower band gap.
Be specific embodiment below.
Embodiment 1
The present embodiment discloses the benzo two thiophene-based multipolymers that a kind of structure is following:
Figure BDA00002316997600111
n=60；
The preparation process of above-mentioned benzo two thiophene-based multipolymers is as follows:
One, 1, the preparation of 3-bis-(2-thiophene) acetone:
Figure BDA00002316997600112
First; the methylene dichloride of processing with 70mL is by 7.6g (36.8mmol) DCC; 1.23g (10mmol) DMAP dissolves; under nitrogen protection; the 70mL dichloromethane solution that is dissolved with 5g (35.2mmol) 2-thiophene acetic acid is dropwise added in above-mentioned reaction solution, and reaction is spent the night.After reaction finishes, by reacting liquid filtering, and with normal hexane recrystallization twice, then obtain product through column chromatographic isolation and purification.
MALDI-TOF-MS(m/z):222.3(M +).
Two, 2,7-bis-octyloxy benzos [1,2-b:4,3-b '] two thiophene-4, the preparation of 5-diketone:
Figure BDA00002316997600121
Get 25.4g (60mmol) 4; 4 '-bis-(2-octyloxy) thiophene be added to 400mL dry 1; in 2-ethylene dichloride, then by 3mL(34.5mmol) oxalyl chloride point was added in reaction flask for three times in 5 days, and under argon shield back flow reaction 15day.After reaction finishes, reaction solution is cooled to room temperature, freeze overnight in refrigerator, filters to obtain red solid, obtains product successively by normal hexane and washing with alcohol.
MALDI-TOF-MS(m/z):477.0(M +).
Three, 2,5-bis-octyloxy-7, the preparation of 9-bis-(2-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
In the single port bottle of 250mL, add successively 1.2g (5.4mmol) 1,3-bis-(2-thiophene) acetone, 2.7g (5.4mmol) 2,7-bis-octyloxy-4,5-diketone, 40mL ethanol, is heated to reflux.Again by a small amount of potassium hydroxide 2mL dissolve with ethanol, and be dropwise added in reaction flask with syringe.React again 10min stopped reaction when reaction solution becomes after blackish green, and reaction solution is poured in ice-water bath.Filter, repeatedly wash with the normal hexane of ethanol, heat, be dried and obtain solid product.
MALDI-TOF-MS(m/z):663.0(M +).
Four, 2,5-bis-octyloxy-7, the preparation of 9-bis-(2-tin trimethyl-5-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Figure BDA00002316997600123
Under nitrogen protection, by 6.79g (10mmol) be cooled to-78 ℃ with the anhydrous THF of 120mL, slowly add the hexane solution (2.5M) of 5mL (12mmol) n-Butyl Lithium.Finish, at-78 ℃, after insulation reaction 2h, add the trimethyltin chloride of 4.5mL (15mmol), after insulation reaction 0.5h, naturally return to room temperature, stopped reaction after continuation reaction 24h.Add the dilution of 50mL normal hexane, reaction solution is slowly poured in frozen water, and the organic phase that extraction obtains is used respectively 5% NaHCO 3, saturated NaCl solution washing, anhydrous magnesium sulfate drying, filters, and revolves steaming, then carries out underpressure distillation, steams excessive trimethyltin chloride, obtains product.
MALDI-TOF-MS(m/z):988.6(M +).
Five, the preparation of benzo two thiophene-based multipolymers:
Figure BDA00002316997600131
Under nitrogen protection; by 0.5g (0.5mmol) 2; 5-bis-octyloxy-7,9-bis-(2-tin trimethyl-5-thiophene)-8H-cyclopentadiene benzo [1,2-b:4; 3-b '] two thiophene-8-ketone and 0.20g (0.5mmol) 2; the bromo-4-methylene dicyanoethyl-4H-of 6-bis-cyclopenta [2,1-b:3,4-b '] two thiophene are added in the reaction flask that fills 50mL dry toluene; after the logical nitrogen gas stirring 15min of reaction mixture, add rapidly catalyst P d 2(dba) 3(14mg, 3%) and P (o-Tol) 3(28mg) to reaction flask.After logical nitrogen stirring at room temperature 15min, be heated to reflux, stirring reaction 48h.After reaction stops, question response liquid is cooled to room temperature, is poured into and in methyl alcohol, has precipitation generate, and filters, and after vacuum-drying, dissolves and after column chromatographic isolation and purification, obtains target product with methyl alcohol sedimentation.
GPC:Mn＝53940，PDI＝1.9。
Embodiment 2
The present embodiment discloses the benzo two thiophene-based multipolymers that a kind of structure is following:
Figure BDA00002316997600132
n=30；
The preparation process of above-mentioned benzo two thiophene-based multipolymers is as follows:
One, 1, the preparation of 3-bis-(4-hexyl-2-thiophene) acetone:
First; the methylene dichloride of processing with 70mL is by 8.26g (40mmol) DCC; 1.23g (10mmol) DMAP dissolves; under nitrogen protection; the 70mL dichloromethane solution that is dissolved with 6.78g (30mmol) 4-hexyl-2-thiophene acetic acid is dropwise added in above-mentioned reaction solution, and reaction is spent the night.After reaction finishes, by reacting liquid filtering, and with normal hexane recrystallization twice, then obtain product through column chromatographic isolation and purification.
MALDI-TOF-MS(m/z):391(M +).
Two, 2,7-bis-(n-Hexadecane oxygen base) benzo [1,2-b:4,3-b '] two thiophene-4, the preparation of 5-diketone:
Figure BDA00002316997600142
Get 40.2g (62.1mmol) 4; 4 '-bis-(2-n-Hexadecane oxygen base) thiophene be added to 400mL dry 1; in 2-ethylene dichloride, then by 3mL(34.5mmol) oxalyl chloride point was added in reaction flask for three times in 3 days, and under argon shield back flow reaction 12day.After reaction finishes, reaction solution is cooled to room temperature, freeze overnight in refrigerator, filters to obtain red solid, obtains product successively by normal hexane and washing with alcohol.
MALDI-TOF-MS(m/z):701.0(M +).
Three, 2,5-bis-(n-Hexadecane oxygen base)-7, the preparation of 9-bis-(4-hexyl-2-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
In the single port bottle of 150mL, add successively 1.8g (4.5mmol) 1,3-bis-(4-hexyl-2-thiophene) acetone, 2.1g (3.0mmol) 2,7-bis-(n-Hexadecane oxygen base)-4,5-diketone, 40mL ethanol, is heated to reflux.Again by a small amount of potassium hydroxide 2mL dissolve with ethanol, and be dropwise added in reaction flask with syringe.React again 15min stopped reaction when reaction solution becomes after blackish green, and reaction solution is poured in ice-water bath.Filter, repeatedly wash with the normal hexane of ethanol, heat, be dried and obtain solid product.
MALDI-TOF-MS(m/z):1056.0(M +).
Four, 2,5-bis-(n-Hexadecane oxygen base)-7, the preparation of 9-bis-(3-hexyl-2-tin trimethyl-5-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Figure BDA00002316997600151
Under nitrogen protection; by 2 of 5.3g (5mmol); 5-bis-(n-Hexadecane oxygen base)-7; 9-bis-(4-hexyl-2-thiophene)-8H-cyclopentadiene benzo [1; 2-b:4; 3-b '] two thiophene-8-ketone and the anhydrous THF of 120mL be cooled to-78 ℃, slowly adds the hexane solution (2.5M) of 5mL (12mmol) n-Butyl Lithium.Finish, at-78 ℃, after insulation reaction 2h, add the trimethyltin chloride of 4.5mL (15mmol), after insulation reaction 0.5h, naturally return to room temperature, stopped reaction after continuation reaction 24h.Add the dilution of 50mL normal hexane, reaction solution is slowly poured in frozen water, and the organic phase that extraction obtains is used respectively 5% NaHCO3, saturated NaCl solution washing, anhydrous magnesium sulfate drying, filters, and revolves steaming, carry out again underpressure distillation, steam excessive trimethyltin chloride, obtain product.
MALDI-TOF-MS(m/z):1381(M +).
Five, the preparation of benzo two thiophene-based multipolymers:
Under nitrogen protection; by 0.83g (0.6mmol) 2; 5-bis-(n-Hexadecane oxygen base)-7,9-bis-(3-hexyl-2-tin trimethyl-5-thiophene)-8H-cyclopentadiene benzo [1,2-b:4; 3-b '] two thiophene-8-ketone and 0.20g (0.5mmol) 2; the bromo-4-methylene dicyanoethyl-4H-of 6-bis-cyclopenta [2,1-b:3,4-b '] two thiophene are added in the reaction flask that fills 60mL dry toluene; after the logical nitrogen gas stirring 15min of reaction mixture, add rapidly catalyst P d 2(dba) 3(27mg, 0.03mmol) and P (o-Tol) 3(18mg, 0.06mmol) is to reaction flask.After logical nitrogen stirring at room temperature 15min, be heated to reflux, stirring reaction 24h.After reaction stops, question response liquid is cooled to room temperature, is poured into and in methyl alcohol, has precipitation generate, and filters, and after vacuum-drying, dissolves and after column chromatographic isolation and purification, obtains target product with methyl alcohol sedimentation.
GPC:Mn＝38760，PDI＝21。
Embodiment 3
The present embodiment discloses the benzo two thiophene-based multipolymers that a kind of structure is following:
Figure BDA00002316997600161
n=20；
The preparation process of above-mentioned benzo two thiophene-based multipolymers is as follows:
One, 1, the preparation of 3-bis-(4-hexadecyl-2-thiophene) acetone:
Figure BDA00002316997600162
First; the methylene dichloride of processing with 70mL is by 6.2g (30mmol) DCC; 1.23g (10mmol) DMAP dissolves; under nitrogen protection; the 70mL dichloromethane solution that is dissolved with 5g (30mmol) 4-hexadecyl-2-thiophene acetic acid is dropwise added in above-mentioned reaction solution, reacts 15 hours.After reaction finishes, by reacting liquid filtering, and with normal hexane recrystallization twice, then obtain product through column chromatographic isolation and purification.
MALDI-TOF-MS(m/z):671(M +).
Two, 1,2,6,7-tetramethoxy benzo [1,2-b:4,3-b '] two thiophene-4, the preparation of 5-diketone:
Figure BDA00002316997600163
Get 14.9g (52mmol) 4; 4 '-bis-(2,3-dimethoxy) thiophene be added to 400mL dry 1, in 2-ethylene dichloride; again by 3mL(34.5mmol) oxalyl chloride point was added in reaction flask for three times in 3 days, and under argon shield back flow reaction 12day.After reaction finishes, reaction solution is cooled to room temperature, freeze overnight in refrigerator, filters to obtain red solid, obtains product successively by normal hexane and washing with alcohol.
MALDI-TOF-MS(m/z):340.0(M +).
Three, 2,3,4,5-tetramethoxy-7, the preparation of 9-bis-(4-hexadecyl-2-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Figure BDA00002316997600164
In the single port bottle of 150mL, add successively 3.2g (4.8mmol) 1,3-bis-(4-hexadecyl-2-thiophene) acetone, 2.7g (3.0mmol) 1,2,6,7-tetramethoxy-4,5-diketone, 40mL propyl alcohol, is heated to reflux.Again a small amount of potassium hydroxide is dissolved with 2mL propyl alcohol, and be dropwise added in reaction flask with syringe.React again 13min stopped reaction when reaction solution becomes after blackish green, and reaction solution is poured in ice-water bath.Filter, repeatedly wash with the normal hexane of propyl alcohol, heat, be dried and obtain solid product.
MALDI-TOF-MS(m/z):976.0(M +).
Four, 2,3,4,5-tetramethoxy-7, the preparation of 9-bis-(2-tin trimethyl-3-hexadecyl-5-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Under nitrogen protection; by 2 of 2.9g (3mmol); 3; 4; 5-tetramethoxy-7,9-bis-(4-hexadecyl-2-thiophene)-8H-cyclopentadiene benzo [1,2-b:4; 3-b '] two thiophene-8-ketone and the anhydrous THF of 80mL be cooled to-78 ℃, slowly adds the hexane solution (2.5M) of 2.7mL (6.6mmol) n-Butyl Lithium.Finish, at-78 ℃, after insulation reaction 2.5h, add the trimethyltin chloride of 2mL (6.6mmol), after insulation reaction 1h, naturally return to room temperature, stopped reaction after continuation reaction 20h.Add the dilution of 50mL normal hexane, reaction solution is slowly poured in frozen water, and the organic phase that extraction obtains is used respectively 5% NaHCO3, saturated NaCl solution washing, anhydrous magnesium sulfate drying, filters, and revolves steaming, carry out again underpressure distillation, steam excessive trimethyltin chloride, obtain product.
MALDI-TOF-MS(m/z):1301(M +).
Five, the preparation of benzo two thiophene-based multipolymers:
Figure BDA00002316997600172
Under nitrogen protection, by 0.98g (0.75mmol) 2, 3, 4, 5-tetramethoxy-7, 9-bis-(2-tin trimethyl-3-hexadecyl-5-thiophene)-8H-cyclopentadiene benzo [1, 2-b:4, 3-b '] two thiophene-8-ketone and 0.20g (0.5mmol) 2, the bromo-4-methylene dicyanoethyl-4H-of 6-bis-cyclopenta [2, 1-b:3, 4-b '] two thiophene are added in the reaction flask that fills 60mL dry tetrahydrofuran, after the logical nitrogen gas stirring 15min of reaction mixture, add rapidly catalyst P d2 (dba) 3(9mg, 0.01mmol) and P (o-Tol) 3(60mg, 0.2mmol) to reaction flask.After logical nitrogen stirring at room temperature 15min, be heated to reflux, stirring reaction 48h.After reaction stops, question response liquid is cooled to room temperature, is poured into and in methyl alcohol, has precipitation generate, and filters, and after vacuum-drying, dissolves and after column chromatographic isolation and purification, obtains target product with methyl alcohol sedimentation.
GPC:Mn＝24240，PDI＝1.7。
Embodiment 4
The present embodiment discloses the benzo two thiophene-based multipolymers that a kind of structure is following:
Figure BDA00002316997600181
n=15；
The preparation process of above-mentioned benzo two thiophene-based multipolymers is as follows:
One, 1, the preparation of 3-bis-(3-hexyloxy-2-thiophene) acetone:
Figure BDA00002316997600182
First; the methylene dichloride of processing with 70mL is by 7.6g (36.8mmol) DCC; 1.23g (10mmol) DMAP dissolves; under nitrogen protection; the 80mL dichloromethane solution that is dissolved with 8.5g (35.0mmol) 3-hexyloxy-2-thiophene acetic acid is dropwise added in above-mentioned reaction solution, reacts 14 hours.After reaction finishes, by reacting liquid filtering, and with normal hexane recrystallization twice, then obtain product through column chromatographic isolation and purification.
MALDI-TOF-MS(m/z):423(M +).
Two, 2,7-bis-octyloxy benzos [1,2-b:4,3-b '] two thiophene-4, the preparation of 5-diketone:
Figure BDA00002316997600191
Get 25.4g (60mmol) 4; 4 '-bis-(2-octyloxy) thiophene be added to 400mL dry 1; in 2-ethylene dichloride, then by 3mL(34.5mmol) oxalyl chloride point was added in reaction flask for three times in 5 days, and under argon shield back flow reaction 15day.After reaction finishes, reaction solution is cooled to room temperature, freeze overnight in refrigerator, filters to obtain red solid, obtains product successively by normal hexane and washing with alcohol.
MALDI-TOF-MS(m/z):477.0(M +).
Three, 2,3,4,5-tetra-octyl group-7, the preparation of 9-bis-(3-hexyloxy-2-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Figure BDA00002316997600192
In the single port bottle of 150mL, add successively 1.7g (4mmol) 1,3-bis-(3-hexyloxy-2-thiophene) acetone, 1.4g (3mmol) 1,2,6,7-tetra-octyl group-4,5-diketone, 40mL ethanol, is heated to reflux.Again by a small amount of potassium hydroxide 2mL dissolve with ethanol, and be dropwise added in reaction flask with syringe.React again 15min stopped reaction when reaction solution becomes after blackish green, and reaction solution is poured in ice-water bath.Filter, repeatedly wash with the normal hexane of ethanol, heat, be dried and obtain solid product.
MALDI-TOF-MS(m/z):1056.0(M +).
Four, 2,3,4,5-tetra-octyl group-7, the preparation of 9-bis-(3-hexyloxy-5-tin trimethyl-2-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Figure BDA00002316997600193
Under nitrogen protection; by 2 of 4.2g (4mmol); 3; 4; 5-tetra-octyl group-7,9-bis-(3-hexyloxy-2-thiophene)-8H-cyclopentadiene benzo [1,2-b:4; 3-b '] two thiophene-8-ketone and the anhydrous THF of 70mL be cooled to-78 ℃, slowly adds the hexane solution (2.5M) of 4mL (10mmol) n-Butyl Lithium.Finish, at-78 ℃, after insulation reaction 2.5h, add the trimethyltin chloride of 3mL (10mmol), after insulation reaction 0.5h, naturally return to room temperature, stopped reaction after continuation reaction 24h.Add the dilution of 50mL normal hexane, reaction solution is slowly poured in frozen water, and the organic phase that extraction obtains is used respectively 5% NaHCO3, saturated NaCl solution washing, anhydrous magnesium sulfate drying, filters, and revolves steaming, carry out again underpressure distillation, steam excessive trimethyltin chloride, obtain product.
MALDI-TOF-MS(m/z):1381(M +).
Five, the preparation of benzo two thiophene-based multipolymers:
Under nitrogen protection; by 0.83g (0.6mmol) 2; 3; 4; 5-tetra-octyl group-7; 9-bis-(3-hexyloxy-5-tin trimethyl-2-thiophene)-8H-cyclopentadiene benzo [1; 2-b:4; 3-b '] two thiophene-8-ketone and 0.20g (0.5mmol) 2; the bromo-4-methylene dicyanoethyl-4H-of 6-bis-cyclopenta [2,1-b:3,4-b '] two thiophene are added in the reaction flask that fills 10mL dry toluene; after the logical nitrogen gas stirring 15min of reaction mixture, add rapidly catalyzer 0.06mg (0.00005mmol) Pd (PPh 3) 4to reaction flask.After logical nitrogen stirring at room temperature 15min, be heated to reflux, stirring reaction 60h.After reaction stops, question response liquid is cooled to room temperature, is poured into and in methyl alcohol, has precipitation generate, and filters, and after vacuum-drying, dissolves and after column chromatographic isolation and purification, obtains target product with methyl alcohol sedimentation.
GPC:Mn＝19380，PDI＝1.8。
Embodiment 5.
The present embodiment discloses the benzo two thiophene-based multipolymers that a kind of structure is following:
n=14；
The preparation process of above-mentioned benzo two thiophene-based multipolymers is as follows:
One, 1, the preparation of 3-bis-(3-methoxyl group-2-thiophene) acetone:
First; the methylene dichloride of processing with 70mL is by 7.6g (36.8mmol) DCC; 1.23g (10mmol) DMAP dissolves; under nitrogen protection; the 65mL dichloromethane solution that is dissolved with 6.05g (35.2mmol) 3-methoxyl group-2-thiophene acetic acid is dropwise added in above-mentioned reaction solution, and reaction is spent the night.After reaction finishes, by reacting liquid filtering, and with normal hexane recrystallization twice, then obtain product through column chromatographic isolation and purification.
MALDI-TOF-MS(m/z):282(M +).
Two, 2,7-bis-(hexadecyl) benzo [1,2-b:4,3-b '] two thiophene-4, the preparation of 5-diketone:
Figure BDA00002316997600212
Get 33.8g (55mmol) 4; 4 '-bis-(2-hexadecyl) thiophene be added to 400mL dry 1; in 2-ethylene dichloride, then by 3mL(34.5mmol) oxalyl chloride point was added in reaction flask for three times in 5 days, and under argon shield back flow reaction 15day.After reaction finishes, reaction solution is cooled to room temperature, freeze overnight in refrigerator, filters to obtain red solid, obtains product successively by normal hexane and washing with alcohol.
MALDI-TOF-MS(m/z):669.0(M +).
Three, 2,5-bis-(hexadecyl)-7, the preparation of 9-bis-(3-methoxyl group-2-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
In the single port bottle of 150mL, add successively 1.5g (5.4mmol) 1,3-bis-(3-methoxyl group-2-thiophene) acetone, 3.6g (5.4mmol) 2,7-bis-(hexadecyl) benzo [1,2-b:4,3-b '] two thiophene-4,5-diketone, 40mL ethanol, is heated to reflux.Again by a small amount of potassium hydroxide 2mL dissolve with ethanol, and be dropwise added in reaction flask with syringe.React again 10min stopped reaction when reaction solution becomes after blackish green, and reaction solution is poured in ice-water bath.Filter, repeatedly wash with the normal hexane of ethanol, heat, be dried and obtain solid product.
MALDI-TOF-MS(m/z):915.0(M +).
Four, 2,5-bis-octyloxy-7, the preparation of 9-bis-(2-tin trimethyl-5-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Figure BDA00002316997600221
Under nitrogen protection; by 2 of 4.6g (5mmol); 5-bis-(hexadecyl)-7; 9-bis-(3-methoxyl group-2-thiophene)-8H-cyclopentadiene benzo [1; 2-b:4; 3-b '] two thiophene-8-ketone and the anhydrous THF of 80mL be cooled to-78 ℃, slowly adds the hexane solution (2.5M) of 5mL (12mmol) n-Butyl Lithium.Finish, at-78 ℃, after insulation reaction 2h, add the trimethyltin chloride of 3.6mL (12mmol), after insulation reaction 0.5h, naturally return to room temperature, stopped reaction after continuation reaction 24h.Add the dilution of 50mL normal hexane, reaction solution is slowly poured in frozen water, and the organic phase that extraction obtains is used respectively 5% NaHCO3, saturated NaCl solution washing, anhydrous magnesium sulfate drying, filters, and revolves steaming, carry out again underpressure distillation, steam excessive trimethyltin chloride, obtain product.
MALDI-TOF-MS(m/z):1241(M +).
Five, the preparation of benzo two thiophene-based multipolymers:
Figure BDA00002316997600222
Under nitrogen protection; by 0.6g (0.5mmol) 2; 5-bis-octyloxy-7; 9-bis-(2-tin trimethyl-5-thiophene)-8H-cyclopentadiene benzo [1; 2-b:4; 3-b '] two thiophene-8-ketone and 0.20g (0.5mmol) 2; the bromo-4-methylene dicyanoethyl-4H-of 6-bis-cyclopenta [2; 1-b:3; 4-b '] two thiophene are added in the reaction flask that fills the dry DMF of 40mL; after the logical nitrogen gas stirring 15min of reaction mixture, add rapidly catalyzer 17mg (0.025mmol) Pd (PPh3) 2Cl2 to reaction flask.After logical nitrogen stirring at room temperature 15min, be heated to reflux, stirring reaction 72h.After reaction stops, question response liquid is cooled to room temperature, is poured into and in methyl alcohol, has precipitation generate, and filters, and after vacuum-drying, dissolves and after column chromatographic isolation and purification, obtains target product with methyl alcohol sedimentation.
GPC:Mn＝16128，PDI＝1.7。
Embodiment 6
The present embodiment discloses the benzo two thiophene-based multipolymers that a kind of structure is following:
Figure BDA00002316997600231
n=10；
The preparation process of above-mentioned benzo two thiophene-based multipolymers is as follows:
One, 1, the preparation of 3-bis-(4-hexyl-2-thiophene) acetone:
Figure BDA00002316997600232
First, the methylene dichloride of processing with 70mL is by 7.6g (36.8mmol) DCC, 1.23g (10mmol) DMAP dissolves, under condition of nitrogen gas, the 60mL dichloromethane solution that is dissolved with 8.0g (35.2mmol) 3-hexyl-5-thiophene acetic acid is dropwise added in above-mentioned reaction solution, and reaction is spent the night.After reaction finishes, by reacting liquid filtering, and with normal hexane recrystallization twice, then obtain product through column chromatographic isolation and purification.
MALDI-TOF-MS(m/z):391(M +).
Two, 2,7-bis-(2-methyl-5-thiophene) benzo [1,2-b:4,3-b '] two thiophene-4, the preparation of 5-diketone:
Figure BDA00002316997600233
Get 21.5g (60mmol) 4; 4 '-bis-[2-(2-methyl-5-thiophene)] thiophene be added to 350mL dry 1; in 2-ethylene dichloride, then by 3mL(34.5mmol) oxalyl chloride point was added in reaction flask for three times in 5 days, and under argon shield back flow reaction 15day.After reaction finishes, reaction solution is cooled to room temperature, freeze overnight in refrigerator, filters to obtain red solid, obtains product successively by normal hexane and washing with alcohol.
MALDI-TOF-MS(m/z):413.0(M +).
Three, 2,5-bis-(2-methyl-5-thiophene)-7, the preparation of 9-bis-(3-hexyl-5-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Figure BDA00002316997600241
In the single port bottle of 250mL, add successively 2.1g (5.4mmol) 1,3-bis-(3-hexyl-5-thiophene) acetone, 2.2g (5.4mmol) 2,7-bis-(2-methyl-5-thiophene) benzo [1,2-b:4,3-b '] two thiophene-4,5-diketone, 60mL ethanol, is heated to reflux.Again by a small amount of potassium hydroxide 2mL dissolve with ethanol, and be dropwise added in reaction flask with syringe.React again 10min stopped reaction when reaction solution becomes after blackish green, and reaction solution is poured in ice-water bath.Filter, repeatedly wash with the normal hexane of ethanol, heat, be dried and obtain solid product.
MALDI-TOF-MS(m/z):767.0(M +).
Four, 2,5-bis-(2-methyl-5-thiophene)-7, the preparation of 9-bis-(3-hexyl-2-tin trimethyl-5-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Figure BDA00002316997600242
Under nitrogen protection; by 2 of 7.7g (10mmol); 5-bis-(2-methyl-5-thiophene)-7; 9-bis-(3-hexyl-5-thiophene)-8H-cyclopentadiene benzo [1; 2-b:4; 3-b '] two thiophene-8-ketone and the anhydrous THF of 150mL be cooled to-78 ℃, slowly adds the hexane solution (2.5M) of 5mL (12mmol) n-Butyl Lithium.Finish, at-78 ℃, after insulation reaction 2h, add the trimethyltin chloride of 4.5mL (15mmol), after insulation reaction 0.5h, naturally return to room temperature, stopped reaction after continuation reaction 24h.Add the dilution of 50mL normal hexane, reaction solution is slowly poured in frozen water, and the organic phase that extraction obtains is used respectively 5% NaHCO 3, saturated NaCl solution washing, anhydrous magnesium sulfate drying, filters, and revolves steaming, then carries out underpressure distillation, steams excessive trimethyltin chloride, obtains product.
MALDI-TOF-MS(m/z):1093(M +).
Five, the preparation of benzo two thiophene-based multipolymers:
Figure BDA00002316997600251
Under nitrogen protection; by 0.63g (0.5mmol) 2; 5-bis-(2-methyl-5-thiophene)-7; 9-bis-(3-hexyl-2-tin trimethyl-5-thiophene)-8H-cyclopentadiene benzo [1; 2-b:4; 3-b '] two thiophene-8-ketone and 0.20g (0.5mmol) 2; the bromo-4-methylene dicyanoethyl-4H-of 6-bis-cyclopenta [2; 1-b:3; 4-b '] two thiophene are added in the reaction flask that fills 50mL dry toluene; after the logical nitrogen gas stirring 15min of reaction mixture, add rapidly catalyst P d 2(dba) 3(14mg, 3%) and P (o-Tol) 3(28mg) to reaction flask.After logical nitrogen stirring at room temperature 15min, be heated to reflux, stirring reaction 48h.After reaction stops, question response liquid is cooled to room temperature, is poured into and in methyl alcohol, has precipitation generate, and filters, and after vacuum-drying, dissolves and after column chromatographic isolation and purification, obtains target product with methyl alcohol sedimentation.
GPC:Mn＝10030，PDI＝2.1.
Embodiment 7
The present embodiment discloses the benzo two thiophene-based multipolymers that a kind of structure is following:
Figure BDA00002316997600252
n=1；
The preparation process of above-mentioned benzo two thiophene-based multipolymers is as follows:
One, 1, the preparation of 3-bis-(4-methyl-2-thiophene) acetone:
Figure BDA00002316997600253
First; the methylene dichloride of processing with 70mL is by 7.6g (36.8mmol) DCC; 1.23g (10mmol) DMAP dissolves; under nitrogen protection; the 70mL dichloromethane solution that is dissolved with 5.5g (35.2mmol) 4-methyl-2-thiophene acetic acid is dropwise added in above-mentioned reaction solution, and reaction is spent the night.After reaction finishes, by reacting liquid filtering, and with normal hexane recrystallization twice, then obtain product through column chromatographic isolation and purification.
MALDI-TOF-MS(m/z):250(M +).
Two, 2,7-bis-(5-n-Hexadecane oxygen base-2-thiophene) benzo [1,2-b:4,3-b '] two thiophene-4, the preparation of 5-diketone:
Figure BDA00002316997600261
Get 46.7g (60mmol) 4; 4 '-bis-(2-(5-n-Hexadecane oxygen base-2-thiophene)) thiophene be added to 400mL dry 1; in 2-ethylene dichloride; again by 3mL(34.5mmol) oxalyl chloride point was added in reaction flask for three times in 4 days, and under argon shield back flow reaction 13day.After reaction finishes, reaction solution is cooled to room temperature, freeze overnight in refrigerator, filters to obtain red solid, obtains product successively by normal hexane and washing with alcohol.
MALDI-TOF-MS(m/z):833.0(M +).
Three, 2,5-bis-(5-hexadecyl-2-thiophene)-7, the preparation of 9-bis-(4-methyl-2-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Figure BDA00002316997600262
In the single port bottle of 150mL, add successively 1.4g (5.4mmol) 1,3-bis-(4-methyl-2-thiophene) acetone, 4.2g (5.0mmol) 2,7-bis-(5-hexadecyl-2-thiophene) benzo [1,2-b:4,3-b '] two thiophene-4,5-diketone, 40mL ethanol, is heated to reflux.Again by a small amount of potassium hydroxide 2mL dissolve with ethanol, and be dropwise added in reaction flask with syringe.React again 10min stopped reaction when reaction solution becomes after blackish green, and reaction solution is poured in ice-water bath.Filter, repeatedly wash with the normal hexane of ethanol, heat, be dried and obtain solid product.
MALDI-TOF-MS(m/z):1048.0(M +).
Four, 2,5-bis-octyloxy-7, the preparation of 9-bis-(2-tin trimethyl-5-thiophene)-8H-cyclopentadiene benzo [1,2-b:4,3-b '] two thiophene-8-ketone:
Under nitrogen protection; by 2 of 5.2g (5mmol); 5-bis-(5-hexadecyl-2-thiophene)-7; 9-bis-(4-methyl-2-thiophene)-8H-cyclopentadiene benzo [1; 2-b:4; 3-b '] two thiophene-8-ketone and the anhydrous THF of 80mL be cooled to-78 ℃, slowly adds the hexane solution (2.5M) of 5mL (12mmol) n-Butyl Lithium.Finish, at-78 ℃, after insulation reaction 2.2h, add the trimethyltin chloride of 3.6mL (12mmol), after insulation reaction 0.6h, naturally return to room temperature, stopped reaction after continuation reaction 22h.Add the dilution of 50mL normal hexane, reaction solution is slowly poured in frozen water, and the organic phase that extraction obtains is used respectively 5% NaHCO3, saturated NaCl solution washing, anhydrous magnesium sulfate drying, filters, and revolves steaming, carry out again underpressure distillation, steam excessive trimethyltin chloride, obtain product.
MALDI-TOF-MS(m/z):1373(M +).
Five, the preparation of benzo two thiophene-based multipolymers:
Figure BDA00002316997600272
Under nitrogen protection; by 0.7g (0.5mmol) 2; 5-bis-octyloxy-7; 9-bis-(2-tin trimethyl-5-thiophene)-8H-cyclopentadiene benzo [1; 2-b:4; 3-b '] two thiophene-8-ketone and 0.20g (0.5mmol) 2; the bromo-4-methylene dicyanoethyl-4H-of 6-bis-cyclopenta [2; 1-b:3; 4-b '] two thiophene are added in the reaction flask that fills 50mL dry toluene; after the logical nitrogen gas stirring 15min of reaction mixture, add rapidly catalyzer 17mg (0.025mmol) Pd (PPh 3) 2cl 2to reaction flask.After logical nitrogen stirring at room temperature 15min, be heated to reflux, stirring reaction 30h.After reaction stops, question response liquid is cooled to room temperature, is poured into and in methyl alcohol, has precipitation generate, and filters, and after vacuum-drying, dissolves and after column chromatographic isolation and purification, obtains target product with methyl alcohol sedimentation.
GPC:Mn＝1284，PDI＝19。
Embodiment 8
Refer to Fig. 2, the solar cell device 40 of an embodiment comprises the substrate 41, anode 42, buffer layer 43, active coating 44 and the negative electrode 45 that stack gradually.
In the present embodiment, substrate 41 is glass.
Anode 42 is formed at a side surface of substrate 41.In the present embodiment, anode 42 is ITO(tin indium oxide), preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth.In present embodiment, the thickness of lining anode 42 is 120nm.Preferably, substrate 41, before forming anode 42, first cleans, with oxygen-Plasma processing.
Buffer layer 43 is formed at the surface of anode 42.The material of buffer layer 43 comprises poly-3,4-Ethylenedioxy Thiophene and polystyrolsulfon acid (PEDOT:PSS, ": " represents the two mixing).The thickness of buffer layer 43 is 40nm.Buffer layer 43 is prepared by spin coating.
Active coating 44 is formed at the surface of buffer layer 43.The material of active coating 44 comprises the methyl-butyrate derivative (PCBM) of soccerballene and has the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units of following structural formula:
P:
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
r ' is C 1~ C 16alkyl.
Specifically in the present embodiment, the material of active coating 44 comprises the methyl-butyrate derivative (PCBM) of soccerballene and the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units prepared by embodiment 5.
Be wherein 1:1 containing the benzo two thiophene-based copolymer ps 1 of methylene dicyanoethyl cyclopenta two thiophene units with the mass ratio of PCBM.The thickness of active coating 44 is 120nm.Active coating 44 is prepared by spin coating.
Negative electrode 45 is formed at the surface of active coating 44.The material of negative electrode 45 is aluminium (Al).The thickness of negative electrode 45 is 80nm.Negative electrode 45 is prepared by vacuum evaporation.
It should be noted that, substrate 41, anode 42, buffer layer 43 and negative electrode 45 material used are not limited to above cited material, also can be conventional in the industry other materials, also can more need to arrange other functional layers.
Solar cell device 40 is carried out to open circuit voltage, packing factor, current density and energy conversion efficiency test, the results are shown in following table.
Figure BDA00002316997600291
As can be seen from the above table, the energy conversion efficiency of solar cell device 40 is higher.
Active layer material adopts the similar of the current density of solar cell device of the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units of other embodiment and the solar cell device of the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units of open circuit voltage, packing factor, current density and energy conversion efficiency and active layer material employing embodiment 5, repeats no more below.
Embodiment 9
Refer to Fig. 3, a kind of organic electroluminescence device 70 comprises the substrate 71, anode 72, luminescent layer 73, buffer layer 74 and the negative electrode 75 that stack gradually.
In the present embodiment, substrate 71 is glass.
Anode 72 is formed at a side surface of substrate 71.In the present embodiment, anode 72 is for being ITO(tin indium oxide), preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth.The thickness of anode 72 is 120nm.
The material of luminescent layer 73 is the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units with following structural formula:
P:
Figure BDA00002316997600292
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600293
r ' is C 1~ C 16alkyl.
Specifically in the present embodiment, the material of luminescent layer 73 is the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units prepared by embodiment 3.
The thickness of luminescent layer 73 is 80nm.In present embodiment, luminescent layer 73 is prepared by spin coating.
Buffer layer 74 is formed at the surface of luminescent layer 73.The material of buffer layer 74 is lithium fluoride (LiF).The thickness of buffer layer 74 is 1nm.Buffer layer 74 is formed by evaporation.
Negative electrode 75 is formed at the surface of buffer layer 74.The material of negative electrode is aluminium (Al).The thickness of negative electrode 75 is 120nm.
It should be noted that, substrate 71, anode 72, buffer layer 74 and negative electrode 75 material used are not limited to above cited material, also can be conventional in the industry other materials, also can more need to arrange other functional layers.
Embodiment 10
Refer to Fig. 4, a kind of organic field effect tube 80 comprises substrate 81, insulation layer 82, decorative layer 83, organic semiconductor layer 84, source electrode 85 and drain electrode 86.Wherein substrate 81, insulation layer 82, decorative layer 83, organic semiconductor layer 84 stack gradually.Source electrode 85 and drain electrode 86 are formed at organic semiconductor layer 84 surfaces.
The material of substrate 81 is highly doped silicon chip.The thickness of substrate 81 is 2mm.
Insulation layer 82 is formed at the surface of substrate 81.The material of insulation layer 82 is silicon-dioxide (SiO 2).The thickness of insulation layer 82 is 450nm.
Decorative layer 83 is formed at the surface of insulation layer 82.The material of decorative layer 83 is octadecyl trichlorosilane alkane (OTS).The thickness of decorative layer 83 is 2nm.
Organic semiconductor layer 84 is formed at the surface of decorative layer 83.The material of organic semiconductor layer 84 is the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units with following structural formula:
P:
Figure BDA00002316997600301
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure BDA00002316997600302
r ' is C 1~ C 16alkyl.Organic semiconductor layer 84 is prepared by spin coating.
Specifically in the present embodiment, the material of organic semiconductor layer 84 is the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units prepared by embodiment 1.
The thickness of organic semiconductor layer 84 is 50nm.In the surperficial spin coating of decorative layer 83,10mg is dissolved in to dry formation after the solution that the dimethylbenzene of 0.4ml forms containing the polymer P 1 of benzo two (diazosulfide) unit.
The material of source electrode 85 and drain electrode 86 is aluminium.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. containing benzo two thiophene-based multipolymers for methylene dicyanoethyl cyclopenta two thiophene units, it is characterized in that thering is following structural formula:
P:
Figure FDA00002316997500011
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure FDA00002316997500012
r ' is C 1~ C 16alkyl.
2. a preparation method who contains the benzo two thiophene-based multipolymers of methylene dicyanoethyl cyclopenta two thiophene units, is characterized in that, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
Figure FDA00002316997500013
b is:
Figure FDA00002316997500014
wherein, R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure FDA00002316997500015
r ' is C 1~ C 16alkyl;
Under nitrogen protection; the compd A that is 1:1 ~ 1.5:1 by mol ratio and compd B carry out coupling reaction in the organic solvent that contains organic palladium catalyzer, obtain the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units that following structural formula represents after separating-purifying:
P:
Figure FDA00002316997500021
Wherein, the integer that n is 1 ~ 60.
3. the preparation method of the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units according to claim 2, it is characterized in that, described organic palladium catalyzer is selected from least one in the mixture of three (dibenzalacetone) two palladiums and tri-o-tolyl phosphine, two (triphenylphosphine) palladium chloride and tetrakis triphenylphosphine palladium, and the mol ratio of described organic palladium catalyzer and described compd B is 1: 10000 ~ 1:20.
4. the preparation method of the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units according to claim 2, is characterized in that, described coupling reaction carries out under refluxing, and the time of described coupling reaction is 24 ~ 72 hours.
5. the preparation method of the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units according to claim 2, it is characterized in that, described separating-purifying is as follows containing the step of the benzo two thiophene-based copolymer ps of methylene dicyanoethyl cyclopenta two thiophene units: the reaction solution carrying out after coupling reaction to described compd A and compd B adds methyl alcohol carry out precipitating and filter, by chromatographic separation after dry the solids obtaining after filtering, again obtain the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units of purifying with methyl alcohol precipitating filtration.
6. the preparation method of the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units according to claim 2, is characterized in that, the preparation process of described compd A comprises the steps:
Under nitrogen protection; the dichloromethane solution of the Compound C that following structural formula is represented drops to and contains 1; in the methylene dichloride of 3-dicyclohexylcarbodiimide and DMAP, under normal temperature, react 12 hours ~ 15 hours; wherein said Compound C, 1; the mol ratio of 3-dicyclohexylcarbodiimide and DMAP is 3:3:1 ~ 4:3.5:1; after being purified, reaction solution obtains the Compound D that following structural formula represents
C is:
Figure FDA00002316997500031
d is:
Figure FDA00002316997500032
wherein, R 1, R 2for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; ;
The Compound D that by mol ratio is 1: 1 ~ 1.5:1 adds in solvent and is heated to backflow formation mixed solution at 78-100 ℃ with the compd E that following structural formula represents, described solvent is selected from least one in ethanol and propyl alcohol, to the alcohol saturated solution that drips potassium hydroxide or sodium hydroxide in described mixed solution, when described mixed solution become blackish green after continuation reaction 10 ~ 15 minutes, after purification, obtain the compound F 17-hydroxy-corticosterone that following structural formula represents
E is:
Figure FDA00002316997500033
f is: wherein, R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or or the alkylthrophene that represents of following structural formula:
Figure FDA00002316997500035
r ' is C 1~ C 16alkyl, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group;
Under nitrogen protection; to the hexane solution that adds n-Butyl Lithium in the tetrahydrofuran solution of the compound F 17-hydroxy-corticosterones of-78 ℃; the mol ratio of described compound F 17-hydroxy-corticosterone and described n-Butyl Lithium is 1:2.0 ~ 1:2.5; at-78 ℃, stirring reaction adds trimethyltin chloride reaction to be warming up to room temperature after 0.5 ~ 1 hour after 2 ~ 2.5 hours; the mol ratio of described compound F 17-hydroxy-corticosterone and described trimethyltin chloride is 1:2 ~ 1:2.5, continues after reaction is purified for 20 ~ 24 hours to obtain described compd A.
7. the preparation method of the benzo two thiophene-based multipolymers containing methylene dicyanoethyl cyclopenta two thiophene units according to claim 6, is characterized in that, the preparation process of described compd E comprises the steps:
Oxalyl chloride point was added in 3～5 days to 1 of compound G that following structural formula represents for three times; in 2-dichloroethane solution; the mol ratio of described oxalyl chloride and described compound G is 1:1.5 ~ 1:1.8; under argon shield, back flow reaction obtains reaction mixture for 10～15 days; to after reaction mixture freeze overnight, filter and obtain described compd E
G is:
Figure FDA00002316997500041
wherein, R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure FDA00002316997500042
r ' is C 1~ C 16alkyl, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group.
8. a solar cell device, comprises active coating, it is characterized in that, the material of described active coating comprises the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units with following structural formula:
P:
Figure FDA00002316997500043
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure FDA00002316997500044
r ' is C 1~ C 16alkyl.
9. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, the material of described luminescent layer is the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units with following structural formula:
P:
Figure FDA00002316997500051
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
r ' is C 1~ C 16alkyl.
10. an organic field effect tube, comprises organic semiconductor layer, it is characterized in that, the material of described organic semiconductor layer is the benzo two thiophene-based copolymer ps containing methylene dicyanoethyl cyclopenta two thiophene units with following structural formula:
P:
Figure FDA00002316997500053
Wherein, the integer that n is 1 ~ 60; R 1, R 2, R 4for H, C 1~ C 16alkyl or C 1~ C 16alkoxyl group; R 3for C 1~ C 16alkyl, C 1~ C 16alkoxyl group or the alkylthrophene that represents of following structural formula:
Figure FDA00002316997500054
r ' is C 1~ C 16alkyl.
CN201210417333.5A 2012-10-26 2012-10-26 Copolymer containing cyclopentadiene bithiophene-benzo-bis (benzothiadiazole) and preparation method and application thereof Pending CN103772659A (en)

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Publication number Priority date Publication date Assignee Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116157406A (en) * 2020-07-30 2023-05-23 保土谷化学工业株式会社 Compound, hole-transporting material for photoelectric conversion element, hole-transporting layer, photoelectric conversion element using same, and solar cell

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