CN104045812B - A kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers and preparation method and application - Google Patents
A kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers and preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers and preparation method and application, and described is the compound P with following structural formula, wherein, R containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched, R2For C1～C12Straight or branched alkyl,Described R ' is expressed as C1～C12The alkyl of straight or branched, n is the integer between 5～60.Described contain 4 containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, 8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants, thioxothiazole unit and dithieno pyrrole unit, high with the matching degree of solar spectrum, energy conversion efficiency can be improved.
Description
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of containing thioxothiazole-dithieno pyrroles-benzo
Two thiophene copolymers and preparation method and application.
Background technology
The solaode that preparation cost is low, usefulness is high is always study hotspot and the difficult point of photovoltaic art.Business the most
The silicon solar cell of industry is high due to complex manufacturing, cost, and application is restricted.In order to reduce cost, expansive approach
Scope, people always search for novel solar cell material for a long time.Polymer solar battery is because of cost of material
The mode large area such as cheap, light weight, flexibility, production technology simple, available coating, printing the advantage such as are prepared and are had superior
Market prospect.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz,
A.J.Heeger, et al.Science, 1992,258,1474) above report conjugated polymer and C60Between Photoinduced Electron turn
After moving phenomenon, people have put into numerous studies in terms of polymer solar battery, and achieve development at full speed.
One of polymer solar battery facing challenges in future is exactly the P-type conjugated polymer of synthesizing new, and it needs
Possesses following characteristics: the dissolubility that (a) is good, beneficially solvent are processed, it is achieved industrialized production；B () is to whole sunlight light
Spectrum has a width and strong absorption；C carrier mobility that () is high, beneficially carrier transport.The most how to widen polymeric material
Light abstraction width so that it is light abstraction width farthest cover whole sunlight spectrum will be research emphasis.
Summary of the invention
For solving the problems referred to above, it is total to it is desirable to provide a kind of containing thioxothiazole-dithieno pyrroles-benzene 1,4-Dithiapentalene
Polymers, containing 4 in this copolymer, 8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants, sulfur
For thiazole unit and dithieno pyrrole unit, by 4, and 8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophenes
Fen analog derivative and dithieno pyrroles's donor monomer are as main polymer chain, and will be derived by body unit 2-sulfur generation-4-thiazole
Thing, as polymer lateral chain, by main chain with side chain to the interaction of this in receptor " push-pull electronics ", adds master interchain
The two-dimentional conjugated system formed, reduces the energy gap of conjugated polymer simultaneously, substantially increases the light abstraction width of material.This
Bright purpose also resides in the preparation method and application providing above-mentioned thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers.
First aspect, the present invention provides a kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, for tool
There is a copolymer p of following structural formula:
In formula, R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched, R2For
C1～C12Straight or branched alkyl,Described R ' is expressed as C1～C12Straight chain or
The alkyl of chain, n is the integer between 5～60.
Benzo [1,2-b:4,5-b '] two thiophene are a class up-and-coming electron donor unit, and it is led at organic electronic etc.
The application in territory, is particularly widely studied in terms of organic polymer solar cell.Due to benzo [1,2-b:4,5-
B '] two thiophene-based monomers have good symmetry and a flatness, and therefore polymer based on it has good carrier and moves
Shifting rate.And 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants be benzo [1,2-b:
4,5-b '] two thiophene-4, the 4 of 8-diketone, 8 introduce 1,3-bis-mercaptan-2-aldehyde derivative.1,3-bis-mercaptan-2-aldehydes spreads out
The biological electron donor material good as a class, its introducing further enhances benzo [1,2-b:4,5-b '] two thiophene-based
Derivant to Electronic Performance.Therefore, just because of 4, and 8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophenes
Electronics that fen analog derivative has itself and geometrical property, it will expand at polymer solar as excellent donor monomer
Application in battery.
By 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants and dithieno pyrrole
Cough up donor monomer as main polymer chain, and will be by body unit 2-sulfur generation-4-thiazole as polymer lateral chain, by master
Chain and side chain are to the interaction of this in receptor " push-pull electronics ", and the conjugated system of two dimension between this main chain and side chain,
Reduce the energy gap of conjugated polymer, substantially increase the light abstraction width of material.
Second aspect, the present invention provides a kind of preparation containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers
Method, including following operating procedure:
Compound A and B that following structural formula represents is provided respectively,
In formula, R1 is H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched, R2
For C1～C12Straight or branched alkyl,Described R ' is expressed as C1～C12Straight chain or
The alkyl of side chain, n is the integer between 5～60.
In atmosphere of inert gases, compound A that mol ratio is 1:1～1.5:1 and compound B is added first organic molten
Dissolving in agent, then add catalyst formation mixed liquor in the first organic solvent, this mixed liquor is carried out at 60～120 DEG C
Stille coupled reaction 24～72 hours, after stopped reaction, isolated and purified obtain copolymer p, and the structural formula of this copolymer p is such as
Under:
In formula, R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched, R2For
C1～C12Straight or branched alkyl,Described R ' is expressed as C1～C12Straight or branched
Alkyl, n is the integer between 5～60；
Reaction equation is:
Preferably, described catalyst is the mixture of organic palladium or organic palladium and organophosphorus ligand.
It is highly preferred that described organic palladium is double (triphenylphosphine) palladium chloride (Pd (PPh3)2Cl2) or four (triphenylphosphines)
Palladium (Pd (PPh3)4), described organic palladium is three (dibenzalacetone) two palladium (Pd with the mixture of organophosphorus ligand2(dba)3)
With three (2-tolyl) phosphine (P (o-Tol)3) mixture；Described organic palladium and Pd in the mixture of organophosphorus ligand2(dba)3
With P (o-Tol)3Mol ratio be 1:2～1:20.
Preferably, the mole dosage of described organic palladium is the 0.01%～5% of compound B mole dosage.
Preferably, described first organic solvent is oxolane, DMF or toluene.
Preferably, in described inert atmosphere, gas is nitrogen or argon.
Preferably, described isolation and purification method is:
After the completion of reaction, by the decompression distillation of copolymer p reactant liquor, remove the first organic solvent of excess, then be added drop-wise to
Settling in methanol, sucking filtration, methanol washs, and is dried；Then by column chromatography, chloroform drip washing, distillation, remove organic solvent,
Methanol settles, sucking filtration, and with acetone surname extraction for several times, methanol settles gained solid, and sucking filtration is pumped through under vacuum pump and is produced night
Thing.
Preferably, described compound A can be prepared by following methods:
(1) compound a and compound b that following structural formula represents be provided respectively:
R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched.
In atmosphere of inert gases, the anhydrous tetrahydrofuran solution of compound b is cooled to-78 DEG C, is slowly added to two different
The cyclohexane solution of propyl group amido lithium, at-78 DEG C after stirring reaction 2～3h, adds the tetrahydrofuran solution of compound a,
Carry out Wittig-Horner reaction, after insulation reaction 0.5～1h, return to room temperature, continue reaction 12～15h, isolated and purified after
Obtain product, i.e. compound c；Wherein, the mol ratio of lithium diisopropyl amido (LDA) and b be 1:1～1.5:1, a and b mole
Ratio is 1:2.0～1:2.5, and its reaction equation is as follows:
(2) in atmosphere of inert gases, the anhydrous tetrahydrofuran solution of compound c is cooled to-78 DEG C, is just slowly added to
The hexane solution of butyl lithium (n-BuLi), then stirring reaction 2～3h at-78 DEG C, add trimethyltin chloride
(Me3SnCl) reagent, returns to room temperature after insulation reaction 0.5～1h, continue reaction 20～24h, obtain product, i.e. compound A；
Wherein, the mol ratio of n-BuLi Yu c is 2.2:1～2.5:1, Me3The mol ratio of SnCl Yu c is 2.0:1～2.5:1, its reaction
Formula is as follows:
R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched.
Preferably, preparing compound step A (1) and farther include isolated and purified, described isolation and purification method is: compound
The reactant liquor of c is through silica gel column chromatography separating purification, and eluant is that normal hexane and dichloromethane are by volume for 3:1～5:1 mixing
After obtain.
Preferably, in described inert atmosphere, gas is nitrogen or argon.
Preferably, described compound B can be prepared by following methods:
Compound d and compound e that following structural formula represents be provided respectively:
By compound d and compound e, with mol ratio as 1:2～1:2.5 joins in the second organic solvent, then dropping is a small amount of
Ammonia, is then heated to solid and dissolves, add ammonium chloride solution, is stirred at reflux reaction 2～3h at 80 DEG C, after reaction stops,
Obtaining product B, wherein, the ratio of described compound d and ammonia is that 1mol compound d needs 0.05～0.1L ammonia, compound d with
The mol ratio of ammonium chloride is 0.7:1～0.9:1, and reaction equation is as follows:
In formula, R2For C1～C12Straight or branched alkyl,Described R ' represents
For C1～C12The alkyl of straight or branched.
Preferably, described second organic solvent is ethanol.
Preferably, preparing compound step B and farther include isolated and purified, described isolation and purification method is:
After the reacting liquid filtering of compound B, after filtering residue uses distilled water, washing with alcohol successively, more heavily tie through dehydrated alcohol
Crystalline substance, obtains product B.
In an embodiment, for convenience of statement, compound A uses compound A1 respectively, and A2, A3 etc. represent, polymer B is used respectively
Polymer B 1, B2, B3 etc. represents, copolymer p uses copolymer p 1, P2 respectively, and P3 etc. represents, compound b uses compound b1 respectively,
B2, b3 etc. represent, compound c uses compound c1 respectively, and c2, c3 etc. represent, the tables such as compound e uses compound e1 respectively, e2, e3
Showing, name is all as the criterion with the title in each embodiment.
Owing to benzo [1,2-b:4,5-b '] two thiophene-based monomers have good symmetry and flatness, therefore based on it
Polymer there is good carrier mobility.And 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two
Thiophene derivants is in benzo [1,2-b:4,5-b '] two thiophene-4, the 4 of 8-diketone, and 8 introduce 1,3-bis-mercaptan-2-aldehydes
Derivant.1,3-bis-mercaptan-2-aldehyde derivative is as the good electron donor material of a class, and its introducing further enhances
Benzo [1,2-b:4,5-b '] two thiophene derivants to Electronic Performance.Therefore, just because of 4,8-bis-(1,3-bis-mercaptan-
2-aldehyde) electronics that has of benzo [1,2-b:4,5-b '] two thiophene derivants itself and geometrical property, it is using as excellent
Donor monomer expands the application in polymer solar battery.
By 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants and dithieno pyrrole
Cough up donor monomer as main polymer chain, and will be by body unit 2-sulfur generation-4-thiazole as polymer lateral chain, by master
Chain and side chain are to the interaction of this in receptor " push-pull electronics ", and the conjugated system of two dimension between this main chain and side chain,
Reduce the energy gap of conjugated polymer, substantially increase the light abstraction width of material.
Preparation method of the present invention is simple, and productivity is high, and mild condition, product is easily controllable.
The third aspect, the present invention provides a kind of answering containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers
With, described it is applied to prepare polymer solar battery activity containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers
Layer material, organic electroluminescence device emitting layer material and organic field effect tube.Described containing thioxothiazole-dithieno pyrrole
Cough up-benzo two thiophene copolymers as described in the first aspect of the invention.
The one that the present invention provides is containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers and preparation method thereof
With application, have the advantages that
The present invention containing in thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers containing 4,8-bis-(1,3-bis-sulfur
Alcohol-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants, thioxothiazole unit and dithieno pyrrole unit, by 4,
8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants are made with dithieno pyrroles's donor monomer
For main polymer chain, and will be by body unit 2-sulfur generation-4-thiazole as polymer lateral chain, by main chain with side chain to being subject to
Interaction this " push-pull electronics " in body, adds the two-dimentional conjugated system that master interchain is formed, reduces conjugation poly-simultaneously
The energy gap of compound, substantially increases the light abstraction width of material.Improve electricity conversion.
Containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers currently without document report and Patents Shen
Please disclose, be a kind of new photoelectric material, energy conversion efficiency is high, and preparation method is simple, and productivity is high, and mild condition, product is easy
In control so that it is in field of photovoltaic materials such as polymer solar battery, organic electroluminescent and organic field effect tubes
Have a extensive future.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic solar batteries device in embodiment 8；
Fig. 2 is the structural representation of organic electroluminescence device in embodiment 9；
Fig. 3 is the structural representation of organic field effect tube in embodiment 10.
Detailed description of the invention
The following stated is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications are also considered as
Protection scope of the present invention.
The present invention relates to containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, for having following structural formula
Compound P:
In formula, R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched, R2For
C1～C12Straight or branched alkyl,Described R ' is expressed as C1～C12Straight or branched
Alkyl, n is the integer between 5～60.
Embodiment 1
A kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 1(n=10), structure
Formula is as follows:
Preparation method comprises the following steps:
One, compound 2,6-bis-(tin trimethyl)-4,8-two (4,5-diformazan sulfydryl-1,3-two mercaptan-2-aldehyde) benzene is prepared
And [1,2-b:4,5-b '] two thiophene, it is designated as A1；
(1) compound 4,8-bis-(4,5-diformazan sulfydryl-1,3-two mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two is prepared
Thiophene, is designated as c1:
Compound b1 and a, i.e. 2-dimethoxy phosphono-4,5-diformazan sulfydryl-1,3-bis-mercaptan and benzo [1,2-are provided
B:4,5-b '] two thiophene-4,8-diketone；
Under nitrogen protection, the 60mL anhydrous tetrahydrofuran solution of 1.22g (4.0mmol) b1 is cooled to-78 DEG C, slowly
Add the cyclohexane solution (4mmol) of 2.7mL1.5M LDA, at-78 DEG C after stirring reaction 3h, add 0.44g
(2.0mmol) the 10mL anhydrous tetrahydrofuran solution of a carries out Wittig-Horner reaction, returns to room after insulation reaction 0.5h
Temperature, continues reaction 12h, stopped reaction.Rotation is steamed, and removes the reactant liquor of excess, and the crude on silica gel column chromatography for separation obtained is pure
Change, obtain product c1；Eluant is to obtain after normal hexane and dichloromethane mix with volume ratio for 3:1, and productivity 51%, mass spectrum is surveyed
Test result is MS (EI) m/z:577 (M+);Its reaction equation is as follows:
(2) preparing compound A1, reaction equation is:
Under nitrogen protection, the 60mL anhydrous tetrahydrofuran solution of 1.15g (2.0mmol) c1 is cooled to-78 DEG C, slowly
Add the hexane solution (4.4mmol) of 1.6mL2.5M n-BuLi, at-78 DEG C after stirring reaction 2h, add 1.2mL
(4mmol) Me3SnCl, returns to room temperature after insulation reaction 0.5h, continue reaction 24h, obtain product, i.e. A1, mass spectrometric measurement
Result is MS (EI) m/z:903 (M+)；
Two, preparation polymer B 1, structural formula is as follows:
Compound d and e1, i.e. 2,6-bis-bromo-4-(4-benzaldehyde is provided) and-4H-dithieno [3,2-b:2 ', 3 '-d] pyrrole
Cough up and 3-ethyl-2-sulfur generation-4-oxo tetrahydro-thiazoles；
6.62g (15.0mmol) d and 4.84g (30.0mmol) e1 is joined in ethanol, then drips 1.5mL ammonia, add
Heat is dissolved to solid.Join in reaction bulb with (80 DEG C) distilled water of 2mL heat after 1.0g (19.0mmol) chloride leach,
Reaction 2h it is stirred at reflux at 80 DEG C.After reaction stops, being cooled to room temperature, after reacting liquid filtering, filtering residue is successively with distilled water, ethanol
After washing, then through dehydrated alcohol recrystallization, obtaining product B1, productivity is 67%, and mass spectrometric measurement result is MS (EI) m/z:584 (M+)；
Reaction equation is:
Three, preparing copolymer p 1, reaction equation is as follows:
Under nitrogen protection, 1.8g (2.0mmol) compound A1 and 1.17g (2.0mmol) compound B-11 is joined
In the toluene that 80mL is dried, bubbling 0.5h removes the oxygen of residual, then is rapidly added 0.07g (0.1mmol) Pd (PPh3)2Cl2Shape
Becoming mixed liquor, mixed liquor bubbling 1h removes the oxygen of residual, back flow reaction 30h at 120 DEG C, after reaction terminates, by mixed liquor
Decompression distillation, removes the toluene of excess, then is added drop-wise in methanol settle.Sucking filtration, methanol washs, and is dried.Then oxygen is passed through
Change the column chromatography of aluminum, chloroform drip washing.Distillation, removes organic solvent, and methanol settles.Sucking filtration, gained solid acetone surname extraction
Three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product P1 night.
Copolymer p 1 after purifying carries out gel permeation chromatography (GPC) test, number-average molecular weight Mn ≈ 10000, polymerization
Thing monodispersity is 2.1.
Embodiment 2
A kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 2(n=60), structure
Formula is as follows:
Preparation method comprises the following steps:
One, compound 2,6-bis-(tin trimethyl)-4,8-two (4,5-bis-pungent sulfydryl-1,3-two mercaptan-2-aldehyde) benzene is prepared
And [1,2-b:4,5-b '] two thiophene, it is designated as A2；
(1) compound 4,8-bis-(4,5-bis-pungent sulfydryl-1,3-two mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two is prepared
Thiophene, is designated as c2:
Compound b2 and a, i.e. 2-dimethoxy phosphono-4, pungent sulfydryl-1 of 5-bis-, 3-bis-mercaptan and benzo [1,2-are provided
B:4,5-b '] two thiophene-4,8-diketone；
Under nitrogen protection, the 60mL anhydrous tetrahydrofuran solution of 2.2g (4.4mmol) b2 is cooled to-78 DEG C, slowly
Add the cyclohexane solution (6mmol) of 4.0mL1.5M LDA, at-78 DEG C after stirring reaction 3h, add 0.44g
(2.0mmol) the 10mL anhydrous tetrahydrofuran solution of a carries out Wittig-Horner reaction, returns to room after insulation reaction 0.5h
Temperature, continues reaction 12h, stopped reaction.Rotation is steamed, and removes the reactant liquor of excess, and the crude on silica gel column chromatography for separation obtained is pure
Change, obtain product c2；Eluant is normal hexane and dichloromethane according to volume ratio is to obtain after 3:1 mixing, productivity 53%, mass spectrum
Test result is MS (EI) m/z:970 (M+);Its reaction equation is as follows:
(2) compound A2 is prepared:
Under nitrogen protection, the 60mL anhydrous tetrahydrofuran solution of 1.15g (2.0mmol) c2 is cooled to-78 DEG C, slowly
Add the hexane solution (4.4mmol) of 1.76mL2.5M n-BuLi, at-78 DEG C after stirring reaction 2h, add 1.3mL
(4.4mmol) Me3SnCl, returns to room temperature after insulation reaction 0.5h, continue reaction 24h, obtain product A2, and mass spectrometric measurement is tied
Fruit is MS (EI) m/z:1295 (M+)；
Two, preparation polymer B 2, structural formula is
Compound d and e2, i.e. 2,6-bis-bromo-4-(4-benzaldehyde is provided) and-4H-dithieno [3,2-b:2 ', 3 '-d] pyrrole
Cough up and 3-methyl-2-sulfur generation-4-oxo tetrahydro-thiazoles；
6.62g (15.0mmol) d and 6.05g (37.5mmol) e2 is joined in ethanol, then drips 1.0mL ammonia, add
Heat is dissolved to solid.After 1.15g (21.4mmol) chloride leach, reaction bulb is joined with (80 DEG C) distilled water of 2mL heat
In, it is stirred at reflux reaction 2.5h at 80 DEG C.After reaction stops, being cooled to room temperature, after reacting liquid filtering, filtering residue is successively with distillation
After water, washing with alcohol, then through dehydrated alcohol recrystallization, obtaining product B2, productivity is 66%, and mass spectrometric measurement result is MS (EI) m/
z:570(M+)；
Three, preparing copolymer p 2, reaction equation is as follows:
Under nitrogen protection, 2.85g (2.2mmol) A2 and 1.14g (2.0mmol) B2 is joined 80mL anhydrous tetrahydrochysene furan
In muttering, bubbling 0.5h removes the oxygen of residual, then is rapidly added 46.2mg (0.04mmol) Pd (PPh3)4, bubbling 1h removes residual
Oxygen, back flow reaction 72h at 60 DEG C, by mixed liquor decompression distillation, remove the oxolane of excess, then be added drop-wise in methanol enter
Row sedimentation.Sucking filtration, methanol washs, and is dried.Then by the column chromatography of aluminium oxide, chloroform drip washing.Distillation, removes organic solvent,
Methanol settles.Sucking filtration, gained solid acetone surname extraction three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product night
P2。
Copolymer p 2 after purifying carries out GPC test, number-average molecular weight Mn ≈ 82680, and polymer monodispersity is
1.9。
Embodiment 3
A kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 3(n=30), structure
Formula is as follows:
Preparation method comprises the following steps:
One, compound 2,6-bis-(tin trimethyl)-4,8-two (4,5-bis-(16 sulfydryl)-1,3-two mercaptan-2-is prepared
Aldehyde) and benzo [1,2-b:4,5-b '] two thiophene, it is designated as A3；
(1) compound 4,8-bis-(4,5-bis-(16 sulfydryl)-1,3-two mercaptan-2-aldehyde) benzo [1,2-b:4,5-is prepared
B '] two thiophene, it is designated as c3:
Compound b3 and a, i.e. 2-dimethoxy phosphono-4,5-bis-(16 sulfydryl)-1,3-bis-mercaptan and benzo are provided
[1,2-b:4,5-b '] two thiophene-4,8-diketone；
Under argon shield, the 60mL anhydrous tetrahydrofuran solution of 2.18g (3.0mmol) b3 is cooled to-78 DEG C, slowly
Add the cyclohexane solution (4.5mmol) of 3.0mL1.5M LDA, at-78 DEG C after stirring reaction 2h, add 0.264g
(1.2mmol) the 15mL anhydrous tetrahydrofuran solution of a carries out Wittig-Horner reaction, returns to room temperature after insulation reaction 1h,
Continue reaction 15h, stopped reaction.Rotation is steamed, and removes the oxolane of excess, and the crude on silica gel column chromatography for separation obtained is pure
Change, obtain product c3；Eluant is normal hexane and dichloromethane according to volume ratio is to obtain after 4:1 mixing, productivity 53%, MS
(EI)m/z:1419(M+);Its reaction equation is as follows:
(2) preparing compound A-13, reaction equation is:
Under nitrogen protection, the 60mL anhydrous tetrahydrofuran solution of 2.84g (2.0mmol) c3 is cooled to-78 DEG C, slowly
Add the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, at-78 DEG C after stirring reaction 3h, add 1.5mL
(5.0mmol) Me3SnCl, returns to room temperature after insulation reaction 1h, continue reaction 23h, obtain product, i.e. A3, mass spectrometric measurement
Result is MS (EI) m/z:1744 (M+)；
Two, preparation polymer B 3, structural formula is
Compound d and e3, i.e. 2,6-bis-bromo-4-(4-benzaldehyde is provided) and-4H-dithieno [3,2-b:2 ', 3 '-d] pyrrole
Cough up and 3-dodecyl-2-sulfur generation-4-oxo tetrahydro-thiazoles；
6.62g (15.0mmol) d and 9.06g (30.0mmol) e3 is joined in ethanol, then drips 0.9mL ammonia, add
Heat is dissolved to solid.After 0.89g (16.67mmol) chloride leach, reaction bulb is joined with (80 DEG C) distilled water of 2mL heat
In, it is stirred at reflux reaction 3h at 80 DEG C.Reaction stop after, be cooled to room temperature, after reacting liquid filtering, filtering residue successively with distilled water,
After washing with alcohol, then through dehydrated alcohol recrystallization, obtaining product B3, productivity is 68%, and mass spectrometric measurement result is MS (EI) m/z:
725(M+)；Reaction equation is:
Three, preparing copolymer p 3, reaction equation is as follows:
Under nitrogen protection, 4.36g (2.5mmol) A3 and 1.45g (2.0mmol) B3 is joined 80Ml and be dried N, N-bis-
In methylformamide, bubbling 0.5h removes the oxygen of residual, then is rapidly added 46.2mg (0.04mmol) Pd (PPh3)4Formed mixed
Close liquid, mixed liquor bubbling 1h is removed the oxygen of residual, back flow reaction 24h at 80 DEG C, after reaction terminates, mixed liquor decompression is steamed
Evaporate, remove the DMF of excess, then be added drop-wise in methanol settle.Sucking filtration, methanol washs, and is dried.Then
By the column chromatography of aluminium oxide, chloroform drip washing.Distillation, removes organic solvent, and methanol settles.Sucking filtration, gained solid acetone rope
Family name extracts three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product P3 night.
Copolymer p 3 after purifying carries out GPC test, number-average molecular weight Mn ≈ 59430, and polymer monodispersity is
1.9。
Embodiment 4
A kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 4(n=15), structure
Formula is as follows:
Preparation method comprises the following steps:
One, compound 2,6-bis-(tin trimethyl)-4,8-two (4,5-dimethyl-1,3-two mercaptan-2-aldehyde) benzo is prepared
[1,2-b:4,5-b '] two thiophene, it is designated as A4；
(1) compound 4,8-bis-(4,5-dimethyl-1,3-two mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophenes are prepared
Fen, is designated as c4:
Compound b4 and a be provided, i.e. 2-dimethoxy phosphono-4,5-dimethyl-1,3-bis-mercaptan and benzo [1,2-b:
4,5-b '] two thiophene-4,8-diketone；
Under argon shield, the 50mL anhydrous tetrahydrofuran solution of 1.2g (5.0mmol) b4 is cooled to-78 DEG C, slowly
Add the cyclohexane solution (6.0mmol) of 2.0mL3M LDA, at-78 DEG C after stirring reaction 3h, add 0.46g
(2.1mmol) the 10mL anhydrous tetrahydrofuran solution of a carries out Wittig-Horner reaction, returns to room after insulation reaction 0.5h
Temperature, continues reaction 12h, stopped reaction.Rotation is steamed, and removes the oxolane of excess, the crude on silica gel column chromatography for separation obtained
Purification, obtains product c4；Eluant is normal hexane and dichloromethane according to volume ratio is to obtain after 4:1 mixing, productivity 53%, matter
Spectrum test result is MS (EI) m/z:449 (M+);Its reaction equation is as follows:
(2) compound A4 is prepared:
Under nitrogen protection, the 40mL anhydrous tetrahydrofuran solution of 0.90g (2.0mmol) c4 is cooled to-78 DEG C, slowly
Add the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, at-78 DEG C after stirring reaction 2.5h, add 1.5mL
(5.0mmol) Me3SnCl, returns to room temperature after insulation reaction 0.7h, continue reaction 20h, obtain product, i.e. A4, and mass spectrum is surveyed
Test result is MS (EI) m/z:774 (M+)；
Two, preparation polymer B 4, structural formula is as follows:
Compound d and e4, i.e. 2,6-bis-bromo-4-(4-benzaldehyde is provided) and-4H-dithieno [3,2-b:2 ', 3 '-d] pyrrole
Cough up and 3-(4-Nitrobenzol)-2-sulfur generation-4-oxo tetrahydro-thiazoles；
6.62g (15.0mmol) d and 9.525g (37.5mmol) e4 is joined in ethanol, then drips 0.75mL ammonia,
It is heated to solid to dissolve.After 1.0g (18.75mmol) chloride leach, reaction bulb is joined with (80 DEG C) distilled water of 2mL heat
In, it is stirred at reflux reaction 2h at 80 DEG C.Reaction stop after, be cooled to room temperature, after reacting liquid filtering, filtering residue successively with distilled water,
After washing with alcohol, then through dehydrated alcohol recrystallization, obtaining product B4, productivity is 61%, and mass spectrometric measurement result is MS (EI) m/z:
677(M+)；Its reaction equation is as follows:
Three, preparing copolymer p 4, reaction equation is as follows:
Under argon shield, 0.93g (1.2mmol) A4 and 0.54g (0.8mmol) B4 is joined 80mL and is dried N, N-bis-
In methylformamide, bubbling 0.5h removes the oxygen of residual, then is rapidly added catalyst Pd2(dba)3(0.073mg, 8 × 10- 5And P (o-Tol) mmol)3(0.00486mg, 1.6 × 10-4Mmol) form mixed liquor, mixed liquor bubbling 1h is removed residual
Oxygen, back flow reaction 30h at 80 DEG C, after reaction terminates, by mixed liquor decompression distillation, remove N, the N-dimethyl formyl of excess
Amine, then be added drop-wise in methanol settle.Sucking filtration, methanol washs, and is dried.Then by the column chromatography of aluminium oxide, chloroform drip washing.
Distillation, removes organic solvent, and methanol settles.Sucking filtration, gained solid acetone surname extraction three days.Methanol settles, sucking filtration.Vacuum
It is pumped through under pump and obtains product P4 night.
Copolymer p 4 after purifying carries out GPC test, number-average molecular weight Mn ≈ 14460, and polymer monodispersity is
1.7。
Embodiment 5
A kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 5(n=18), structure
Formula is as follows:
Preparation method comprises the following steps:
One, compound 2,6-bis-(tin trimethyl)-4,8-two (4,5-dihexyl-1,3-two mercaptan-2-aldehyde) benzo is prepared
[1,2-b:4,5-b '] two thiophene, it is designated as A5；
(1) compound 4,8-bis-(4,5-dihexyl-1,3-two mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophenes are prepared
Fen, is designated as c5:
Compound b5 and a be provided, i.e. 2-dimethoxy phosphono-4,5-dihexyl-1,3-bis-mercaptan and benzo [1,2-b:
4,5-b '] two thiophene-4,8-diketone；
Under argon shield, the 45mL anhydrous tetrahydrofuran solution of 0.76g (2.0mmol) b5 is cooled to-78 DEG C, slowly
Add the cyclohexane solution (3.0mmol) of 2.0mL1.5M LDA, finish, at-78 DEG C after stirring reaction 3h, add 0.22g
(1.0mmol) the 6mL anhydrous tetrahydrofuran solution of a carries out Wittig-Horner reaction, returns to room after insulation reaction 0.5h
Temperature, continues reaction 12h, stopped reaction.Rotation is steamed, and removes the oxolane of excess, the crude on silica gel column chromatography for separation obtained
Purification, obtains product c5；Eluant is normal hexane and dichloromethane according to volume ratio is to obtain after 4:1 mixing, productivity 49%, matter
Spectrum test result MS (EI) m/z:729 (M+);Its reaction equation is as follows:
(2) compound A-45 is prepared:
Under nitrogen protection, the 60mL anhydrous tetrahydrofuran solution of 1.6g (2.2mmol) c5 is cooled to-78 DEG C, slowly
Add the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, at-78 DEG C after stirring reaction 2h, add 1.5mL
(5.0mmol) Me3SnCl, returns to room temperature after insulation reaction 0.5h, continue reaction 24h, obtain product, i.e. A5, and mass spectrum is surveyed
Test result is MS (EI) m/z:1055 (M+)；
Two, preparation polymer B 5, structural formula is
Compound d and e5, i.e. 2,6-bis-bromo-4-(4-benzaldehyde is provided) and-4H-dithieno [3,2-b:2 ', 3 '-d] pyrrole
Cough up and 3-(4-cyano group benzene)-2-sulfur generation-4-oxo tetrahydro-thiazoles；
6.62g (15.0mmol) d and 7.90g (33.75mmol) e5 is joined in ethanol, then drips 0.75mL ammonia,
It is heated to solid to dissolve.After 1.0g (18.75mmol) chloride leach, reaction bulb is joined with (80 DEG C) distilled water of 2mL heat
In, it is stirred at reflux reaction 2h at 80 DEG C.Reaction stop after, be cooled to room temperature, after reacting liquid filtering, filtering residue successively with distilled water,
After washing with alcohol, then through dehydrated alcohol recrystallization, obtaining product B5, productivity is 53%, mass spectrometric measurement result MS (EI) m/z:657
(M+)；
Reaction equation is:
Three, preparing copolymer p 5, reaction equation is as follows:
Under nitrogen protection, 2.11g (2.0mmol) A5 and 1.18g (1.8mmol) B5 is joined 80mL dry toluene
In, bubbling 0.5h removes the oxygen of residual, then is rapidly added catalyst Pd2(dba)3(16.5mg, 0.018mmol) and P (o-
Tol)3(54.8mg, 0.18mmol) forms mixed liquor, and mixed liquor bubbling 1h removes the oxygen of residual, back flow reaction at 110 DEG C
36h, after reaction terminates, by mixed liquor decompression distillation, removes the toluene of excess, then is added drop-wise in methanol settle.Sucking filtration, first
Alcohol washs, and is dried.Then by the column chromatography of aluminium oxide, chloroform drip washing.Distillation, removes organic solvent, and methanol settles.Sucking filtration,
Gained solid acetone surname extraction three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product P5 night.
Copolymer p 5 after purifying carries out GPC test, number-average molecular weight Mn ≈ 22050, and polymer monodispersity is
2.4。
Embodiment 6
A kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 6(n=20), structure
Formula is as follows:
Preparation method comprises the following steps:
One, compound 2,6-bis-(tin trimethyl)-4,8-two (4,5-bis-(cetyl)-1,3-two mercaptan-2-is prepared
Aldehyde) and benzo [1,2-b:4,5-b '] two thiophene, it is designated as A6；
(1) compound 4,8-bis-(4,5-bis-(cetyl)-1,3-two mercaptan-2-aldehyde) benzo [1,2-b:4,5-is prepared
B '] two thiophene, it is designated as c6:
Compound b6 and a, i.e. 2-dimethoxy phosphono-4,5-bis-(cetyl)-1,3-bis-mercaptan and benzo are provided
[1,2-b:4,5-b '] two thiophene-4,8-diketone；
Under argon shield, the 60mL anhydrous tetrahydrofuran solution of 1.32g (2.0mmol) b6 is cooled to-78 DEG C, slowly
Add the cyclohexane solution (3.0mmol) of 2.0mL1.5M LDA, at-78 DEG C after stirring reaction 2.5h, add 0.22g
(1.0mmol) the 10mL anhydrous tetrahydrofuran solution of a carries out Wittig-Horner reaction, returns to room after insulation reaction 0.7h
Temperature, continues reaction 13h, stopped reaction.Rotation is steamed, and removes the oxolane of excess, the crude on silica gel column chromatography for separation obtained
Purification, obtains product c6；Eluant is normal hexane and dichloromethane according to volume ratio is to obtain after 4:1 mixing, productivity 47%, MS
(EI)m/z:1290(M+);Its reaction equation is as follows:
(2) compound A6 is prepared:
Under nitrogen protection, the 60mL anhydrous tetrahydrofuran solution of 2.58g (2.0mmol) c6 is cooled to-78 DEG C, slowly
Add the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, at-78 DEG C after stirring reaction 2h, add 1.5mL
(5.0mmol) Me3SnCl, returns to room temperature after insulation reaction 0.5h, continue reaction 24h, obtain product, i.e. A6, and mass spectrum is surveyed
Test result is MS (EI) m/z:1616 (M+)；
Two, preparation polymer B 6, structural formula is:
Compound d and e6, i.e. 2,6-bis-bromo-4-(4-benzaldehyde is provided) and-4H-dithieno [3,2-b:2 ', 3 '-d] pyrrole
Cough up and 3-methyl acetate-2-sulfur generation-4-oxo tetrahydro-thiazoles；
6.62g (15.0mmol) d and 6.16g (30.0mmol) e6 is joined in ethanol, then drips 0.75mL ammonia, add
Heat is dissolved to solid.After 1.0g (18.75mmol) chloride leach, reaction bulb is joined with (80 DEG C) distilled water of 2mL heat
In, it is stirred at reflux reaction 2h at 80 DEG C.Reaction stop after, be cooled to room temperature, after reacting liquid filtering, filtering residue successively with distilled water,
After washing with alcohol, then through dehydrated alcohol recrystallization, obtaining product B6, productivity is 63%, mass spectrometric measurement result MS (EI) m/z:628
(M+)；Reaction equation is:
Three, preparing copolymer p 6, reaction equation is as follows:
Under nitrogen protection, 1.938g (1.2mmol) A6 and 0.50g (0.8mmol) B6 is joined 80mL dry toluene
In, bubbling 0.5h removes the oxygen of residual, then is rapidly added catalyst Pd2(dba)3(0.073mg, 8 × 10-5And P (o-mmol)
Tol)3(0.00486mg, 1.6 × 10-4Mmol) form mixed liquor, mixed liquor bubbling 1h is removed the oxygen of residual, at 110 DEG C
Back flow reaction 30h, after reaction terminates, by mixed liquor decompression distillation, removes the toluene of excess, then is added drop-wise in methanol sink
Fall.Sucking filtration, methanol washs, and is dried.Then by the column chromatography of aluminium oxide, chloroform drip washing.Distillation, removes organic solvent, methanol
Sedimentation.Sucking filtration, gained solid acetone surname extraction three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product P6 night.
Copolymer p 6 after purifying carries out GPC test, number-average molecular weight Mn ≈ 35140, and polymer monodispersity is
2.2。
Embodiment 7
A kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 7(n=5), structural formula
As follows:
Preparation method comprises the following steps:
One, compound 2,6-bis-(tin trimethyl)-4,8-two (1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-is prepared
B '] two thiophene, it is designated as A7；
(1) compound 4 is prepared, 8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene, it is designated as c7:
Compound b7 and a be provided, i.e. 2-dimethoxy phosphono-1,3-bis-mercaptan and benzo [1,2-b:4,5-b '] two thiophenes
Fen-4,8-diketone；
Under argon shield, the 40mL anhydrous tetrahydrofuran solution of 0.42g (2.0mmol) b7 is cooled to-78 DEG C, slowly
Add the cyclohexane solution (3.0mmol) of 2.0mL1.5M LDA, at-78 DEG C after stirring reaction 3h, add 0.22g
(1.0mmol) the 10mL anhydrous tetrahydrofuran solution of a carries out Wittig-Horner reaction, returns to room after insulation reaction 0.5h
Temperature, continues reaction 12h, stopped reaction.Rotation is steamed, and removes the oxolane of excess, the crude on silica gel column chromatography for separation obtained
Purification, obtains product c7；Eluant is to obtain after normal hexane and dichloromethane mix for 5:1 by volume, productivity 55%, mass spectrum
Test result MS (EI) m/z:393 (M+);Its reaction equation is as follows:
(2) preparing compound A7, reaction equation is:
Under nitrogen protection, the 40mL anhydrous tetrahydrofuran solution of 0.79g (2.0mmol) c7 is cooled to-78 DEG C, slowly
Add the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, at-78 DEG C after stirring reaction 2h, add 1.5mL
(5.0mmol) Me3SnCl, returns to room temperature after insulation reaction 0.5h, continue reaction 24h, obtain product, i.e. A7, and mass spectrum is surveyed
Test result MS (EI) m/z:718 (M+)；
Two, preparation polymer B 7, structural formula is
Compound d and e7, i.e. 2,6-bis-bromo-4-(4-benzaldehyde is provided) and-4H-dithieno [3,2-b:2 ', 3 '-d] pyrrole
Cough up and 3-dodecyl acetate-2-sulfur generation-4-oxo tetrahydro-thiazoles；
6.62g (15.0mmol) d and 10.8g (30.0mmol) e7 is joined in ethanol, then drips 0.75mL ammonia, add
Heat is dissolved to solid.After 1.0g (18.75mmol) chloride leach, reaction bulb is joined with (80 DEG C) distilled water of 2mL heat
In, it is stirred at reflux reaction 2h at 80 DEG C.Reaction stop after, be cooled to room temperature, after reacting liquid filtering, filtering residue successively with distilled water,
After washing with alcohol, then through dehydrated alcohol recrystallization, obtaining product B7, productivity is 61%, and mass spectrometric measurement result is MS (EI) m/z:
783(M+)；
Reaction equation is:
Three, preparing copolymer p 7, reaction equation is as follows:
Under nitrogen protection, 1.44g (2.0mmol) A7 and 1.57g (2.0mmol) B7 is joined 80mL and be dried N, N-bis-
In methylformamide, bubbling 0.5h removes the oxygen of residual, then is rapidly added catalyst Pd2(dba)3(7.3mg, 0.008mmol)
With P (o-Tol)3(48.6mg, 0.16mmol) forms mixed liquor, and mixed liquor bubbling 1h removes the oxygen of residual, and 80 DEG C next time
Stream reaction 30h, after reaction terminates, by mixed liquor decompression distillation, removes the DMF of excess, then is added drop-wise to methanol
In settle.Sucking filtration, methanol washs, and is dried.Then by the column chromatography of aluminium oxide, chloroform drip washing.Distillation, removes organic molten
Agent, methanol settles.Sucking filtration, gained solid acetone surname extraction three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains night
Product P7.
Copolymer p 7 after purifying carries out GPC test, number-average molecular weight Mn ≈ 5056, and monodispersity is 1.92.
Embodiment 8
With the embodiment of the present invention 3 preparation containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers P3 as activity
Layer, prepares organic solar batteries device, including the substrate of glass 1 stacked gradually, anode 2, middle auxiliary layer 3, active layer 4 He
Negative electrode 5, this device architecture specifically can be briefly described as: substrate of glass/anode/centre auxiliary layer/active layer/negative electrode, sees Fig. 1.
Wherein, anode 2 is ITO(tin indium oxide), the material of middle auxiliary layer 3 uses poly-(3,4-Ethylenedioxy Thiophene) (PEDOT)
With the composite of polystyrolsulfon acid (PSS), it is called for short PEDOT:PSS；Active layer 4 includes electron donor material and electron acceptor
Material, the material of electron donor is being total to containing thioxothiazole-dithieno pyrroles-benzene 1,4-Dithiapentalene of the embodiment of the present invention 3 preparation
Polymers P3, the material of electron acceptor is [6,6] phenyl-C61-methyl butyrate (being called for short PCBM)；The material of negative electrode 5 is aluminum.
Wherein, substrate of glass 1, as bottom, chooses ito glass (with anode ITO layer, commercially available), Jing Guochao during making
After sound wave cleans, process with oxygen plasma (oxygen-Plasma), to improve its work function；Then auxiliary in the middle of coating on ito glass
Help a layer 3PEDOT:PSS, after P3 and PCBM is mixed for 1:1 with mass ratio, be spun on PEDOT:PSS film layer, obtain active layer
4；Evaporation cathode metallic aluminium 5 under vacuum, obtains organic solar batteries device.
By the I-E characteristic of Keithley236 current/voltage source-measurement system test device, obtain device
Performance data is shown in Table 1.
Table 1 preparing for active layer containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers P3 with the present invention
The performance data of organic solar batteries device
As seen from the data in Table 1, with the present invention containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers conduct
The energy conversion efficiency of organic solar batteries device prepared by active layer is 1.53%.Show the present invention containing thioxothiazole-two
Thienopyrroles-benzene 1,4-Dithiapentalene contains 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene-based and spreads out
Biology, dithieno pyrrole unit and thioxothiazole unit, by 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-
B '] two thiophene derivants and dithieno pyrroles's donor monomer are as main polymer chain, and using thioxothiazole as receptor list
Unit is articulated on side chain, by main chain with side chain to the interaction of this in receptor " push-pull electronics ", adds master interchain shape
The two-dimentional conjugated system become, reduces the energy gap of conjugated polymer simultaneously, substantially increases the light abstraction width of material, improves light
Electricity transformation efficiency.
Embodiment 9
With embodiment 1 preparation containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers P1 as luminescent layer, system
Have organic electroluminescence devices, including the glass substrate 01 stacked gradually, transparent anode 02, luminescent layer 03, cathode buffer layer 04
With negative electrode 05, this device architecture specifically can be briefly described as: substrate of glass/transparent anode/luminescent layer/cathode buffer layer/negative electrode,
See Fig. 2, but the structure of practical devices is not limited to this.Wherein, transparent anode 02 material is tin indium oxide (ITO), luminescent layer 03 material
Matter is the copolymer p 1 of the embodiment of the present invention 1 preparation, uses spin coating technique to prepare luminescent layer on ITO, cathode buffer layer 04
Material is lithium fluoride (LiF), and the material of negative electrode 05 is metallic aluminium, and the preparation method of each layer is carried out by existing spin coating method,
To organic electroluminescence device.
Measured system (Keithley2400Sourcemeter) by Keithley source and test above-mentioned organic electroluminescence device
Current versus brightness-voltage characteristic, with France JY company SPEX its electroluminescent spectrum of CCD3000 spectrometer measurement, all surveys
Amount all completes in atmosphere at room temperature, and the high-high brightness efficiency recording organic electroluminescence device is 2.13cd/A, and high-high brightness is
1090cd/m2。
Embodiment 10
With embodiment 5 preparation copolymer p 5 as organic semiconductor layer, prepare organic field effect tube, its structure as figure
Shown in 3, including the substrate 001 stacked gradually, insulating barrier 002, decorative layer 003, organic semiconductor layer 004, source electrode (S) 005
And drain electrode (D) 006.This device architecture specifically can be briefly described as: substrate/insulating barrier/decorative layer/organic semiconductor layer/source
Electrode/drain electrode, wherein, the material of substrate 001 can be but not limited to highly doped silicon chip (Si), the material of insulating barrier 002
The SiO that thickness is 450nm can be but not limited to2, the material of decorative layer 003 can be but not limited to octadecyl trichlorosilane alkane
(OTS), the material of organic semiconductor layer 004 is the copolymer of the embodiment of the present invention 5 preparation, source electrode (S) 005 and drain electrode
(D) 006 all use gold as electrode.
By time-of-flight method (Time of Flight, TOF), 7.0 × 105Vcm-1Electric field in test containing this
The mean void mobility of the organic field effect tube of the copolymer p 5 of bright embodiment 5 preparation is 1.32 × 10-4m2/ Vs, table
Hole transport performance containing thioxothiazole-dithieno pyrroles-benzo two thiophen polymer prepared by the bright present invention.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (10)
1. one kind contains thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, it is characterised in that for having following structure
The copolymer p of formula:
In formula, R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched, R2For C1~
C12Straight or branched alkyl,Described R ' is expressed as C1～C12Straight or branched
Alkyl, n is the integer between 5～60.
2. the preparation method containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers, it is characterised in that include
Following operating procedure:
Compound A and B that following structural formula represents is provided respectively,
In formula, R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched, R2For C1~
C12Straight or branched alkyl,Described R ' is expressed as C1～C12Straight or branched
Alkyl；
In atmosphere of inert gases, compound A and the compound B that mol ratio is 1:1～1.5:1 is added in the first organic solvent
Dissolving, then add catalyst formation mixed liquor in the first organic solvent, this mixed liquor carries out Stille coupling at 60～120 DEG C
Closing reaction 24～72 hours, after stopped reaction, isolated and purified obtain copolymer p, the structural formula of this copolymer p is as follows:
In formula, n is the integer between 5～60；
Reaction equation is:
3. the preparation method containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers as claimed in claim 2, its
Being characterised by, described catalyst is the mixture of organic palladium or organic palladium and organophosphorus ligand.
4. the preparation method containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers as claimed in claim 3, its
Being characterised by, described organic palladium is double (triphenylphosphine) palladium chloride or tetrakis triphenylphosphine palladium, described organic palladium and organic phosphine
The mixture of part is three (dibenzalacetone) two palladium and the mixture of three (2-tolyl) phosphine；
Rubbing of described organic palladium and three (dibenzalacetone) in the mixture of organophosphorus ligand two palladium and three (2-tolyl) phosphines
That ratio is 1:2～1:20.
5. the preparation method containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers as claimed in claim 3, its
Being characterised by, the mole dosage of described organic palladium is the 0.01%～5% of compound B mole dosage.
6. the preparation method containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers as claimed in claim 2, its
Being characterised by, described first organic solvent is oxolane, DMF or toluene.
7. the preparation method containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers as claimed in claim 2, its
Being characterised by, described isolation and purification method is:
After the completion of reaction, by the decompression distillation of copolymer p reactant liquor, remove the first organic solvent of excess, then be added drop-wise to methanol
In settle, sucking filtration, methanol wash, be dried；Then by column chromatography, chloroform drip washing；Distillation, removes organic solvent, methanol
Sedimentation, sucking filtration, with acetone surname extraction for several times, methanol settles gained solid, and sucking filtration is pumped through under vacuum pump and obtains product night.
8. the preparation method containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers as claimed in claim 2, its
Being characterised by, described compound A can be prepared by following methods:
(1) compound a and compound b that following structural formula represents be provided respectively:
R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched；
In atmosphere of inert gases, the anhydrous tetrahydrofuran solution of compound b is cooled to-78 DEG C, is slowly added to diisopropyl
The cyclohexane solution of amido lithium, at-78 DEG C after stirring reaction 2～3h, adds the tetrahydrofuran solution of compound a, carries out
Wittig-Horner reacts, and returns to room temperature after insulation reaction 0.5～1h, continues reaction 12～15h, obtains product, i.e. chemical combination
Thing c；Wherein, the mol ratio of lithium diisopropyl amido and b be the mol ratio of 1:1～1.5:1, a and b be 1:2.0～1:2.5, its
Reaction equation is as follows:
(2) in atmosphere of inert gases, the anhydrous tetrahydrofuran solution of compound c is cooled to-78 DEG C, is slowly added to normal-butyl
The hexane solution of lithium, then stirring reaction 2～3h at-78 DEG C, add trimethyl ammonia chloride tin reagent, insulation reaction 0.5
～after 1h, return to room temperature, continue reaction 20～24h, obtain product, i.e. compound A；Wherein, n-BuLi and the mol ratio of c
For 2.2:1～2.5:1, trimethyltin chloride is 2.0:1～2.5:1 with the mol ratio of c, and its reaction equation is as follows:
9. the preparation method containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers as claimed in claim 2, its
Being characterised by, described compound B can be prepared by following methods:
Compound d and compound e that following structural formula represents be provided respectively:
By compound d and compound e, with mol ratio as 1:2～1:2.5 joins in the second organic solvent, drips ammonia, then
It is heated to solid to dissolve, adds ammonium chloride solution, be then stirred at reflux reaction 2～3h at 80 DEG C, after reaction stops, being produced
Thing B, wherein, the ratio of described compound d and ammonia is that 1mol compound d needs 0.05～0.1L ammonia, compound d and ammonium chloride
Mol ratio be 0.7:1～0.9:1, reaction equation is as follows:
10. thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers that contains as claimed in claim 1 is at the polymer sun
Application in energy battery, organic electroluminescence device and organic field effect tube.
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