CN103848968B - A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer and preparation and application thereof - Google Patents

A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer and preparation and application thereof Download PDF

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CN103848968B
CN103848968B CN201210495110.0A CN201210495110A CN103848968B CN 103848968 B CN103848968 B CN 103848968B CN 201210495110 A CN201210495110 A CN 201210495110A CN 103848968 B CN103848968 B CN 103848968B
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reaction
thiophene
compound
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CN103848968A (en
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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 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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention provides one containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer and preparation and application thereof, described polymkeric substance is the polymer P with following general formula, in formula, and R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is: r ' is C 6~ C 10alkyl, n is the natural number between 1 ~ 80.Polymkeric substance of the present invention contains new dibenzothiophene benzene 1,4-Dithiapentalene and Thienopyrroles-4,6-dione unit, there is new conjugate planes structure, excellent sunlight matching and carrier mobility performance, preparation method is simply controlled, has good application prospect in the field of photovoltaic materials such as polymer solar battery, organic electroluminescence device.P:

Description

A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer and preparation and application thereof
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophene-based conjugated polymers and preparation method thereof and application.
Background technology
Organic solar batteries is owing to having some incomparable advantages of inorganic solar cell, as with low cost, manufacture craft is simple, and product weight is light, the advantage such as can to prepare and get more and more people's extensive concerning as the potential renewable energy source of one by large area flexible.In the past ten years, the performance of organic solar batteries is steadily improved, and effciency of energy transfer is close to 10%.But up to the present, the photoelectric transformation efficiency of organic solar batteries is than inorganic solar cell or much lower.
The effciency of energy transfer of current organic polymer solar cell is still low than silicon solar cell, one of reason is the carrier mobility of polymkeric substance several orders of magnitude lower than the mobility of inorganic monocrystalline material, and the absorption spectrum of polymer photo-voltaic cell material can not mate well with solar spectrum, it is another major reason causing energy transfer efficiency low.For improving the performance of polymer solar battery further, the pole narrow band gap polymkeric substance had compared with wide absorption spectrum can be adopted to do to body and acceptor, improve the absorption and use efficiency to sunlight.
Improving one of method of the effciency of energy transfer of polymer solar battery is synthesizing new P-type conjugated polymers, and novel P-type conjugated polymers needs to possess following characteristics: (a) good solubility, is beneficial to solvent processing, realizes suitability for industrialized production; B () has wide and strong absorption to whole solar spectrum; C () carrier mobility is high, be beneficial to carrier transport.Wherein, the emphasis that the light abstraction width how widening polymkeric substance will be research, by selecting suitable structural unit composition semi-conducting polymer, being beneficial to and the light abstraction width of polymkeric substance is widened infrared, near-infrared region.For realizing the commercialization of organic solar batteries, developing new polymer materials, improving the great significance of effciency of energy transfer for organic solar batteries of photoelectric material.
Summary of the invention
For solving the problem, the present invention aims to provide a kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer.
The present invention also aims to provide the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer and application.
First aspect, the invention provides a kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, for having the polymer P of following general formula:
P:
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is: r ' is C 6~ C 10alkyl, n is the natural number between 1 ~ 80.
Of the present invention containing in the structure of Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer contains dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene units, this unit is derived by the benzene 1,4-Dithiapentalene with plane rigid structure to obtain, benzo two thiophene unit has higher carrier mobility speed and thermostability, is used widely in field of photovoltaic materials.And dibenzothiophene benzene 1,4-Dithiapentalene expands conjugated backbone on the conjugated structure basis of original benzene 1,4-Dithiapentalene, there is unique keystone ring heptacene rigid planar structure, effectively can reduce the bandwidth of polymkeric substance, the transfer of current carrier in molecular skeleton is become be more prone to, improve carrier mobility speed, make polymkeric substance have good thermostability and environmental stability simultaneously.In addition, by introducing the heteroatoms such as nitrogen, sulphur in the trapezoidal conjugated structure unit of this heptacene, the band gap of adjustable polymkeric substance and photo absorption performance, make the polymkeric substance containing dibenzothiophene benzo two thiophene unit have good application prospect in organic photoelectrical material field.
Meanwhile, thieno-[3,4-c] pyrroles-4 is contained of the present invention containing in Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer structure, 6-dione unit, this unit be excellent property by body unit, first, the two dimensional structure that it has, is beneficial to electronics along polymer backbone delocalization; Secondly, the strong sucting electronic effect that thieno-[3,4-c] pyrroles-4,6-dione unit has can regulate HOMO and the lumo energy of subject polymer effectively, and meanwhile, atom N is introduced alkyl can improve its solvability effectively.Therefore, the application of this structural unit in the photoelectric materials such as Organic Light Emitting Diode, organic solar batteries, field-effect transistor widely.
Of the present inventionly contain above two kinds of unit containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, there is new conjugate planes structure, and the sunlight matching of excellence and carrier mobility performance, effciency of energy transfer is high, has a extensive future.
Second aspect, the invention provides a kind of preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, comprises following operation steps:
There is provided compd A and compd B, the structural formula of compd A and B is respectively:
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is: r ' is C 6~ C 10alkyl;
Under protection of inert gas; compd A and compd B add in organic solvent by 1:1 ~ 1:1.5 in molar ratio; add catalyzer; Stille coupling reaction is carried out 24 ~ 72 hours at 60 ~ 120 DEG C; obtain containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer after separation and purification, described is the polymer P with following general formula containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer:
P:
In formula, n is the natural number between 1 ~ 80.
Preferably, described catalyzer is two (triphenylphosphine) palladium chloride (Pd (PPh 3) 2cl 2), tetrakis triphenylphosphine palladium (Pd (PPh 3) 4) and three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in one.
Preferably, the mole dosage of described catalyzer is 0.01% ~ 5% of compd A mole dosage, for three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture, described three (dibenzalacetone) two palladium (Pd 2(dba) 3) mole dosage be 0.01% ~ 5% of compd A mole dosage.Preferably, described three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in, three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mol ratio be 1:2 ~ 1:20.
Preferably, described rare gas element is nitrogen.
Preferably, described organic solvent is the one in toluene, tetrahydrofuran (THF) (THF) and DMF (DMF), and solvent is enough.Solvent for use carries out drying before use, and reaction is carried out under water-less environment.
Preferably, the operation of described separation and purification is specially: remove reaction solution under reduced pressure organic solvent, is added drop-wise to by surplus materials in methyl alcohol and carries out sedimentation, suction filtration, with dry after methanol wash, is then that elutriant alumina chromatographic column carries out separating-purifying with chloroform, steam again except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction three days, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, and obtains containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer.
The reaction formula of described Stille coupling reaction is:
Preferably; the operating process of described Stille coupling reaction is: under protection of inert gas; compd A is added in organic solvent with compd B and mixes; logical bubbling inert gas 0.5h removes residual oxygen; add catalyzer rapidly; after logical bubbling inert gas 1h removes residual oxygen again, be warming up to 60 ~ 120 DEG C of stirring and refluxing reaction 24 ~ 72h, obtain after separation and purification containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer.
The preparation method of described compd A comprises following operation steps:
(1) under protection of inert gas; compound a is added in tetrahydrofuran (THF) (THF); be cooled to-78 DEG C; slowly add n-Butyl Lithium (n-BuLi); compound a: the mol ratio of n-Butyl Lithium (n-BuLi) is 1:2.2 ~ 1:2.5; then stirring reaction 2h at-78 DEG C, then add trimethyltin chloride (Me 3snCl), compound a: trimethyltin chloride (Me 3snCl) mol ratio is 1:2 ~ 1:2.5, returns to room temperature after insulation reaction 0.5h, and continue reaction 24h, obtain compound b, reaction formula is:
Preferably, described n-Butyl Lithium (n-BuLi) is 2.5:1 with the mol ratio of compound a, trimethyltin chloride (Me 3snCl) be 2.5:1 with the mol ratio of compound a.
(2) under rare gas element and oxygen free condition, be that compound b and the compound c2-brooethyl thionyl benzene of 1:2 ~ 1:2.5 adds in solvent, add catalyzer by mol ratio, at 80 DEG C, Stille coupling reaction 48h occurs, obtain compound d, reaction formula is:
Preferably, described solvent is DMF (DMF), toluene or tetrahydrofuran (THF) (THF).
Preferably, described catalyzer is two (triphenylphosphine) palladium chloride (Pd (PPh 3) 2cl 2), tetrakis triphenylphosphine palladium (Pd (PPh 3) 4) and three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in one.
Preferably, the mole dosage of described catalyzer is 0.01% ~ 5% of compound b mole dosage, for three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture, three (dibenzalacetone) two palladium (Pd 2(dba) 3) mole dosage be 0.01% ~ 5% of compound b mole dosage.Preferably, described three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in, three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mol ratio be 1:2 ~ 1:20.
(3) in trifluoromethanesulfonic acid, after compound d and Vanadium Pentoxide in FLAKES react, reactant is poured into cancellation reaction in ice-water bath, be precipitated, gained precipitation added in pyridine and carry out back flow reaction, obtain Verbindung, reaction formula is:
Preferably, described reaction with Vanadium Pentoxide in FLAKES is at room temperature reaction 72h, and the mol ratio of described compound d and Vanadium Pentoxide in FLAKES is 1.5:1 ~ 2.0:1, and the temperature of described back flow reaction is 110 DEG C, and the reaction times is 12h.
(4), under lucifuge condition, there is bromination reaction with Verbindung in N-bromo-succinimide (NBS), obtain compd A, reaction formula is in dimethyl formamide (DMF):
Preferably, described N-bromo-succinimide (NBS): the mol ratio of Verbindung is 3:1, and described bromination reaction at room temperature reacts 15h.
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, the skeleton symbol of described alkylthrophene group is: r ' is C 6~ C 10alkyl.
In embodiment below, for convenience of statement, the compd A of different substituents uses A1 respectively, A2, A3, A4, A5, A6, A7 etc. represent, intermediate reaction thing and product also according to said method represent, the compound a a1 of such as different substituents, a2, a3 etc. represent, name and are as the criterion with the title in each embodiment.
The preparation method of described compd B comprises following operation steps:
I, there is condensation reaction in compound f thiophene-3,4-dioctyl phthalate in acetic anhydride, obtains the crude product of compound g, and react with thionyl chloride after described crude product and compound h react again, obtain compound i, reaction formula is:
Preferably, described setting-up point is 140 DEG C, and the time is 12h; The mol ratio of described compound f and compound h is 1:1.2 ~ 1:1.5; Described is 110 DEG C with compound h temperature of reaction, and the reaction times is 24h, and described temperature of reacting with thionyl chloride is 80 DEG C, and the time is 4h.
II, under lucifuge condition, in the mixed solution that sulfuric acid and trifluoroacetic acid are formed, compound i and N-bromo-succinimide (NBS) at room temperature react and spend the night, and obtain compound j, reaction formula is as follows:
Preferably, described sulfuric acid to be massfraction be 98% the vitriol oil, the mol ratio of described compound i:N-bromo-succinimide (NBS) is 1:3, and described N-bromo-succinimide (NBS) point adds for four times.
III, in anaerobic and atmosphere of inert gases, add in tetrahydrofuran (THF), add catalyzer by compound j and compound k with mol ratio 1:2, be heated to 60 DEG C and carry out Stille coupling reaction 24h, obtain compound n, reaction formula is:
Preferably, described rare gas element is the one in nitrogen and argon gas.
Preferably, described catalyzer is two (triphenylphosphine) palladium chloride (Pd (PPh 3) 2cl 2), tetrakis triphenylphosphine palladium (Pd (PPh 3) 4) and three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in one.
Preferably, the mole dosage of described catalyzer is 0.01% ~ 5% of compound j mole dosage, for three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture, three (dibenzalacetone) two palladium (Pd 2(dba) 3) mole dosage be 0.01% ~ 5% of compound j mole dosage.Preferably, described three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in, three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mol ratio be 1:2 ~ 1:20.
IV, in atmosphere of inert gases, compound n is added in anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution of n-Butyl Lithium (n-BuLi), n-Butyl Lithium (n-BuLi): the mol ratio of compound n is 2.2:1 ~ 2.5:1, finish, at-78 DEG C after stirring reaction 2h, add trimethyltin chloride (Me 3snCl), trimethyltin chloride (Me 3snCl): the mol ratio 2:1 ~ 2.5:1 of compound n, returns to room temperature after insulation reaction 0.5h, continue reaction 24h, obtain compd B, reaction formula is:
Preferably, described rare gas element is the one in nitrogen and argon gas.
Preferably, described n-Butyl Lithium (n-BuLi): the mol ratio of compound n is 2.5:1.Preferably, described trimethyltin chloride (Me 3snCl): the mol ratio 2.5:1 of compound n.
Wherein, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl.
In embodiment below, for convenience of statement, the compd B of different substituents uses B1 respectively, B2, B3, B4, B5 etc. represent, intermediate reaction thing and product also according to said method represent, the compound f f1 of such as different substituents, f2, f3 etc. represent, name and are as the criterion with the title in each embodiment.
The third aspect, the invention provides a kind of application containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, is described containing the Thienopyrroles diketone-application of dibenzothiophene benzo two thiophen polymer in polymer solar cell device, organic electroluminescence device and organic field effect tube.Described containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer as described in the first aspect of the invention.
One provided by the invention, containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer and preparation method thereof and application, has following beneficial effect:
Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer that contains of the present invention introduces Thienopyrroles diketone by body unit and dibenzothiophene benzene 1,4-Dithiapentalene donor monomer in polymer backbone, by giving " pushing away-La electronics " between acceptor effect, reduce the energy gap of polymkeric substance, the absorption band of polymkeric substance is moved to infrared and near infrared low energy wave band, widen the light abstraction width of polymkeric substance, make its absorption spectrum generation red shift, high with the matching degree of solar spectrum, carrier mobility speed improves, and effciency of energy transfer is also improved.
Bibliographical information and related application is not had at present openly containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, it is a kind of new photoelectric material, effciency of energy transfer is high, preparation method is simple, productive rate is high, mild condition, product is easy to control, and makes its having a extensive future in field of photovoltaic materials such as polymer solar batteries.
Accompanying drawing explanation
Fig. 1 is the structural representation of the polymer solar cell device of embodiment 9.
Fig. 2 is the structural representation of the organic electroluminescence device of embodiment 10.
Fig. 3 is the structural representation of the organic field effect tube of embodiment 11.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
What the present invention relates to contains Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, for having the polymer P of following general formula:
P:
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is: r ' is C 6~ C 10alkyl, n is the natural number between 1 ~ 80.
Alkyl in polymer architecture prepared by following examples, unless otherwise indicated, is the alkyl of linear chain structure, such as-C 10h 21for positive certain herbaceous plants with big flowers base, be called for short certain herbaceous plants with big flowers base.
Embodiment 1
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, be specially poly-{ 7,8-bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-octyl group-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 1, wherein, n=80:
P1：
Preparation method comprises the following steps:
One, the reaction scheme preparing 4,11-bis-bromo-7,8-bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A1) is as follows:
Concrete operations are as follows:
(1) 4,5-bis-certain herbaceous plants with big flowers base-2,7-tin trimethyl benzo [2,1-b:3,4-b '] two thiophene (b1) are prepared:
By 2.36g (5mmol) 4 in nitrogen atmosphere, 5-bis-certain herbaceous plants with big flowers base benzo [2, 1-b:3, 4-b '] two thiophene (a1) add in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, stirring reaction 2h at-78 DEG C, add the trimethyltin chloride (12.5mmol) of 3.7mL, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 4, 5-bis-certain herbaceous plants with big flowers base-2, 7-tin trimethyl benzo [2, 1-b:3, 4-b '] two thiophene (b1), mass spectrometric measurement data are MS (EI) m/z:796 (M+).
(2) 4,5-bis-certain herbaceous plants with big flowers base-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d1) are prepared:
By 0.74g (3.36mmol) 2-brooethyl thionyl benzene (c), 1.22g (1.53mmol) 4,5-bis-certain herbaceous plants with big flowers base-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b1) add in 30mL dry DMF, logical nitrogen bubble 30min, adds rapidly 0.087g (0.075mmol) Pd (PPh 3) 4, be heated to 80 DEG C of stirring reaction 24h, after stopped reaction, remove excessive DMF under reduced pressure, by ethyl acetate, residue is dissolved, and wash, through MgSO with Potassium monofluoride (KF) aqueous solution that massfraction is 10% 4after drying, filter, revolve steaming, the normal hexane/tetrahydrofuran (THF) mixed solvent taking volume ratio as 3:1, for elutriant is through silica gel column chromatography column separating purification, obtains 4,5-bis-certain herbaceous plants with big flowers base-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d1), productive rate is 82%, and mass spectrometric measurement data are MS (EI) m/z:747 (M+);
(3) 7,8-bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e1) are prepared:
By 0.22g (0.3mmol) 4; 5-bis-certain herbaceous plants with big flowers base-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d1) and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; then reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter; join in 30mL pyridine after vacuum-drying; be heated to 110 DEG C of back flow reaction 12h, reaction solution be cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4steaming is revolved after drying, take volume ratio as the methylene dichloride/normal hexane mixed solvent of 1:9 be elutriant, separation and purification is carried out to revolving the rear surplus materials of steaming with silica gel column chromatography, obtain 7,8-bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e1), productive rate 63%, mass spectrometric measurement data are MS (MALDI) m/z:683 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 2.94g (4.31mmol) 7, 8-bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e1) add in 60mLDMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, add anhydrous magnesium sulfate drying and revolve steaming after filtration, be the ethyl acetate/petroleum ether mixed solvent of 5:1 again with volume ratio be elutriant, separating-purifying is carried out with silica gel column chromatography, obtain 4, 11-bis-bromo-7, 8-bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A1), productive rate is 71%.
The mass spectrometric measurement result of compd A 1 is MS (MALDI) m/z:841 (M+);
The structural analysis data of compd A 1 are: 1hNMR (300MHz, CD 2cl 2): δ (ppm)=7.91 (s, 2H), 7.86 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 2.55 (t, J=7.13Hz, 4H), 1.62-1.29 (m, 32H), 0.93-0.84 (t, J=13.44Hz, 6H).
Two, compound B-11 is prepared, wherein-C 8h 17for n-octyl, reaction scheme is as follows:
Specifically comprise the following steps:
I, 5-thiotolene also [3, 4-c] pyrroles-4, the preparation method of 6-diketone (i1) comprises the following steps: by 0.86g (5mmol) thiophene-3, 4-dioctyl phthalate (f) adds in 25mL acetic anhydride, be heated to 140 DEG C, stirring reaction 12h, be cooled to room temperature, remove reaction solution, be precipitated, for the crude product of compound g, gained crude product 50mL toluene is dissolved, add 0.24g (7.5mmol) methylamine (h1), be heated to 110 DEG C of back flow reaction 24h, be cooled to room temperature, remove toluene under reduced pressure, with 50mL thionyl chloride, remaining solid thing in matrass is dissolved again, cool after being heated to 80 DEG C of stirring and refluxing 4h, remove thionyl chloride under reduced pressure, take volume ratio as the methylene dichloride/sherwood oil mixed solvent of 3:2 be elutriant, separating-purifying is carried out with silica gel column chromatography, 5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (i1), productive rate 56%.
II, the bromo-5-thiotolene of 1,3-bis-also [3,4-c] pyrroles-4,6-diketone (j1) is prepared:
By 1.67g (10mmol) 5-thiotolene also [3,4-c] pyrroles-4,6-diketone (i1) is dissolved in the 10mL vitriol oil, and (mass concentration is 98%, lower with) and 33mL trifluoroacetic acid mixed solution in, under lucifuge condition, 5.34g (30mmol) N-bromo-succinimide (NBS) point is joined in reaction flask four times, stirred at ambient temperature reaction is spent the night, reaction solution is poured in distilled water, with chloroform extraction, merge organic phase, use anhydrous MgSO 4dried overnight, revolves except chloroform, is that the methylene dichloride/sherwood oil mixed solvent of 1:1 is elutriant with volume ratio, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain the bromo-5-thiotolene of 1,3-bis-also [3,4-c] pyrroles-4,6-diketone (j1), productive rate 80%.
III, 1,3-bis-(4-octyl group-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone (n1) is prepared:
Under nitrogen protection; by 0.84g (5mmol) 1; the bromo-5-thiotolene of 3-bis-also [3; 4-c] pyrroles-4; 6-diketone (j1) and 3.59g (10mmol) 4-octyl group-2-tin trimethyl thiophene (k1) add in tetrahydrofuran (THF) successively; logical nitrogen bubble 0.5h removes residual oxygen, then adds rapidly 0.11g (0.15mmol) catalyst P d (PPh 3) 2cl 2, logical nitrogen bubble 1h removes residual oxygen, in 60 DEG C of stirring and refluxing reaction 24h, is cooled to room temperature, reaction solution is poured into cancellation reaction in distilled water, with chloroform extraction, merges organic phase, use anhydrous MgSO 4dried overnight, filter, revolve and steam except chloroform, take volume ratio as the methylene dichloride/sherwood oil mixed solvent of 1:1 be elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 1,3-bis-(4-octyl group-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone (n1).
IV, 1,3-bis-(4-octyl group-5-tin trimethyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone (B1) is prepared:
Under nitrogen protection, by 2.78g (5mmol) 1, 3-bis-(4-octyl group-2-thiophene)-5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (n1) adds in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, at-78 DEG C after stirring reaction 2h, add 3.7mL (12.5mmol) trimethyltin chloride again, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 1, 3-bis-(4-octyl group-5-tin trimethyl-2-thiophene)-5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (B1), mass spectrometric measurement data are MS (MALDI) m/z:881 (M+).
Three, gather 7,8-bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-octyl group-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone }, namely the preparation method of polymer P 1 comprises following operation steps:
Under nitrogen protection; 1.68g (2.0mmol) compd A 1 and 1.76g (2.0mmol) compound B-11 are added in the toluene of 30mL drying; logical nitrogen bubble 0.25h removes residual oxygen, then adds rapidly 46mg (0.04mmol) Pd (PPh 3) 4, logical nitrogen bubble 1h removes residual oxygen, is heated to 120 DEG C of back flow reaction 24h, remove reaction solution under reduced pressure toluene, surplus materials is added drop-wise in methyl alcohol and carries out sedimentation, suction filtration, with dry after methanol wash, be then that elutriant alumina chromatographic column carries out separating-purifying with chloroform, then steam except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction three days, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 1, reaction formula is:
Carry out GPC test to polymer P 1, moving phase is THF, records Mn=89760, Mw/Mn=1.8, n=80.
Embodiment 2
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, be specially poly-{ 7,8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(2-thiophene)-5-(3-butyl certain herbaceous plants with big flowers base) thieno-[3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 2, wherein, n=45:
Preparation method comprises the following steps:
One, the reaction scheme preparing 4,11-bis-bromo-7,8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A2) is as follows:
Concrete operations are as follows:
(1) 4,5-bis-(2-ethyl pentyl group)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b2) are prepared:
By 1.93g (5mmol) 4 in nitrogen atmosphere, 5-bis-(2-ethyl pentyl group) benzo [2, 1-b:3, 4-b '] two thiophene (a2) add in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 4.4mL n-Butyl Lithium, 11mmol), finish, at-78 DEG C after stirring reaction 2h, add the trimethyltin chloride of 3.3mL (11mmol) again, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 4, 5-bis-(2-ethyl pentyl group)-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b2), mass spectrometric measurement data are MS (EI) m/z:712 (M+).
(2) 4,5-bis-(2-ethyl pentyl group)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d2) are prepared:
By 0.74g (3.36mmol) 2-brooethyl thionyl benzene (c), 0.96g (1.34mmol) 4,5-bis-(2-ethyl pentyl group)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b2) add in the tetrahydrofuran (THF) of 30mL drying, logical nitrogen bubble 30min, adds rapidly 0.047g (0.067mmol) Pd (PPh 3) 2cl 2, be heated to 60 DEG C of stirring reaction 48h, after stopped reaction, remove excessive DMF under reduced pressure, by ethyl acetate, reaction residues is dissolved, and wash, through MgSO with the KF aqueous solution of 10% 4after drying, filter, revolve steaming, the mixed solvent taking volume ratio as the normal hexane/tetrahydrofuran (THF) of 1:3, for elutriant is through silica gel column chromatography column separating purification, obtains 4,5-bis-(2-ethyl pentyl group)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d2), productive rate is 79%, and mass spectrometric measurement data are MS (EI) m/z:663 (M+);
(3) prepare 7,8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e2), comprise the following steps:
By 0.66g (1mmol) 4, 5-bis-(2-ethyl pentyl group)-2, 7-bis-(2-methyl sulfinyl benzene) benzo [2, 1-b:3, 4-b '] two thiophene (d2) and 0.071g (0.5mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid, stirring at room temperature reaction 72h, then reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter, join in 30mL pyridine after vacuum-drying, be heated to 110 DEG C of back flow reaction 12h, reaction solution is cooled to room temperature, add dichloromethane extraction, merge organic phase, use anhydrous MgSO 4steaming is revolved after drying, take volume ratio as the methylene dichloride/normal hexane mixed solvent of 1:9 be elutriant, separation and purification is carried out to revolving the rear surplus materials of steaming with silica gel column chromatography, obtain 7,8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e2), productive rate is 76%, and mass spectrometric measurement data are MS (MALDI) m/z:599 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 2.46g (4.31mmol) 7, 8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e2) add in 60mLDMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, add anhydrous magnesium sulfate drying and revolve steaming after filtration, take volume ratio as the ethyl acetate/petroleum ether mixed solvent of 1:5 be elutriant, separation and purification is carried out to revolving the rear surplus materials of steaming with silica gel column chromatography, obtain 4, 11-bis-bromo-7, 8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A2),
The mass spectrometric measurement data of compd A 2 are MS (MALDI) m/z:757 (M+);
The hydrogen spectrum analysis data of compd A 2 are: 1hNMR (300MHz, CD 2cl 2): δ (ppm)=7.91 (s, 2H), 7.86 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 2.76 (m, 1H), 1.62-1.29 (m, 16H), 0.91 (tt, J=13.44,6.74,6.74Hz, 9H).
Two, the reaction scheme preparing 1,3-bis-(5-tin trimethyl-2-thiophene)-5-(3-butyl certain herbaceous plants with big flowers base) thieno-[3,4-c] pyrroles-4,6-diketone (B2) is as follows:
Comprise following operation steps:
I, 5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (i2) is prepared:
By 0.86g (5mmol) thiophene-3, 4-dioctyl phthalate (f) adds in 25mL acetic anhydride, be heated to 140 DEG C, stirring reaction 12h, be cooled to room temperature, remove reaction solution, obtain the crude product of compound g, gained crude product 50mL toluene is dissolved, add 1.28g (6.0mmol) 3-butyl certain herbaceous plants with big flowers amine (h2), be heated to 110 DEG C of back flow reaction 24h, be cooled to room temperature, remove toluene under reduced pressure, with 50mL thionyl chloride, remaining solid thing in matrass is dissolved again, cool after being heated to 80 DEG C of stirring and refluxing 4h, remove thionyl chloride under reduced pressure, take volume ratio as the methylene dichloride/sherwood oil mixed solvent of 3:2 be elutriant, separation and purification is carried out to revolving the rear surplus materials of steaming with silica gel column chromatography, obtain 5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3, 4-c] pyrroles-4, 6-diketone (i2), productive rate 54%.
II, 1,3-bis-bromo-5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (j2) is prepared:
By 3.50g (10mmol) 5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (i2) is dissolved in the mixed solution of the 10mL vitriol oil and 33mL trifluoroacetic acid, under lucifuge condition, add 5.34g (30mmol) N-bromo-succinimide (NBS) point for four times in the single port bottle of 150mL, stirring at room temperature reaction is spent the night, reaction solution is poured in distilled water, with chloroform extraction, merge organic phase, use anhydrous MgSO 4dried overnight, revolving and steam removing chloroform, is that the methylene dichloride/sherwood oil mixed solvent of 1:1 is elutriant with volume ratio, through silica gel column chromatography column separating purification, obtain the bromo-5-of 1,3-bis-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (j2).
III, 1,3-bis-(2-thiophene)-5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (n2) is prepared:
Under nitrogen protection; by 2.54g (5mmol) 1; the bromo-5-of 3-bis-(3-butyl) certain herbaceous plants with big flowers base thieno-[3; 4-c] pyrroles-4; 6-diketone (j2) and 3.09g (12.5mmol) 2-tin trimethyl thiophene (k2) add in tetrahydrofuran (THF) successively; bubbling 0.5h removes residual oxygen, then adds rapidly 0.35mg (0.0005mmol) Pd (PPh 3) 2cl 2, bubbling 1h removes residual oxygen, in 60 DEG C of stirring and refluxing reaction 24h, is cooled to room temperature, reaction solution is poured into cancellation reaction in distilled water, with chloroform extraction, merges organic phase, use anhydrous MgSO 4dried overnight, filter, revolve and steam removing chloroform, take volume ratio as the methylene dichloride/sherwood oil mixed solvent of 1:1.5 be elutriant, carrying out separation and purification with silica gel column chromatography to revolving the rear surplus materials of steaming, obtaining 1,3-bis-(2-thiophene)-5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (n2).
IV, under nitrogen protection, by 2.57g (5mmol) 1, 3-bis-(2-thiophene)-5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3, 4-c] pyrroles-4, 6-diketone (n2) adds in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 4.4mL n-Butyl Lithium, 11mmol), finish, at-78 DEG C after stirring reaction 2h, add 3.3mL (11mmol) trimethyltin chloride again, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 1, 3-bis-(5-tin trimethyl-2-thiophene)-5-(3-butyl certain herbaceous plants with big flowers base) thieno-[3, 4-c] pyrroles-4, 6-diketone (B2), the mass spectrometric measurement data of compd B 2 are MS (MALDI) m/z:839 (M+).
Three, poly-{ 7,8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(2-thiophene)-5-(3-butyl certain herbaceous plants with big flowers base) thieno-[3,4-c] pyrroles-4,6-diketone }, namely the preparation method of polymer P 2 comprises following operation steps:
Under nitrogen protection; 1.51g (2.0mmol) compd A 2 and 2.52g (3.0mmol) compd B 2 are added in 30ml tetrahydrofuran (THF); bubbling 0.5h removes residual oxygen, adds rapidly 0.14mg (0.0002mmol) Pd (PPh 3) 2cl 2bubbling 1h removes residual oxygen, be heated to 60 DEG C of back flow reaction 48h, remove reaction solution under reduced pressure excessive tetrahydrofuran (THF), surplus materials is added drop-wise in methyl alcohol and carries out sedimentation, suction filtration, with dry after methanol wash, then be that elutriant alumina chromatographic column carries out separating-purifying to dried surplus materials with chloroform, steam except organic solvent again, use methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction three days, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 2, reaction formula is as follows:
Carry out GPC test to polymer P 2, moving phase is THF, records Mn=49860, Mw/Mn=1.9, n=45.
Embodiment 3
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, be specially poly-{ 7,8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 3, wherein, n=1:
P3：
Preparation method comprises the following steps:
One, the reaction scheme preparing 4,11-bis-bromo-7,8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A3) is as follows:
Specifically comprise the following steps:
(1) 4,5-bis-(5-hexyl-2-thiophene)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b3) are prepared:
By 2.62g (5mmol) 4 in nitrogen atmosphere, 5-bis-(5-hexyl-2-thiophene) benzo [2, 1-b:3, 4-b '] two thiophene (a3) add in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, at-78 DEG C after stirring reaction 2h, add 3.6mL (12mmol) trimethyltin chloride again, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 4, 5-bis-(5-hexyl-2-thiophene)-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b3), mass spectrometric measurement data are MS (EI) m/z:712 (M+).
(2) 4,5-bis-(5-hexyl-2-thiophene)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d3) are prepared:
By 1.1g (5.0mmol) 2-brooethyl thionyl benzene (c), 1.70g (2.0mmol) 4,5-bis-(5-hexyl-2-thiophene)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b3) add in the toluene of 30mL drying, logical nitrogen bubble 30min, adds Pd rapidly 2(dba) 3(0.092g, 0.1mmol) and P (o-Tol) 3the mixture of (0.061g, 0.2mmol) as catalyzer, Pd 2(dba) 3amount of substance be 5%, Pd of compound b3 2(dba) 3with P (o-Tol) 3mol ratio is 1:2, is heated to 110 DEG C of stirring reaction 48h, after stopped reaction, removes toluene under reduced pressure, dissolved by reaction residues by ethyl acetate, and washes, through MgSO with the KF aqueous solution that massfraction is 10% 4after drying; filter, revolving steaming, is that the normal hexane/tetrahydrofuran (THF) mixed solvent of 3:1 is elutriant with volume ratio; separation and purification is carried out to revolving the rear surplus materials of steaming with silica gel column chromatography; obtain 4,5-bis-(5-hexyl-2-thiophene)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d3), productive rate 81%, mass spectrometric measurement data are MS (EI) m/z:635 (M+).
(3) prepare 7,8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e3), comprise the following steps:
By 0.32g (0.40mmol) 4, 5-bis-(5-hexyl-2-thiophene)-2, 7-bis-(2-methyl sulfinyl benzene) benzo [2, 1-b:3, 4-b '] two thiophene (d3) and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid, stirring at room temperature reaction 72h, then reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter, join in 30mL pyridine after vacuum-drying, be heated to 110 DEG C of back flow reaction 12h, reaction solution is cooled to room temperature, add dichloromethane extraction, merge organic phase, use anhydrous MgSO 4steaming is revolved after drying, take volume ratio as the methylene dichloride/normal hexane mixed solvent of 1:9 be elutriant, separation and purification is carried out to revolving the rear surplus materials of steaming with silica gel column chromatography, obtain 7,8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e3), productive rate 73%, mass spectrometric measurement data are MS (MALDI) m/z:735 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 3.17g (4.31mmol) 7, 8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e3) add in 60mLDMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, add dried over mgso and revolve steaming after filtration, take volume ratio as the ethyl acetate/petroleum ether mixed solvent of 1:5 be elutriant, separation and purification is carried out to revolving the rear surplus materials of steaming with silica gel column chromatography, obtain 4, 11-bis-bromo-7, 8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A3), productive rate 68%.
The mass spectrometric measurement data of compound A-13 are MS (MALDI) m/z:893 (M+);
The hydrogen spectrum analysis data of compound A-13 are: 1hNMR (300MHz, CD 2cl 2): δ (ppm)=7.95 (s, 2H), 7.82 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 6.67 (d, J=13.44Hz, 4H), 2.56 (t, J=6.34Hz, 4H), 1.62-1.29 (m, 16H), 0.93 (dt, J=6.74,6.74Hz, 6H).
Two, the reaction scheme preparing 1,3-bis-(3-dodecyl-5-tin trimethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (B3) is:
Specifically comprise following operation steps:
I, 5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (i3) is prepared:
By 0.86g (5mmol) thiophene-3, 4-dioctyl phthalate (f) adds in 25mL acetic anhydride, be heated to 140 DEG C, stirring reaction 12h, be cooled to room temperature, remove reaction solution, be precipitated, for the crude product of compound g, gained crude product 50mL toluene is dissolved, add 0.71g (7.0mmol) hexylamine (h3), be heated to 120 DEG C of back flow reaction 24h, be cooled to room temperature, remove toluene under reduced pressure, with 50mL thionyl chloride, remaining solid thing in matrass is dissolved again, cool after being heated to 80 DEG C of stirring and refluxing 4h, remove thionyl chloride under reduced pressure, take volume ratio as the methylene dichloride/sherwood oil mixed solvent of 2:3 be elutriant, separation and purification is carried out to revolving the surplus materials after steaming with silica gel column chromatography, obtain 5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (i3), productive rate 51%.
II, the bromo-5-hexyl thiophene of 1,3-bis-also [3,4-c] pyrroles-4,6-diketone (j3) is prepared:
By 2.37g (10mmol) 5-hexyl base thieno-[3,4-c] pyrroles-4,6-diketone (i3) is dissolved in the mixed solution of the 10mL vitriol oil and 33mL trifluoroacetic acid, under lucifuge condition, divided by 5.34g (30mmol) N-bromo-succinimide and join in reaction flask four times, stirred at ambient temperature reaction is spent the night, reaction solution is poured in appropriate distilled water, with chloroform extraction, merge organic phase, use anhydrous MgSO 4dried overnight, revolves except chloroform, is that the methylene dichloride/sherwood oil mixed solvent of 1:1 is elutriant with volume ratio, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain the bromo-5-hexyl thiophene of 1,3-bis-also [3,4-c] pyrroles-4,6-diketone (j3).
III, 1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (n3) is prepared:
Under nitrogen protection; by 1.98g (5mmol) 1; the bromo-5-hexyl thiophene of 3-bis-also [3; 4-c] pyrroles-4; 6-diketone (j3) and 4.57g (11mmol) 3-dodecyl-2-tin trimethyl thiophene (k3) add in tetrahydrofuran (THF) successively; logical nitrogen bubble 0.5h removes residual oxygen, then adds Pd rapidly 2(dba) 3(0.23g, 0.25mmol) and P (o-Tol) 3the mixture of (0.15g, 0.5mmol) as catalyzer, Pd 2(dba) 3amount of substance be 5%, Pd of compound j3 2(dba) 3with P (o-Tol) 3mol ratio is 1:2, and logical nitrogen bubble 1h removes residual oxygen, in 60 DEG C of stirring and refluxing reaction 24h, is cooled to room temperature, reaction solution is poured into cancellation reaction in distilled water, with chloroform extraction, merges organic phase, use anhydrous MgSO 4dried overnight, filter, revolve and steam except chloroform, take volume ratio as the methylene dichloride/sherwood oil mixed solvent of 1:1 be elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (n3).
IV, 1,3-bis-(3-dodecyl-5-tin trimethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (B3) is prepared:
Under nitrogen protection, by 3.69g (5mmol) 1, 3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (n3) adds in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, at-78 DEG C after stirring reaction 2h, add 3.6mL (12mmol) trimethyltin chloride again, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 1, 3-bis-(3-dodecyl-5-tin trimethyl-2-thiophene)-5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (B3), structure mass spectrometric measurement data are MS (MALDI) m/z:1064 (M+).
Three, poly-{ 7,8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, namely the preparation method of polymer P 3 comprises the following steps:
Under nitrogen protection, add in 30mLDMF by 1.79g (2.0mmol) compound A-13 and 2.34g (2.2mmol) compd B 3, bubbling 0.5h removes residual oxygen, then adds Pd rapidly 2(dba) 3(0.06g, 0.066mmol) and P (o-Tol) 3the mixture of (0.04g, 0.132mmol) as catalyzer, Pd 2(dba) 3amount of substance be 3.3%, Pd of compound A-13 2(dba) 3with P (o-Tol) 3mol ratio is 1:2, bubbling 1h removes residual oxygen, be heated to 80 DEG C of back flow reaction 72h, remove reaction solution under reduced pressure DMF, be added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, with dry after methanol wash, be that elutriant alumina chromatographic column carries out separating-purifying with chloroform, steam again except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction three days, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 3, GPC test is carried out to polymer P 3, moving phase is THF, record Mn=1469, Mw/Mn=2.3, n=1, reaction formula is as follows:
Embodiment 4
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, be specially poly-{ 7,8-didecyl oxygen base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-hexyl-4-ethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 4, wherein, n=65:
P4：
Preparation method comprises the following steps:
One, the reaction scheme preparing 4,11-bis-bromo-7,8-didecyl oxygen base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A4) is as follows:
Concrete operations are as follows:
(1) 4,5-bis-certain herbaceous plants with big flowers oxygen base-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b4) are prepared:
In nitrogen atmosphere, by 2.52g (5mmol) 4, 5-bis-certain herbaceous plants with big flowers oxygen base benzo [2, 1-b:3, 4-b '] two thiophene (a4) add in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 4.5mL n-Butyl Lithium, 11.25mmol), finish, stirring reaction 2h at-78 DEG C, add 3.0mL (10mmol) trimethyltin chloride, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 4, 5-bis-certain herbaceous plants with big flowers oxygen base-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b4), mass spectrometric measurement data are MS (EI) m/z:712 (M+).
(2) 4,5-bis-certain herbaceous plants with big flowers oxygen base-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d4) are prepared:
By 1.1g (5.0mmol) 2-brooethyl thionyl benzene (c), 2.07g (2.5mmol) 4,5-bis-certain herbaceous plants with big flowers oxygen base-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b4) add in 30mL dry DMF, logical nitrogen bubble 30min, adds Pd rapidly 2(dba) 3(0.092g, 0.1mmol) and P (o-Tol) 3the mixture of (0.61g, 1.0mmol) as catalyzer, Pd 2(dba) 3amount of substance be 4%, Pd of compound b4 2(dba) 3with P (o-Tol) 3mol ratio is 1:10, is heated to 80 DEG C of stirring reaction 48h, after stopped reaction, removes excessive DMF under reduced pressure, is dissolved by reaction residues by ethyl acetate, and washes, through MgSO with the KF aqueous solution that massfraction is 10% 4after drying; filter; revolve steaming, be that the tetrahydrofuran (THF)/normal hexane mixed solvent of 1:3 is elutriant with volume ratio, carry out separation and purification with silica gel column chromatography; obtain 4; 5-bis-certain herbaceous plants with big flowers oxygen base-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3; 4-b '] two thiophene (d4), mass spectrometric measurement data are MS (EI) m/z:779 (M+).
(3) 7,8-bis-certain herbaceous plants with big flowers oxygen base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e4) are prepared:
By 0.39g (0.5mmol) 4; 5-bis-certain herbaceous plants with big flowers oxygen base-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d4) and 0.036g (0.25mmol) Vanadium Pentoxide in FLAKES add in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter; add in 30mL pyridine after vacuum-drying; be heated to 110 DEG C of back flow reaction 12h, reaction solution be cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4steaming is revolved after drying, be that the methylene dichloride/normal hexane mixed solvent of 1:9 carries out separating-purifying for elutriant silica gel column chromatography with volume ratio, obtain 7,8-bis-certain herbaceous plants with big flowers oxygen base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e4), mass spectrometry results is MS (MALDI) m/z:715 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 4.08g (4.31mmol) 7, 8-bis-certain herbaceous plants with big flowers oxygen base dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e4) add in 60mLDMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, add dried over mgso and revolve steaming after filtration, be that the ethyl acetate/petroleum ether mixed solvent of 1:5 carries out separation and purification for elutriant silica gel column chromatography with volume ratio, obtain 4, 11-bis-bromo-7, 8-didecyl oxygen base dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A4).
The mass spectrometric measurement data of compd A 4 are: MS (MALDI) m/z:873 (M+); The hydrogen spectrum analysis data of compd A 4 are: 1hNMR (300MHz, CD 2cl 2), δ (ppm)=7.92 (s, 2H), 7.83 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 3.94 (t, J=13.44Hz, 4H), 1.72-1.29 (m, 32H), 0.96 (t, J=6.74,6H).
Two, the reaction scheme preparing 1,3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (B4) is:
Specifically comprise the following steps:
I, 5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (i4) is prepared:
By 0.86g (5mmol) thiophene-3, 4-dioctyl phthalate (f) adds in 25mL acetic anhydride, be heated to 140 DEG C, stirring reaction 12h, be cooled to room temperature, remove reaction solution, obtain the crude product of compound g, gained crude product 50mL toluene is dissolved, add 0.66g (6.5mmol) hexylamine (h4), be heated to 120 DEG C of back flow reaction 24h, be cooled to room temperature, remove toluene under reduced pressure, with 50mL thionyl chloride, remaining solid thing in matrass is dissolved again, cool after being heated to 80 DEG C of stirring and refluxing 4h, remove thionyl chloride under reduced pressure, be that the methylene dichloride/sherwood oil mixed solvent of 3:2 carries out separating-purifying for elutriant silica gel column chromatography with volume ratio, obtain 5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (i4), productive rate 56%.
II, 1 is prepared, the bromo-5-hexyl thiophene of 3-bis-also [3,4-c] pyrroles-4,6-diketone (j4): by 2.37g (10mmol) 5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (i4) is dissolved in the mixed solution of the 10mL vitriol oil and 33mL trifluoroacetic acid, under lucifuge condition, 5.34g (30mmol) N-bromo-succinimide (NBS) point is joined in reaction flask four times, stirred at ambient temperature reaction is spent the night, and is poured into by reaction solution in appropriate distilled water, with chloroform extraction, merge organic phase, use anhydrous MgSO 4dried overnight, revolves except chloroform, is that the methylene dichloride/sherwood oil mixed solvent of 1:1 is elutriant, carries out separation and purification with silica gel column chromatography with volume ratio, obtains the bromo-5-hexyl thiophene of 1,3-bis-also [3,4-c] pyrroles-4,6-diketone (j4).
III, 1,3-bis-(3-hexyl-4-ethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (n4) is prepared:
Under nitrogen protection; by 1.98g (5mmol) 1; the bromo-5-hexyl thiophene of 3-bis-also [3; 4-c] pyrroles-4; 6-diketone (j4) and 3.59g (10mmol) 3-hexyl-4-ethyl-2-tin trimethyl thiophene (k4) add in tetrahydrofuran (THF) successively; bubbling 0.5h removes residual oxygen, then adds Pd rapidly 2(dba) 3(0.14g, 0.15mmol) and P (o-Tol) 3the mixture of (0.46g, 1.5mmol) as catalyzer, Pd 2(dba) 3amount of substance be 3%, Pd of compound j4 2(dba) 3with P (o-Tol) 3mol ratio is 1:10, and bubbling 1h removes residual oxygen, is warming up to 60 DEG C of stirring and refluxing reaction 24h, is cooled to room temperature, reaction solution is poured into cancellation reaction in distilled water, with chloroform extraction, merges organic phase, use anhydrous MgSO 4dried overnight, filter, revolve and steam removing chloroform, be that the methylene dichloride/sherwood oil mixed solvent of 1:1 carries out separation and purification for elutriant silica gel column chromatography with volume ratio, obtain 1,3-bis-(3-hexyl-4-ethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (n4), productive rate is 71%.
IV, 1,3-bis-(3-hexyl-4-ethyl-5-tin trimethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (B4) is prepared:
Under nitrogen protection, by 3.13g (5mmol) 1, 3-bis-(-hexyl-4-ethyl-2-thiophene)-5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (n4) adds in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 4.5mL n-Butyl Lithium, 11.25mmol), finish, at-78 DEG C after stirring reaction 2h, add 3.0mL (10mmol) trimethyltin chloride again, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 1, 3-bis-(3-hexyl-4-ethyl-5-tin trimethyl-2-thiophene)-5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (B4), mass spectrometric measurement data are MS (MALDI) m/z:952 (M+).
Three, poly-{ 7,8-didecyl oxygen base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-hexyl-4-ethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, namely the preparation method of polymer P 4 comprises the following steps:
Under nitrogen protection, add in 30mL toluene by 1.75g (2.0mmol) compd A 4 and 1.90g (2.0mmol) B4, bubbling 0.5h removes residual oxygen, adds rapidly 46mg (0.04mmol) Pd (PPh 3) 4, bubbling 1h removes residual oxygen, is heated to 120 DEG C of back flow reaction 48h, remove reaction solution under reduced pressure toluene, be added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, with dry after methanol wash, be that elutriant alumina chromatographic column carries out separating-purifying with chloroform, then steam except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction three days, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 4, reaction formula is as follows:
Carry out GPC test to polymer P 4, moving phase is THF, records Mn=86905, Mw/Mn=1.7, n=65.
Embodiment 5
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, be specially poly-{ dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone }, have following logical, be designated as polymer P 5, wherein, n=25:
P5：
Preparation method comprises the following steps:
One, the reaction scheme of 4,11-dibromo dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A5) is prepared:
Concrete operations are as follows:
(1) 2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b5) are prepared:
In nitrogen atmosphere, by 0.95g (5mmol) benzo [2, 1-b:3, 4-b '] two thiophene (a5) add in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, at-78 DEG C after stirring reaction 2h, add 3.7mL (12.5mmol) trimethyltin chloride again, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b5), mass spectrometric measurement data are MS (EI) m/z:516 (M+).
(2) 2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d5) are prepared:
By 1.1g (5mmol) 2-brooethyl thionyl benzene (c), 1.29g (2.5mmol) 2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b5) add in 30mL dry DMF, logical nitrogen bubble 30min, adds Pd rapidly 2(dba) 3(0.069g, 0.075mmol) and P (o-Tol) 3the mixture of (0.46g, 1.5mmol) as catalyzer, Pd 2(dba) 3amount of substance be 3%, Pd of compound b5 2(dba) 3with P (o-Tol) 3mol ratio is 1:20, is heated to 80 DEG C of stirring reaction 48h, after stopped reaction, removes DMF under reduced pressure, dissolved by reaction residues by ethyl acetate, and washes, through MgSO with the KF aqueous solution that massfraction is 10% 4after drying, filter, revolve steaming, be that the tetrahydrofuran (THF)/normal hexane solvent of 1:3 is for elutriant is through silica gel column chromatography column separating purification with volume ratio, obtain 2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d5), mass spectrometric measurement data are MS (EI) m/z:467 (M+);
(3) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e5) are prepared:
By 0.17g (0.36mmol) 2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d5) and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; then reaction mixture is poured into cancellation reaction in 100mL ice-water bath; precipitated in a large number; filter, join after vacuum-drying in 30mL pyridine, be heated to 110 DEG C of back flow reaction 12h; reaction solution is cooled to room temperature; add dichloromethane extraction, merge organic phase, use anhydrous MgSO 4steaming is revolved after drying, be that the methylene dichloride/normal hexane mixed solvent of 1:9 is for elutriant is through silica gel column chromatography column separating purification with volume ratio, obtain dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e5), mass spectrometric measurement data are MS (MALDI) m/z:403 (M+)
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 1.74g (4.31mmol) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e5) add in 60mLDMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, add dried over mgso and revolve steaming after filtration, be that the ethyl acetate/petroleum ether mixed solvent of 1:5 is for elutriant is through silica gel column chromatography column separating purification with volume ratio, obtain 4, 11-dibromo dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A5).
The mass spectrometric measurement data of compound A-45 are MS (MALDI) m/z:560 (M+);
The hydrogen spectrum analysis data of compound A-45 are 1hNMR (300MHz, CD 2cl 2), δ (ppm)=8.03 (s, 2H), 7.67 (d, J=7.87Hz, 2H), 7.50 (d, J=7.83Hz, 2H).
Two, the reaction scheme preparing 1,3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone (B5) is as follows:
Specifically comprise following operation steps:
I, 5-thiotolene also [3,4-c] pyrroles-4,6-diketone (i5) is prepared:
By 0.86g (5mmol) thiophene-3, 4-dioctyl phthalate (f) adds in 25mL acetic anhydride, be heated to 140 DEG C, stirring reaction 12h, be cooled to room temperature, remove reaction solution, obtain the crude product of compound g, gained crude product 50mL toluene is dissolved, add 0.24g (7.5mmol) methylamine (h5), be heated to 110 DEG C of back flow reaction 24h, be cooled to room temperature, remove toluene under reduced pressure, with 50mL thionyl chloride, remaining solid thing in matrass is dissolved again, cool after being heated to 80 DEG C of stirring and refluxing 4h, remove thionyl chloride under reduced pressure, be that the methylene dichloride/sherwood oil mixed solvent of 2:3 is for elutriant is through silica gel column chromatography separating-purifying with volume ratio, obtain 5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (i5), productive rate 54%.
II, the bromo-5-thiotolene of 1,3-bis-also [3,4-c] pyrroles-4,6-diketone (j5) is prepared:
By 1.67g (10mmol) 5-thiotolene also [3,4-c] pyrroles-4,6-diketone (i5) is dissolved in the mixed solution of the 10mL vitriol oil and 33mL trifluoroacetic acid, under lucifuge condition, join in reaction flask four times by 5.34g (30mmol) N-bromo-succinimide (NBS) point, stirred at ambient temperature reaction is spent the night, reaction solution is poured in appropriate distilled water, with chloroform extraction, merge organic phase, use anhydrous MgSO 4dried overnight, revolves except chloroform, and the methylene dichloride/sherwood oil mixed solvent taking volume ratio as 1:1, for elutriant is through silica gel column chromatography column separating purification, obtains the bromo-5-thiotolene of 1,3-bis-also [3,4-c] pyrroles-4,6-diketone (j5).
III, 1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone (n5) is prepared:
Under nitrogen protection; by 1.63g (5mmol) 1; the bromo-5-thiotolene of 3-bis-also [3; 4-c] pyrroles-4; 6-diketone (j5) and 3.59g (10mmol) 3-hexyl-4-ethyl-2-tin trimethyl thiophene (k4) add in 80ml tetrahydrofuran (THF) successively; bubbling 0.5h removes residual oxygen, then adds Pd rapidly 2(dba) 3(0.14g, 0.15mmol) and P (o-Tol) 3the mixture of (0.92g, 3.0mmol) as catalyzer, Pd 2(dba) 3amount of substance be 3%, Pd of compound j5 2(dba) 3with P (o-Tol) 3mol ratio is 1:20, and bubbling 1h removes residual oxygen, in 60 DEG C of stirring and refluxing reaction 24h, is cooled to room temperature, reaction solution is poured into cancellation reaction in distilled water, with chloroform extraction, merges organic phase, use anhydrous MgSO 4dried overnight, filter, revolve and steam removing chloroform, be that the methylene dichloride/sherwood oil mixed solvent of 1:1 is for elutriant is through silica gel column chromatography column separating purification with volume ratio, obtain 1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone (n5), productive rate 69%.
IV, 1,3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone (B5) is prepared:
Under nitrogen protection, by 2.78g (5mmol) 1, 3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (n5) adds in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, at-78 DEG C after stirring reaction 2h, add 3.7mL (12.5mmol) trimethyltin chloride again, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 1, 3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene)-5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (B5), mass spectrometric measurement data are MS (MALDI) m/z:881 (M+).
Three, gather dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone }, namely the preparation method of polymer P 5 comprises the following steps:
Under nitrogen protection, add in 30mLDMF by 1.12g (2.0mmol) compound A-45 and 1.76g (2.0mmol) compd B 5, bubbling 0.5h removes residual oxygen, then adds Pd rapidly 2(dba) 3(0.092g, 0.1mmol) and P (o-Tol) 3the mixture of (0.3g, 1.0mmol) as catalyzer, Pd 2(dba) 3amount of substance be 5%, Pd of compound A-45 2(dba) 3with P (o-Tol) 3mol ratio is 1:10, bubbling 1h removes residual oxygen, be heated to 80 DEG C of back flow reaction 48h, remove reaction solution under reduced pressure DMF, be added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, with dry after methanol wash, then be that eluent alumina chromatographic column carries out separating-purifying with chloroform, steam again except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction three days, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 5, GPC test is carried out to polymer P 5, moving phase is THF, record Mn=14310, Mw/Mn=1.9, n=25, reaction formula is as follows:
Embodiment 6
A kind of containing diazosulfide-dibenzothiophene benzo two thiophen polymer, be specially poly-{ 7,8-dimethyl dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 6, wherein, n=30:
P6：
Preparation method comprises the following steps:
One, the reaction scheme of 4,11-bis-bromo-7,8-dimethyl dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A6) is prepared:
Concrete operations are as follows:
(1) 4,5-dimethyl-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b6) are prepared:
In nitrogen atmosphere, by 1.09g (5mmol) 4, 5-dimethylbiphenyl [2, 1-b:3, 4-b '] two thiophene (a6) add in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 4.5mL n-Butyl Lithium, 11.25mmol), finish, at-78 DEG C after stirring reaction 2h, add 3.3mL (11mmol) trimethyltin chloride again, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 4, 5-dimethyl-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b6), mass spectrometric measurement data are MS (EI) m/z:544 (M+).
(2) 4,5-dimethyl-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d6) are prepared:
By 0.74g (3.36mmol) 2-brooethyl thionyl benzene (c), 0.83g (1.53mmol) 4,5-dimethyl-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b6) add in 30mL anhydrous tetrahydro furan, logical nitrogen bubble 30min, adds rapidly 0.018mg (0.00015mmol) Pd (PPh 3) 4as catalyzer, be heated to 60 DEG C of stirring reaction 24h, after stopped reaction, remove tetrahydrofuran (THF) under reduced pressure, by ethyl acetate, reaction residues is dissolved, and wash, through MgSO with the KF aqueous solution that massfraction is 10% 4after drying, filter, revolve steaming, tetrahydrofuran (THF)/normal hexane the solvent taking volume ratio as 1:3, for elutriant is through silica gel column chromatography column separating purification, obtains 4,5-dimethyl-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d6), mass spectrometric measurement data are MS (EI) m/z:495 (M+);
(3) 7,8-dimethyl dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e6) are prepared:
By 0.20g (0.4mmol) 4; 5-dimethyl-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d6) and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; then reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter; join in 30mL pyridine after vacuum-drying; be heated to 110 DEG C of back flow reaction 12h, reaction solution be cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4steaming is revolved after drying, be that the methylene dichloride/normal hexane mixed solvent of 1:9 is for elutriant is through silica gel column chromatography column separating purification with volume ratio, obtain 7,8-dimethyl dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e6), mass spectrometric measurement data are MS (MALDI) m/z:431 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 1.86g (4.31mmol) 7, 8-dimethyl dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e6) add in 60mLDMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, add dried over mgso and revolve steaming after filtration, take volume ratio as the ethyl acetate/petroleum ether mixed solvent of 1:5 be elutriant, through silica gel column chromatography column separating purification, obtain 4, 11-bis-bromo-7, 8-dimethyl dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A6).
The mass spectrometric measurement data of compd A 6 are: MS (MALDI) m/z:588 (M+);
The hydrogen spectrum analysis data of compd A 6 are: 1hNMR (300MHz, CD 2cl 2): δ (ppm)=7.91 (s, 2H), 7.86 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 2.35 (s, 6H).
Two, 1,3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone (B5) is prepared:
Preparation method is with embodiment 5 step 2.
Three, poly-{ 7,8-dimethyl dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone }, namely the preparation method of polymer P 6 comprises the following steps:
Under nitrogen protection, 1.51g (2.0mmol) compd A 6 and 1.76g (2.0mmol) compd B 5 are added in 30mL tetrahydrofuran (THF), bubbling 0.5h removes residual oxygen, then adds rapidly 0.23mg (0.0002mmol) Pd (PPh 3) 4as catalyzer, bubbling 1h removes residual oxygen, be heated to 60 DEG C of back flow reaction 24h, remove reaction solution under reduced pressure tetrahydrofuran (THF), be added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, with dry after methanol wash, then be that eluent alumina chromatographic column carries out separating-purifying with chloroform, steam again except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction three days, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 6, GPC test is carried out to polymer P 6, moving phase is THF, record Mn=29460, Mw/Mn=1.8, n=30, reaction formula is as follows:
Embodiment 7
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, be specially poly-{ 7,8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 7, wherein, n=20:
P7：
Preparation method comprises the following steps:
One, the reaction scheme preparing 4,11-bis-bromo-7,8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A7) is as follows:
Specifically comprise the following steps:
(1) 4,5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b7) are prepared:
By 3.18g (5mmol) 4 in nitrogen atmosphere, 5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) benzo [2, 1-b:3, 4-b '] two thiophene (a3) add in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 4.4mL n-Butyl Lithium, 11mmol), finish, at-78 DEG C after stirring reaction 2h, add 3.6mL (12mmol) trimethyltin chloride again, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 4, 5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b7), mass spectrometric measurement data are MS (EI) m/z:961 (M+).
(2) 4,5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d7) are prepared:
By 1.1g (5.0mmol) 2-brooethyl thionyl benzene (c), 1.92g (2.0mmol) 4,5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b7) add in the toluene of 30mL drying, logical nitrogen bubble 30min, adds Pd rapidly 2(dba) 3(0.092g, 0.1mmol) and P (o-Tol) 3the mixture of (0.061g, 0.2mmol) as catalyzer, Pd 2(dba) 3amount of substance be 5%, Pd of compound b3 2(dba) 3with P (o-Tol) 3mol ratio is 1:2, is heated to 110 DEG C of stirring reaction 48h, after stopped reaction, removes toluene under reduced pressure, dissolved by reaction residues by ethyl acetate, and washes, through MgSO with the KF aqueous solution that massfraction is 10% 4after drying; filter, revolving steaming, is that the normal hexane/tetrahydrofuran (THF) mixed solvent of 3:1 is elutriant with volume ratio; separation and purification is carried out to revolving the rear surplus materials of steaming with silica gel column chromatography; obtain 4,5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d7), productive rate 76%, mass spectrometric measurement data are MS (EI) m/z:911 (M+).
(3) prepare 7,8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e7), comprise the following steps:
By 0.36g (0.40mmol) 4, 5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2, 7-bis-(2-methyl sulfinyl benzene) benzo [2, 1-b:3, 4-b '] two thiophene (d7) and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid, stirring at room temperature reaction 72h, then reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter, join in 30mL pyridine after vacuum-drying, be heated to 110 DEG C of back flow reaction 12h, reaction solution is cooled to room temperature, add dichloromethane extraction, merge organic phase, use anhydrous MgSO 4steaming is revolved after drying, take volume ratio as the methylene dichloride/normal hexane mixed solvent of 1:9 be elutriant, separation and purification is carried out to revolving the rear surplus materials of steaming with silica gel column chromatography, obtain 7,8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e7), productive rate 70%, mass spectrometric measurement data are MS (MALDI) m/z:847 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 3.17g (4.31mmol) 7, 8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e7) add in 60mLDMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, add dried over mgso and revolve steaming after filtration, take volume ratio as the ethyl acetate/petroleum ether mixed solvent of 1:5 be elutriant, separation and purification is carried out to revolving the rear surplus materials of steaming with silica gel column chromatography, obtain 4, 11-bis-bromo-7, 8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A7), productive rate 68%.
The mass spectrometric measurement data of compd A 7 are MS (MALDI) m/z:1005 (M+);
The hydrogen spectrum analysis data of compd A 7 are: 1hNMR (300MHz, CD 2cl 2): δ (ppm)=7.95 (s, 2H), 7.82 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 6.67 (d, J=13.44Hz, 4H), 2.56 (t, J=6.34Hz, 4H), 1.62-1.29 (m, 32H), 0.93 (dt, J=6.74,6.74Hz, 6H).
Two, 1,3-bis-(3-dodecyl-5-tin trimethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (B3) is prepared:
Preparation method is with embodiment 3 step 2.
Three, poly-{ 7,8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, namely the preparation method of polymer P 7 comprises the following steps:
Under nitrogen protection, add in 30mLDMF by 2.01g (2.0mmol) compd A 7 and 2.34g (2.2mmol) compd B 3, bubbling 0.5h removes residual oxygen, then adds Pd rapidly 2(dba) 3(0.055g, 0.06mmol) and P (o-Tol) 3the mixture of (0.36g, 1.2mmol) as catalyzer, Pd 2(dba) 3amount of substance be 3%, Pd of compd A 7 2(dba) 3with P (o-Tol) 3mol ratio is 1:20, bubbling 1h removes residual oxygen, be heated to 80 DEG C of back flow reaction 36h, remove reaction solution under reduced pressure DMF, be added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, with dry after methanol wash, be that elutriant alumina chromatographic column carries out separating-purifying with chloroform, steam again except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction three days, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 7, GPC test is carried out to polymer P 7, moving phase is THF, record Mn=31640, Mw/Mn=2.3, n=20, reaction formula is as follows:
Embodiment 8
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, be specially poly-{ 7,8-dimethoxy dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 8, wherein, n=:
P8：
Preparation method comprises the following steps:
One, the reaction scheme preparing 4,11-bis-bromo-7,8-dimethoxy dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A8) is as follows:
Concrete operations are as follows:
(1) 4,5-dimethoxy-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b8) are prepared:
In nitrogen atmosphere, by 1.40g (5mmol) 4, 5-dimethoxy benzo [2, 1-b:3, 4-b '] two thiophene (a8) add in 60mL anhydrous tetrahydro furan, be cooled to-78 DEG C, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, stirring reaction 2h at-78 DEG C, add 3.6mL (12mmol) trimethyltin chloride, room temperature is returned to after insulation reaction 0.5h, continue reaction 24h, obtain 4, 5-dimethoxy-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b8), mass spectrometric measurement data are MS (EI) m/z:576 (M+).
(2) 4,5-dimethoxy-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d8) are prepared:
By 1.1g (5.0mmol) 2-brooethyl thionyl benzene (c), 1.44g (2.5mmol) 4,5-dimethoxy-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b8) add in 30mL dry DMF, logical nitrogen bubble 30min, adds Pd rapidly 2(dba) 3(0.092g, 0.1mmol) and P (o-Tol) 3the mixture of (0.61g, 1.0mmol) as catalyzer, Pd 2(dba) 3amount of substance be 4%, Pd of compound b8 2(dba) 3with P (o-Tol) 3mol ratio is 1:10, is heated to 80 DEG C of stirring reaction 48h, after stopped reaction, removes excessive DMF under reduced pressure, is dissolved by reaction residues by ethyl acetate, and washes, through MgSO with the KF aqueous solution that massfraction is 10% 4after drying; filter; revolve steaming, be that the tetrahydrofuran (THF)/normal hexane mixed solvent of 1:3 is elutriant with volume ratio, carry out separation and purification with silica gel column chromatography; obtain 4; 5-dimethoxy-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3; 4-b '] two thiophene (d8), mass spectrometric measurement data are MS (EI) m/z:527 (M+).
(3) 7,8-dimethoxy dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e8) are prepared:
By 0.26g (0.5mmol) 4; 5-dimethoxy-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d8) and 0.036g (0.25mmol) Vanadium Pentoxide in FLAKES add in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter; add in 30mL pyridine after vacuum-drying; be heated to 110 DEG C of back flow reaction 12h, reaction solution be cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4steaming is revolved after drying, be that the methylene dichloride/normal hexane mixed solvent of 1:9 carries out separating-purifying for elutriant silica gel column chromatography with volume ratio, obtain 7,8-dimethoxy dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e8), mass spectrometry results is MS (MALDI) m/z:463 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 2.0g (4.31mmol) 7, 8-dimethoxy dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e8) add in 60mLDMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, add dried over mgso and revolve steaming after filtration, be that the ethyl acetate/petroleum ether mixed solvent of 1:5 carries out separation and purification for elutriant silica gel column chromatography with volume ratio, obtain 4, 11-bis-bromo-7, 8-dimethoxy dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A8).
The mass spectrometric measurement data of compound A-28 are: MS (MALDI) m/z:607 (M+);
The hydrogen spectrum analysis data of compound A-28 are: 1hNMR (300MHz, CD 2cl 2), δ (ppm)=7.92 (s, 2H), 7.83 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 3.74 (s, 6H).
Two, 1,3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (B4) is prepared:
Preparation method is with embodiment 4 step 2.
Three, poly-{ 7,8-dimethoxy dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, namely the preparation method of polymer P 8 comprises the following steps:
Under nitrogen protection, add in 30mL toluene by 1.21g (2.0mmol) compd A 4 and 1.90g (2.0mmol) B4, bubbling 0.5h removes residual oxygen, adds rapidly 46mg (0.04mmol) Pd (PPh 3) 4, bubbling 1h removes residual oxygen, is heated to 120 DEG C of back flow reaction 48h, remove reaction solution under reduced pressure toluene, be added drop-wise in methyl alcohol and carry out sedimentation, suction filtration, with dry after methanol wash, be that elutriant alumina chromatographic column carries out separating-purifying with chloroform, then steam except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid acetone surname extraction three days, use methyl alcohol sedimentation again, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 8, reaction formula is as follows:
Carry out GPC test to polymer P 8, moving phase is THF, records Mn=13020, Mw/Mn=1.7, n=12.
Embodiment 9
With the material being active coating containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer P3 prepared by the embodiment of the present invention 3, prepare organic solar batteries device, its structure comprises the substrate of glass 1 stacked gradually, anode 2, middle supplementary layer 3, active coating 4 and negative electrode 5, this device architecture specifically can briefly be described as: substrate of glass/anode/middle supplementary layer/active coating/negative electrode, sees Fig. 1.Wherein, anode 2 is ITO, the tin indium oxide of to be square resistance be 15 Ω/mouth, for being attached to the functional layer of glass basic surface, be called ito glass together with substrate of glass, can buy, the material of middle supplementary layer 3 adopts poly-(3,4-Ethylenedioxy Thiophene): polystyrolsulfon acid matrix material, is called for short PEDOT:PSS (commodity are called CLEVIOSPVPAl4083); The material of active coating 4 comprises electron donor material and electron acceptor material, electron donor(ED) be the embodiment of the present invention 3 prepare containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer P3, electron acceptor(EA) is [6,6] phenyl-C61-methyl-butyrate (PCBM); The material of negative electrode 5 is aluminium.
Wherein, substrate of glass 1, as bottom, chooses ito glass during making, and with ITO layer as anode 2, ito glass thickness is 1.1mm, after ultrasonic cleaning, processes with oxygen plasma (oxygen-Plasma); Then spin coating PEDOT:PSS on ito glass, prepares middle supplementary layer 3, and thickness is 40nm; That the 10mg embodiment of the present invention is prepared is dissolved in 0.4ml dimethylbenzene obtains solution 1 containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer again, get 10mgPCBM to be dissolved in 0.4ml chlorobenzene and to obtain solution 2, solution 1 and solution 2 are spun on middle supplementary layer 3, obtain active coating 4, thickness is 120nm; Be 2 × 10 at pressure -4under the vacuum condition of Pa, evaporation metal aluminium obtains negative electrode 5, and thickness is 80nm, and all preparation process are all carried out in the glove box providing nitrogen inert atmosphere, obtain organic solar batteries device.The preparation method and the structure that contain the organic solar batteries device of Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer containing the present invention are not limited to the present embodiment, can suitably improve device or modify.
By the I-E characteristic of Keithley236 current/voltage source-measuring system test component, the open circuit voltage recording device is 0.52V, and packing factor is 41%, and short-circuit current density is 7.21mA/cm 2, energy conversion efficiency is 1.54%.
Embodiment 10
The material that the polymer P 8 prepared with embodiment 8 is luminescent layer, prepare organic electroluminescence device, its structure comprises the glass substrate 1 stacked gradually, transparent anode 2, luminescent layer 3, buffer layer 4, negative electrode 5, the structure of device is specially: glass substrate/transparent anode/luminescent layer/buffer layer/negative electrode, sees Fig. 2.
Wherein, glass substrate 1 deposits the tin indium oxide (ITO) that square resistance is 15 Ω/mouth, and thickness is 120nm, as transparent anode 2, on transparent anode after spin coating one layer of polymeric P8, prepare luminescent layer 3, thickness is 80nm, buffer layer 4 is prepared in vacuum evaporation, and material is LiF, and thickness is 1nm, last evaporation prepares negative electrode 5, material is metal A l, and thickness is 120nm, and the structure of practical devices is not limited thereto.
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEXCCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency recording organic electroluminescence device is 1.19cd/A, and high-high brightness is 917cd/m 2.
Embodiment 11
The material that the polymer P 3 prepared with the embodiment of the present invention 3 is organic semiconductor layer, prepare organic field effect tube, its structure is as shown in Figure 3, comprise the substrate 1 stacked gradually, insulation layer 2, decorative layer 3, organic semiconductor layer 4, source electrode (S) 5 and drain electrode (D) 6.Wherein, the material of substrate 1 is highly doped silicon chip (Si), and the material of insulation layer 2 can be but be not limited to the SiO that thickness is 450nm 2, the material of decorative layer 3 is octadecyl trichlorosilane alkane (OTS), and the material of organic semiconductor layer 4 is polymer P 3 prepared by the embodiment of the present invention 3, and the material of source electrode (S) 5 and drain electrode (D) 6 is aluminium.
In the preparation of above-mentioned organic field effect tube, the thickness of substrate 1 is 1mm, the thickness of insulation layer 2 is 450nm, the thickness of decorative layer 3 is 2nm, the thickness of source electrode 5 (S) is 50nm, the thickness of drain electrode 6 (D) is 50nm, and all adopt and shelter deposition method preparation, the preparation of organic semiconductor layer is that the polymer P 3 embodiment of the present invention 3 prepared is spun to the insulation layer SiO modified by decorative layer octadecyl trichlorosilane alkane (OTS) 2on, thickness is 2nm, obtains organic field effect tube.
By time of flight method (TimeofFlight, TOF), 7.0 × 10 5vcm -1electric field in the mean void mobility of organic field effect tube of polymer P 3 prepared containing the embodiment of the present invention 3 of test be 1.8 × 10 -4cm 2/ Vs, shows that the hole transport performance containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer prepared by the present invention is good.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (10)

1., containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, it is characterized in that, for having the polymer P of following general formula:
P:
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is: r ' is C 6~ C 10alkyl, n is the natural number between 1 ~ 80.
2., containing a preparation method for Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer, it is characterized in that, comprise following operation steps:
There is provided compd A and compd B, the structural formula of compd A and B is respectively:
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is: r ' is C 6~ C 10alkyl;
Under protection of inert gas; compd A and compd B add in organic solvent by 1:1 ~ 1:1.5 in molar ratio; add catalyzer; Stille coupling reaction is carried out 24 ~ 72 hours at 60 ~ 120 DEG C; obtain containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer after separation and purification, described is the polymer P with following general formula containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer:
P:
In formula, n is the natural number between 1 ~ 80.
3. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer as claimed in claim 2, it is characterized in that, described catalyzer is the one in three (dibenzalacetone) two mixture of palladium and tri-o-tolyl phosphine, two (triphenylphosphine) palladium chloride, tetrakis triphenylphosphine palladium.
4. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer as claimed in claim 3, it is characterized in that, the mole dosage of described catalyzer is 0.01% ~ 5% of compd A mole dosage, for three (dibenzalacetone) two mixture of palladium and tri-o-tolyl phosphine, described three (dibenzalacetone) two the mole dosage of palladium be 0.01% ~ 5% of compd A mole dosage.
5. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer as claimed in claim 3, it is characterized in that, described three (dibenzalacetone) two palladium and tri-o-tolyl phosphine mixture in, three (dibenzalacetone) two the mol ratio of palladium and tri-o-tolyl phosphine be 1:2 ~ 1:20.
6. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer as claimed in claim 2, it is characterized in that, the preparation method of described compd A comprises following operation steps:
(1) under protection of inert gas; compound a is added in tetrahydrofuran (THF), be cooled to-78 DEG C, slowly add n-Butyl Lithium; the mol ratio of n-Butyl Lithium and compound a is 2.2:1 ~ 2.5:1; then stirring reaction 2h at-78 DEG C, then add trimethyltin chloride, the mol ratio of trimethyltin chloride and compound a is 2:1 ~ 2.5:1; room temperature is returned to after insulation reaction 0.5h; continue reaction 24h, obtain compound b, reaction formula is:
(2) under rare gas element and oxygen free condition, be that compound b and the compound c2-brooethyl thionyl benzene of 1:2 ~ 1:2.5 adds in solvent, add catalyzer by mol ratio, at 80 DEG C, Stille coupling reaction 48h occurs, obtain compound d, reaction formula is:
Described catalyzer is the one in three (dibenzalacetone) two mixture of palladium and tri-o-tolyl phosphine, two (triphenylphosphine) palladium chloride, tetrakis triphenylphosphine palladium;
(3) in trifluoromethanesulfonic acid, after compound d and Vanadium Pentoxide in FLAKES react, reactant is poured into cancellation reaction in ice-water bath, be precipitated, gained precipitation added in pyridine and carry out back flow reaction, obtain Verbindung, reaction formula is:
Described reaction with Vanadium Pentoxide in FLAKES is at room temperature reaction 72h, and the mol ratio of described compound d and Vanadium Pentoxide in FLAKES is 1.5:1 ~ 2.0:1, and the temperature of described back flow reaction is 110 DEG C, and the reaction times is 12h;
(4) under lucifuge condition, there is bromination reaction in N-bromo-succinimide and Verbindung, obtain compd A in dimethyl formamide, and reaction formula is:
Described N-bromo-succinimide: the mol ratio of Verbindung is 3:1, and described bromination reaction at room temperature reacts 15h;
Wherein, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, the skeleton symbol of described alkylthrophene group is: r ' is C 6~ C 10alkyl.
7. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer as claimed in claim 6, it is characterized in that, in step (2), the mole dosage of described catalyzer is 0.01% ~ 5% of compound b mole dosage, for three (dibenzalacetone) two mixture of palladium and tri-o-tolyl phosphine, three (dibenzalacetone) two the mole dosage of palladium be compound b mole dosage 0.01% ~ 5%, three (dibenzalacetone) two the mol ratio of palladium and tri-o-tolyl phosphine be 1:2 ~ 1:20.
8. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer as claimed in claim 2, it is characterized in that, the preparation method of described compd B comprises following operation steps:
I, there is condensation reaction in compound f thiophene-3,4-dioctyl phthalate in acetic anhydride, obtains the crude product of compound g, and react with thionyl chloride after described crude product and compound h react again, obtain compound i, reaction formula is:
Described setting-up point is 140 DEG C, and the time is 12h; The mol ratio of described compound f and compound h is 1:1.2 ~ 1:1.5; Described is 110 DEG C with compound h temperature of reaction, and the reaction times is 24h, and described temperature of reacting with thionyl chloride is 80 DEG C, and the time is 4h;
II, under lucifuge condition, in the mixed solution that sulfuric acid and trifluoroacetic acid are formed, compound i and N-bromo-succinimide at room temperature react and spend the night, and obtain compound j, reaction formula is as follows:
Described sulfuric acid to be massfraction be 98% the vitriol oil, the mol ratio of described compound i:N-bromo-succinimide is 1:3, and described N-bromo-succinimide divides four times and adds;
III, in anaerobic and atmosphere of inert gases, add in tetrahydrofuran (THF), add catalyzer by compound j and compound k with mol ratio 1:2, be heated to 60 DEG C and carry out Stille coupling reaction 24h, obtain compound n, reaction formula is:
Described catalyzer is the one in three (dibenzalacetone) two mixture of palladium and tri-o-tolyl phosphine, two (triphenylphosphine) palladium chloride, tetrakis triphenylphosphine palladium;
IV, in atmosphere of inert gases, compound n is added in anhydrous tetrahydro furan, is cooled to-78 DEG C, slowly add the hexane solution of n-Butyl Lithium, n-Butyl Lithium: the mol ratio of compound n is 2.2:1 ~ 2.5:1, finishes, at-78 DEG C after stirring reaction 2h, add trimethyltin chloride, trimethyltin chloride: the mol ratio 2:1 ~ 2.5:1 of compound n, returns to room temperature after insulation reaction 0.5h, continues reaction 24h, obtain compd B, reaction formula is:
Wherein, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl.
9. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer as claimed in claim 8, it is characterized in that, in step III, the mole dosage of described catalyzer is 0.01% ~ 5% of compound j mole dosage, for three (dibenzalacetone) two mixture of palladium and tri-o-tolyl phosphine, three (dibenzalacetone) two the mole dosage of palladium be compound j mole dosage 0.01% ~ 5%, three (dibenzalacetone) two the mol ratio of palladium and tri-o-tolyl phosphine be 1:2 ~ 1:20.
10. according to claim 1 containing the Thienopyrroles diketone-application of dibenzothiophene benzo two thiophen polymer in polymer solar cell device, organic electroluminescence device or organic field effect tube.
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CN102260371A (en) * 2010-05-27 2011-11-30 海洋王照明科技股份有限公司 Organic copolymer, its preparation method and its application
CN102344550A (en) * 2010-07-30 2012-02-08 海洋王照明科技股份有限公司 Perylenetetracarboxylic diimide copolymer containing thiophenepyrrole dione unit, preparation method thereof and application thereof

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