CN104045818B - A kind of containing allene contracting thiourea-carbazole-benzo two thiophene copolymers and preparation method and application - Google Patents
A kind of containing allene contracting thiourea-carbazole-benzo two thiophene copolymers and preparation method and application Download PDFInfo
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- 0 **(C(*(C(C1=C)=O)N=*)=[Au])C1=O Chemical compound **(C(*(C(C1=C)=O)N=*)=[Au])C1=O 0.000 description 5
- JRPWSFGPJTWBBP-UHFFFAOYSA-N C=[Br]c(cc1)cc2c1c(ccc(Br)c1)c1[n]2-c1ccc(C=O)cc1 Chemical compound C=[Br]c(cc1)cc2c1c(ccc(Br)c1)c1[n]2-c1ccc(C=O)cc1 JRPWSFGPJTWBBP-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Cc1ccc(C)cc1 Chemical compound Cc1ccc(C)cc1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a kind of containing allene contracting thiourea-carbazole-benzo two thiophene copolymers and preparation method and application, and described is the compound P with following structural formula, wherein, R containing allene contracting thiourea-carbazole-benzo two thiophene copolymers1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched, R2For C1～C12The alkyl of straight or branched, n is the integer between 5～60.Described contain 4 containing allene contracting thiourea-carbazole-benzo two thiophene copolymers, 8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants, carbazole unit and allene contracting thiourea unit, high with the matching degree of solar spectrum, it it is planar conjugate structure simultaneously, carrier mobility speed is high, improves energy conversion efficiency, has good application prospect in polymer solar battery, organic electroluminescent and organic field effect tube field.
Description
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of containing allene contracting thiourea-carbazole-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.Mesh
Before the silicon solar cell that has been commercialized due to complex manufacturing, cost high, application is restricted.In order to
Reducing cost, expansive approach scope, people always search for novel solar cell material for a long time.
Polymer solar battery is coated with because low in raw material price, light weight, flexibility, production technology are simple, available
The mode large area such as cloth, printing the advantage such as is prepared and is had superior market prospect.From N.S. in 1992
Sariciftci etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science,
1992,258,1474) upper report conjugated polymer and C60Between Photo-induced electron transfer phenomenon after, people
In terms of polymer solar battery, put into numerous studies, 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,
It needs possess following characteristics: the dissolubility that (a) is good, beneficially solvent processing, it is achieved industrialized production；
B () has width and strong absorption to whole sunlight spectrum；C carrier mobility that () is high, beneficially carrier pass
Defeated.The most how to widen the light abstraction width of polymeric material so that it is light abstraction width farthest covers
Whole sunlight spectrum will be the emphasis of research.
Summary of the invention
For solving the problems referred to above, it is total to it is desirable to provide a kind of containing allene contracting thiourea-carbazole-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-based are spread out
Biology, carbazole unit and allene contracting thiourea unit, by 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo
[1,2-b:4,5-b '] two thiophene derivants and carbazole donor monomer are as main polymer chain, and by allene contracting sulfur
Ureas dyestuff is articulated on side chain as by body unit, by main chain with side chain to " push-pull electricity this in receptor
Son " interaction, add the two-dimentional conjugated system that master interchain is formed, reduce conjugated polymer simultaneously
Energy gap, substantially increase the light abstraction width of material.The present invention also aims to provide above-mentioned allene
The preparation method and application of contracting thiourea-carbazole-benzo two thiophene copolymers.
First aspect, the present invention provides a kind of containing allene contracting thiourea-carbazole-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 of straight or branched
Sulfydryl, R2For C1～C12The alkyl of straight or branched, 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 at organic electronic etc.
The application in field, 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 flatness, therefore polymer based on it tool
There is good carrier mobility.And 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene-based
Derivant is in benzo [1,2-b:4,5-b '] two thiophene-4, the 4 of 8-diketone, and 8 introduce 1, and 3-bis-mercaptan-2-aldehydes spreads out
Biological.1,3-bis-mercaptan-2-aldehyde derivative is as the good electron donor material of a class, and its introducing is further
Strengthen benzo [1,2-b:4,5-b '] two thiophene derivants to Electronic Performance.Therefore, just because of 4,8-bis-
Electronics and geometry that (1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants have itself are special
Property, the application that it will expand in polymer solar battery as excellent donor monomer.
By 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants and carbazole donor list
Unit is as main polymer chain, and using allene contracting Thiourea dyestuff as being articulated on side chain by body unit, leads to
Cross main chain and side chain to the interaction of this in receptor " push-pull electronics ", add that master interchain is formed two
Dimension conjugated system, reduces the energy gap of conjugated polymer simultaneously, substantially increases the light abstraction width of material.
Second aspect, the present invention provides a kind of preparation containing allene contracting thiourea-carbazole-benzo two thiophene copolymers
Method, including following operating procedure:
(1) polymer B is prepared;
Compound A and compound d that following structural formula represents be provided respectively:
In formula, R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl of straight or branched
Sulfydryl；
In atmosphere of inert gases, compound A and the compound d that mol ratio is 1:1～1.5:1 is added first
Dissolving in organic solvent, be subsequently adding catalyst and form mixed liquor, this mixed liquor carries out Stille at 60～120 DEG C
Coupled reaction 24～72 hours, after stopped reaction, isolated and purified obtain polymer B, the knot of this polymer B
Structure formula is as follows:
In formula, R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl of straight or branched
Sulfydryl, n is the integer between 5～60；
Reaction equation is:
(2) copolymer p is prepared；
Thering is provided compound e, structural formula is:R in formula2For C1～C12The alkane of straight or branched
Base；
Mol ratio 1:20～the polymer B of 1:25 and compound e are joined in the second organic solvent, drips pyrrole
After pyridine, under the conditions of 30～40 DEG C of lucifuges, stirring reaction 20～24h, after stopped reaction, isolated and purified is total to
Polymers P, reaction equation is:
In formula, R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl of straight or branched
Sulfydryl, R2For C1～C12The alkyl of straight or branched, n is the integer between 5～60.
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 (triphens
Base phosphine) palladium (Pd (PPh3)4), described organic palladium is three (dibenzalacetones) two with the mixture of organophosphorus ligand
Palladium (Pd2(dba)3) and three (2-tolyl) phosphine (P (o-Tol)3) mixture, described organic palladium and organic phosphine
Pd in the mixture of part2(dba)3With P (o-Tol)3Mol ratio is 1:2～1:20.
Preferably, the mole dosage of described organic palladium is the 0.01%～5% of compound d mole dosage.
Preferably, described first organic solvent is in oxolane, DMF and toluene
Kind.
Preferably, described noble gas is nitrogen or argon.
Preferably, described second organic solvent is chloroform.
Preferably, the ratio of described polymer B and pyridine is that 1mol polymer B needs 2.8～3L pyridines.
Preferably, step (1) described isolation and purification method is: after the completion of reaction, polymer B is reacted
Liquid decompression distillation, removes the first organic solvent of excess, then is added drop-wise in methanol settle, sucking filtration, first
Alcohol washs, and is dried；Then by column chromatography, chloroform drip washing, distillation, remove organic solvent, methanol settles,
Sucking filtration, with acetone surname extraction for several times, methanol settles gained solid, sucking filtration.It is pumped through under vacuum pump and obtains night
Product.
Preferably, step (2) described isolation and purification method is: by the decompression distillation of copolymer p reactant liquor, remove
Remove the second organic solvent of excess, then pour in methanol, generate a large amount of precipitation, then filter, obtain crude product；
After being dissolved with chloroform by crude product, after Teflon filtration membrane filtration, rotation is steamed again, and removes major part chlorine
Imitative, then be slowly dropped in methanol and settle, sucking filtration, it is pumped through under vacuum pump and obtains product night.
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, slowly
Add the cyclohexane solution of lithium diisopropyl amido (LDA), at-78 DEG C after stirring reaction 2～3h, then
Add 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, LDA
With the mol ratio of b be 1:1～1.5:1, a and b mol 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,
It is slowly added to the hexane solution of n-BuLi (n-BuLi), at-78 DEG C, then stirs reaction 2～3h, then
Add trimethyltin chloride (Me3SnCl) reagent, returns to room temperature after insulation reaction 0.5～1h, continue anti-
Answer 20～24h, obtain product, be 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, and its reaction equation is as follows:
R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl thiol of straight or branched.
Preferably, the isolation and purification method preparing compound step A (1) is: the reactant liquor warp of compound c
Silica gel column chromatography separating purification, eluant during column chromatography is normal hexane and dichloromethane is by volume
Obtain after 3:1～5:1 mixing.
Preferably, in described inert atmosphere, gas is nitrogen or argon.
In an embodiment, for convenience of statement, compound A uses compound A1 respectively, and A2, A3 etc. represent,
Compound B uses compound B-11 respectively, and B2, B3 etc. represent, compound P uses compound P1 respectively, P2,
P3 etc. represent, compound b uses compound b1 respectively, and b2, b3 etc. represent, compound c uses compound respectively
C1, c2, c3 etc. represent, compound e uses compound e1 respectively, and e2, e3 etc. represent, name is all with each reality
The title executed in example is as the criterion.
Benzo [1,2-b:4,5-b '] two thiophene-based monomers have good symmetry and flatness, therefore based on it
Polymer has good carrier mobility.And 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b ']
Two thiophene derivants are in benzo [1,2-b:4,5-b '] two thiophene-4, the 4 of 8-diketone, and 8 introduce 1,3-bis-mercaptan
-2-aldehyde derivative.1,3-bis-mercaptan-2-aldehyde derivative is as the good electron donor material of a class, drawing of it
Enter to further enhance benzo [1,2-b:4,5-b '] two thiophene derivants to Electronic Performance.Therefore, just by
Electronics itself that have in 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants and
Geometrical property, the application that it will expand in polymer solar battery as excellent donor monomer.
By 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants and carbazole donor list
Unit is as main polymer chain, and using allene contracting Thiourea dyestuff as being articulated on side chain by body unit, leads to
Cross main chain and side chain to the interaction of this in receptor " push-pull electronics ", add that master interchain is formed two
Dimension conjugated system, reduces the energy gap of conjugated polymer simultaneously, substantially increases 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 allene contracting thiourea-carbazole-benzo two thiophene copolymers
With, described it is applied to prepare polymer solar battery containing allene contracting thiourea-carbazole-benzo two thiophene copolymers
Active layer material, organic electroluminescence device emitting layer material and organic field effect tube.Described contain the third two
Alkene contracting thiourea-carbazole-benzo two thiophene copolymers is as described in the first aspect of the invention.
The one that the present invention provides is containing allene contracting thiourea-carbazole-benzo two thiophene copolymers and preparation method thereof
With application, have the advantages that
The present invention containing in allene contracting thiourea-carbazole-benzo two thiophene copolymers containing 4,8-bis-(1,3-bis-mercaptan
-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants, carbazole unit and allene contracting thiourea unit, by 4,8-
Two (1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants and carbazole donor monomer are as poly-
Compound main chain, and using allene contracting Thiourea dyestuff as being articulated on side chain by body unit, by main chain with
Side chain, to the interaction of this in receptor " push-pull electronics ", adds the two-dimentional conjugated body that master interchain is formed
System, reduces the energy gap of conjugated polymer simultaneously, substantially increases the light abstraction width of material, improves photoelectricity
Transformation efficiency.
Containing allene contracting thiourea-carbazole-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, bar
Part is gentle, and product is easily controllable so that it is imitate at polymer solar battery, organic electroluminescent and organic field
Answer having a extensive future of the field of photovoltaic materials such as transistor.
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 the common skill of the art
For art personnel, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, this
A little improvements and modifications are also considered as protection scope of the present invention.
The present invention relates to containing allene contracting thiourea-carbazole-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 of straight or branched
Sulfydryl, R2For C1～C12The alkyl of straight or branched, n is the integer between 5～60.
Embodiment 1
A kind of containing allene contracting thiourea-carbazole-benzo two thiophene copolymers, it is designated as copolymer p 1(n=10), knot
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) is prepared
Benzo [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 '] is prepared
Two thiophene, are designated as c1:
Compound b1 and a, i.e. 2-dimethoxy phosphono-4,5-diformazan sulfydryl-1,3-bis-mercaptan and benzo are provided
[1,2-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, being slowly added to the cyclohexane solution (4mmol) of 2.7mL1.5M LDA, at-78 DEG C, stirring is anti-
After answering 3h, the 10mL anhydrous tetrahydrofuran solution adding 0.44g (2.0mmol) a is carried out
Wittig-Horner reacts, and returns to room temperature after insulation reaction 0.5h, continues reaction 12h, stopped reaction.
Rotation is steamed, and removes the reactant liquor of excess, the crude on silica gel column chromatographic isolation and purification obtained, obtains product c1；
Eluant is to obtain after normal hexane and dichloromethane mix with volume ratio for 3:1, and productivity 51%, mass spectrometric measurement is tied
Fruit 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, it is slowly added to the hexane solution (4.4mmol) of 1.6mL2.5M n-BuLi, at-78 DEG C, stirring is anti-
After answering 2h, add the Me of 1.2mL (4mmol)3SnCl, returns to room temperature after insulation reaction 0.5h,
Continuing 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:
Reaction equation is:
Compound d, i.e. 2,7-bis-bromo-9-(4-benzaldehyde is provided)-9H-carbazole.
Under nitrogen protection, 1.8g (2.0mmol) A1 and 0.86g (2.0mmol) d is joined 80mL
In the toluene being dried, bubbling 0.5h removes the oxygen of residual, then is rapidly added 0.07g
(0.1mmol)Pd(PPh3)2Cl2Form mixed liquor, the oxygen that mixed liquor bubbling 1h removing is remained, 120 DEG C
Lower back flow reaction 30h, after reaction terminates, by mixed liquor decompression distillation, removes the toluene of excess, then drips
Settle in methanol.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.It is pumped through under vacuum pump and obtains product B1 night.Product B1 is carried out gel permeation chromatography
(GPC) test, number-average molecular weight ≈ 8440, monodispersity is 2.1.
Three, preparing copolymer p 1, reaction equation is as follows:
Thering is provided compound e1, structural formula is
147mg (0.175mmol) B1 and 0.7g (3.5mmol) e1 is joined in 15mL chloroform, then
It is added dropwise to 0.5mL pyridine, stirring reaction 20h under the conditions of 40 DEG C of lucifuges.After reaction stops, part is steamed in rotation
Solvent, then residual reaction liquid is poured in 50mL methanol, generate a large amount of precipitation, filter, obtain crude product.
After being dissolved with 15mL chloroform by crude product, after the Teflon filtration membrane filtration of 0.45 μm, rotation is steamed again,
Remove major part chloroform, then be slowly dropped in methanol and settle, sucking filtration, it is pumped through under vacuum pump and obtains night
Product P1.
Copolymer p 1 after purifying carries out gel permeation chromatography (GPC) test, number-average molecular weight
Mn ≈ 10270, polymer monodispersity is 2.02.
Embodiment 2
A kind of containing allene contracting thiourea-carbazole-benzo two thiophene copolymers, it is designated as copolymer p 2(n=60), knot
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) is prepared
Benzo [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 '] is prepared
Two thiophene, are designated as c2:
Compound b2 and a, i.e. 2-dimethoxy phosphono-4, pungent sulfydryl-1 of 5-bis-, 3-bis-mercaptan and benzo are provided
[1,2-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, it is slowly added to the cyclohexane solution (6mmol) of 4.0mL1.5M LDA, at-78 DEG C, stirs reaction 3
After h, the 10mL anhydrous tetrahydrofuran solution adding 0.44g (2.0mmol) a carries out Wittig-Horner
Reaction, returns to room temperature after insulation reaction 0.5h, continue reaction 12h, stopped reaction.Rotation is steamed, and removes
The reactant liquor of amount, the crude on silica gel column chromatographic isolation and purification obtained, obtain product c2；Eluant is just
Hexane and dichloromethane are to obtain after 3:1 mixes according to volume ratio, and productivity 53%, mass spectrometric measurement result is MS
(EI)m/z:970(M+);Its reaction equation is as follows:
(2) preparing compound A2, reaction equation is:
Under nitrogen protection, the 60mL anhydrous tetrahydrofuran solution of 1.15g (2.0mmol) c2 is cooled to-78
DEG C, it is slowly added to the hexane solution (4.4mmol) of 1.76mL2.5M n-BuLi, at-78 DEG C, stirring is anti-
After answering 2h, add the Me of 1.3mL (4.4mmol)3SnCl, returns to room temperature after insulation reaction 0.5h,
Continuing reaction 24h, obtain product A2, mass spectrometric measurement result is MS (EI) m/z:1295 (M+)；
Two, preparation polymer B 2, structural formula is:
Reaction equation is:
Compound d, i.e. 2,7-bis-bromo-9-(4-benzaldehyde is provided)-9H-carbazole.
Under nitrogen protection, 2.85g (2.2mmol) A2 and 0.86g (2.0mmol) d is joined 80mL
In anhydrous tetrahydro furan, bubbling 0.5h removes the oxygen of residual, then is rapidly added 46.2mg
(0.04mmol)Pd(PPh3)4Forming mixed liquor, mixed liquor bubbling 1h removes the oxygen of residual, 60 DEG C next time
Stream reaction 72h, after reaction terminates, by mixed liquor decompression distillation, removes the oxolane of excess, then drips
Settle in methanol.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.It is pumped through under vacuum pump and obtains product B2 night.
Product B2 carries out GPC test, number-average molecular weight ≈ 74220, and monodispersity is 2.2.
Three, preparing copolymer p 2, reaction equation is as follows:
Thering is provided compound e2, structural formula is
247mg (0.2mmol) B2 and 860mg (4.5mmol) e2 is joined in 15mL chloroform, then
It is added dropwise to 0.56mL pyridine, stirring reaction 22h under the conditions of 30 DEG C of lucifuges.After reaction stops, revolving steaming portion
Divide solvent, then residual reaction liquid is poured in 50mL methanol, generate a large amount of precipitation, filter, obtain and slightly produce
Thing.After again crude product being dissolved with 15mL chloroform, after the Teflon filtration membrane filtration of 0.45 μm,
Rotation is steamed, and removes major part chloroform, then is slowly dropped in methanol and settles, and sucking filtration is pumped through under vacuum pump
Obtain product P2 night.
Copolymer p 2 after purifying carries out GPC test, number-average molecular weight Mn ≈ 83460, and polymer list divides
Scattered property is 1.8.
Embodiment 3
A kind of containing allene contracting thiourea-carbazole-benzo two thiophene copolymers, it is designated as copolymer p 3(n=30), knot
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 sulfur is prepared
Alcohol-2-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 is prepared
[1,2-b:4,5-b '] two thiophene, are designated as c3:
Compound b3 and a, i.e. 2-dimethoxy phosphono-4,5-bis-(16 sulfydryl)-1,3-bis-mercaptan are provided
With benzo [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, being slowly added to the cyclohexane solution (4.5mmol) of 3.0mL1.5M LDA, at-78 DEG C, stirring is anti-
After answering 2h, the 15mL anhydrous tetrahydrofuran solution adding 0.264g (1.2mmol) a is carried out
Wittig-Horner reacts, and returns to room temperature after insulation reaction 1h, continues reaction 15h, stopped reaction.
Rotation is steamed, and removes the oxolane of excess, the crude on silica gel column chromatographic isolation and purification obtained, obtains 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) compound A-13 is prepared:
Under nitrogen protection, the 60mL anhydrous tetrahydrofuran solution of 2.84g (2.0mmol) c3 is cooled to-78
DEG C, it is slowly added to the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, at-78 DEG C, stirring is anti-
After answering 3h, add the Me of 1.5mL (5.0mmol)3SnCl, returns to room temperature after insulation reaction 1h,
Continuing 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:
Reaction equation is:
Compound d, i.e. 2,7-bis-bromo-9-(4-benzaldehyde is provided)-9H-carbazole.
Under nitrogen protection, 4.36g (2.5mmol) A3 and 0.86g (2.0mmol) d is joined 80mL
Being dried in DMF, bubbling 0.5h removes the oxygen of residual, then is rapidly added 46.2mg
(0.04mmol)Pd(PPh3)4Form mixed liquor, mixed liquor bubbling 1h is removed the oxygen of residual, at 80 DEG C
Back flow reaction 24h, after reaction terminates, by mixed liquor decompression distillation, removes 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 post of aluminium oxide
Chromatography, 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 B3 night.
Product B3 carries out GPC test, number-average molecular weight ≈ 50580, and monodispersity is 1.9.
Three, preparing copolymer p 3, reaction equation is as follows:
Thering is provided compound e3, structural formula is
337mg (0.2mmol) B3 and 2160mg (4.5mmol) e3 is joined in 15mL chloroform, then
It is added dropwise to 0.6mL pyridine, stirring reaction 24h under the conditions of 40 DEG C of lucifuges.After reaction stops, part is steamed in rotation
Solvent, then residual reaction liquid is poured in 50mL methanol, generate a large amount of precipitation, filter, obtain crude product.
After being dissolved with 15mL chloroform by crude product, after the Teflon filtration membrane filtration of 0.45 μm, rotation is steamed again,
Remove major part chloroform, then be slowly dropped in methanol and settle, sucking filtration, it is pumped through under vacuum pump and obtains night
Product P3.
Copolymer p 3 after purifying carries out GPC test, number-average molecular weight Mn ≈ 64470, and polymer list divides
Scattered property is 1.78.
Embodiment 4
A kind of containing allene contracting thiourea-carbazole-benzo two thiophene copolymers, it is designated as copolymer p 4(n=15), knot
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) is prepared
Benzo [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 is prepared
Thiophene, is designated as c4:
Compound b4 and a, i.e. 2-dimethoxy phosphono-4,5-dimethyl-1,3-bis-mercaptan and benzo are provided
[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, it is slowly added to the cyclohexane solution (6.0mmol) of 2.0mL3M LDA, at-78 DEG C, stirs reaction 3
After h, the 10mL anhydrous tetrahydrofuran solution adding 0.46g (2.1mmol) a carries out Wittig-Horner
Reaction, returns to room temperature after insulation reaction 0.5h, continue reaction 12h, stopped reaction.Rotation is steamed, and removes
The oxolane of amount, the crude on silica gel column chromatographic isolation and purification obtained, obtain product c4；Eluant is
Normal hexane and dichloromethane are to obtain after 4:1 mixes according to volume ratio, and productivity 53%, mass spectrometric measurement 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, it is slowly added to the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, at-78 DEG C, stirring is anti-
After answering 2.5h, add the Me of 1.5mL (5.0mmol)3SnCl, returns to room after insulation reaction 0.7h
Temperature, continues reaction 20h, obtains product, i.e. A4, and mass spectrometric measurement result is MS (EI) m/z:774 (M+)；
Two, preparation polymer B 4, structural formula is:
Reaction equation is:
Compound d, i.e. 2,7-bis-bromo-9-(4-benzaldehyde is provided)-9H-carbazole.
Under argon shield, 0.93g (1.2mmol) A4 and 0.34g (0.8mmol) d is joined 80mL
Being dried in DMF, 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) shape
Become mixed liquor, mixed liquor bubbling 1h is removed the oxygen of residual, back flow reaction 30h at 80 DEG C, reaction knot
Shu Hou, by mixed liquor decompression distillation, removes the DMF of excess, then is 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,
Removing 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 B4 night.
Product B4 carries out GPC test, number-average molecular weight ≈ 10740, and monodispersity is 2.0.
Three, preparing copolymer p 4, reaction equation is as follows:
Compound e1 is provided；
143mg (0.2mmol) B4 and 900mg (4.5mmol) e1 is joined in 15mL chloroform, then
It is added dropwise to 0.6mL pyridine, stirring reaction 24h under the conditions of 35 DEG C of lucifuges.After reaction stops, part is steamed in rotation
Solvent, then residual reaction liquid is poured in 50mL methanol, generate a large amount of precipitation, filter, obtain crude product.
After being dissolved with 15mL chloroform by crude product, after the Teflon filtration membrane filtration of 0.45 μm, rotation is steamed again,
Remove major part chloroform, then be slowly dropped in methanol and settle, sucking filtration, it is pumped through under vacuum pump and obtains night
Product P4.
Copolymer p 4 after purifying carries out GPC test, number-average molecular weight Mn ≈ 13470, and polymer list divides
Scattered property is 1.9.
Embodiment 5
A kind of containing allene contracting thiourea-carbazole-benzo two thiophene copolymers, it is designated as copolymer p 5(n=18), knot
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) is prepared
Benzo [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 is prepared
Thiophene, is designated as c5:
Compound b5 and a, i.e. 2-dimethoxy phosphono-4,5-dihexyl-1,3-bis-mercaptan and benzo are provided
[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, it is slowly added to the cyclohexane solution (3.0mmol) of 2.0mL1.5M LDA, stirs at-78 DEG C
After reaction 3h, the 6mL anhydrous tetrahydrofuran solution adding 0.22g (1.0mmol) a is carried out
Wittig-Horner reacts, and returns to room temperature after insulation reaction 0.5h, continues reaction 12h, stopped reaction.
Rotation is steamed, and removes the oxolane of excess, the crude on silica gel column chromatographic isolation and purification obtained, obtains product
c5；Eluant is normal hexane and dichloromethane according to volume ratio is to obtain after 4:1 mixing, productivity 49%, mass 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, it is slowly added to the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, at-78 DEG C, stirring is anti-
After answering 2h, add the Me of 1.5mL (5.0mmol)3SnCl, returns to room temperature after insulation reaction 0.5h,
Continuing reaction 24h, obtain product, i.e. A5, mass spectrometric measurement result is MS (EI) m/z:1055 (M+)；
Two, preparation polymer B 5, structural formula is:
Reaction equation is:
Compound d, i.e. 2,7-bis-bromo-9-(4-benzaldehyde is provided)-9H-carbazole.
Under nitrogen protection, by 2.11g (2.0mmol) 2,6-bis-(tin trimethyl)-4,8-bis-(4,5-dihexyls
-1,3-two mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene (A5) and 0.77g (1.8mmol) 2,7-dibromo
-9-(4-benzaldehyde)-9H-carbazole (d) joins in 80mL dry toluene, and bubbling 0.5h removes residual
Oxygen, then be rapidly added catalyst Pd2(dba)3(16.5mg, 0.018mmol) and P (o-Tol)3(54.8
Mg, 0.18mmol) form mixed liquor, mixed liquor bubbling 1h is removed the oxygen of residual, 110 DEG C are next time
Stream reaction 36h, after reaction terminates, by mixed liquor decompression distillation, removes the toluene of excess, then is added drop-wise to first
Alcohol settles.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
Sedimentation, sucking filtration.It is pumped through under vacuum pump and obtains product B5 night.
Product B5 carries out GPC test, number-average molecular weight ≈ 17946, and monodispersity is 2.0.
Three, preparing copolymer p 5, reaction equation is as follows:
Compound e1 is provided；
199mg (0.2mmol) B5 and 900mg (4.5mmol) e1 is joined in 15mL chloroform, then
It is added dropwise to 0.6mL pyridine, stirring reaction 22h under the conditions of 40 DEG C of lucifuges.After reaction stops, part is steamed in rotation
Solvent, then residual reaction liquid is poured in 50mL methanol, generate a large amount of precipitation, filter, obtain crude product.
After being dissolved with 15mL chloroform by crude product, after the Teflon filtration membrane filtration of 0.45 μm, rotation is steamed again,
Remove major part chloroform, then be slowly dropped in methanol and settle, sucking filtration, it is pumped through under vacuum pump and obtains night
Product P5.
Copolymer p 5 after purifying carries out GPC test, number-average molecular weight Mn ≈ 21222, and polymer list divides
Scattered property is 1.9.
Embodiment 6
A kind of containing allene contracting thiourea-carbazole-benzo two thiophene copolymers, it is designated as copolymer p 6(n=20), knot
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 sulfur is prepared
Alcohol-2-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 is prepared
[1,2-b:4,5-b '] two thiophene, are designated as c6:
Compound b6 and a, i.e. 2-dimethoxy phosphono-4,5-bis-(cetyl)-1,3-bis-mercaptan are provided
With benzo [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, it is slowly added to the cyclohexane solution (3.0mmol) of 2.0mL1.5M LDA, stirs at-78 DEG C
After reaction 2.5h, the 10mL anhydrous tetrahydrofuran solution adding 0.22g (1.0mmol) a is carried out
Wittig-Horner reacts, and returns to room temperature after insulation reaction 0.7h, continues reaction 13h, stopped reaction.
Rotation is steamed, and removes the oxolane of excess, the crude on silica gel column chromatographic isolation and purification obtained, 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, it is slowly added to the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, at-78 DEG C, stirring is anti-
After answering 2h, add the Me of 1.5mL (5.0mmol)3SnCl, returns to room temperature after insulation reaction 0.5h,
Continuing reaction 24h, obtain product, i.e. A6, mass spectrometric measurement result is MS (EI) m/z:1616 (M+)；
Two, preparation polymer B 6, structural formula is:
Reaction equation is:
Compound d, i.e. 2,7-bis-bromo-9-(4-benzaldehyde is provided)-9H-carbazole.
Under nitrogen protection, 3.23g (2.0mmol) A6 and 0.34g (0.8mmol) d is joined 80mL
In dry toluene, bubbling 0.5h removes the oxygen of residual, then is rapidly added catalyst Pd2(dba)3(0.073
mg,8×10-5Mmol and P (o-Tol)3(0.00486mg, 1.6 × 10-4Mmol) mixed liquor is formed, will be mixed
Closing liquid bubbling 1h and remove the oxygen of residual, back flow reaction 30h at 110 DEG C, after reaction terminates, by mixing
Liquid decompression distillation, removes the toluene of excess, then is added drop-wise in methanol settle.Sucking filtration, methanol washs,
It 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 night
Product B6.
Product B6 carries out GPC test, number-average molecular weight ≈ 31160, and monodispersity is 2.2.
Three, preparing copolymer p 6, reaction equation is as follows:
Compound e1 is provided；312mg (0.2mmol) B6 and 900mg (4.5mmol) e1 is joined 15
In mL chloroform, then it is added dropwise to 0.6mL pyridine, stirring reaction 20h under the conditions of 40 DEG C of lucifuges.Reaction stops
After Zhi, partial solvent is steamed in rotation, then is poured into by residual reaction liquid in 50mL methanol, generates a large amount of precipitation,
Filter, obtain crude product.After again crude product being dissolved with 15mL chloroform, through the politef of 0.45 μm
After filter membrane filters, rotation is steamed, and removes major part chloroform, then is slowly dropped in methanol and 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 ≈ 34800, and polymer list divides
Scattered property is 2.12.
Embodiment 7
A kind of containing allene contracting thiourea-carbazole-benzo two thiophene copolymers, it is designated as copolymer p 7(n=5), knot
Structure formula is 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-b '] is prepared
Two thiophene, are designated as A7；
(1) compound 4 is prepared, and 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 thiophene-4,8-diketone；
Under argon shield, the 40mL anhydrous tetrahydrofuran solution of 0.42g (2.0mmol) b7 is cooled to
-78 DEG C, it is slowly added to the cyclohexane solution (3.0mmol) of 2.0mL1.5M LDA, stirs at-78 DEG C
After reaction 3h, the 10mL anhydrous tetrahydrofuran solution adding 0.22g (1.0mmol) a is carried out
Wittig-Horner reacts, and returns to room temperature after insulation reaction 0.5h, continues reaction 12h, stopped reaction.
Rotation is steamed, and removes the oxolane of excess, the crude on silica gel column chromatographic isolation and purification obtained, obtains product
c7；Eluant is normal hexane and dichloromethane according to volume ratio is to obtain after 5:1 mixing, productivity 55%, mass spectrum
Test result MS (EI) m/z:393 (M+);Its reaction equation is as follows:
(2) compound A7 is prepared:
Under nitrogen protection, the 40mL anhydrous tetrahydrofuran solution of 0.79g (2.0mmol) c7 is cooled to-78
DEG C, it is slowly added to the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, at-78 DEG C, stirring is anti-
After answering 2h, add the Me of 1.5mL (5.0mmol)3SnCl, returns to room temperature after insulation reaction 0.5h,
Continue reaction 24h, obtain product, i.e. A7, mass spectrometric measurement result MS (EI) m/z:718 (M+)；
Two, preparation polymer B 7, structural formula is:
Reaction equation is:
Compound d, i.e. 2,7-bis-bromo-9-(4-benzaldehyde is provided)-9H-carbazole.
Under nitrogen protection, 1.44g (2.0mmol) A7 and 0.86g (2.0mmol) d is joined 80mL
Being dried in DMF, bubbling 0.5h removes the oxygen of residual, then is rapidly added catalyst
Pd2(dba)3(7.3mg, 0.008mmol) and P (o-Tol)3(48.6mg, 0.16mmol) forms mixed liquor,
Mixed liquor bubbling 1h is removed the oxygen of residual, back flow reaction 30h at 80 DEG C, after reaction terminates, will mix
Close liquid decompression distillation, remove the DMF of excess, then be added drop-wise in methanol settle.Take out
Filter, 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.Very
It is pumped through under empty pump and obtains product B7 night.
Product B7 carries out GPC test, number-average molecular weight ≈ 3300, and monodispersity is 2.3.
Three, preparing copolymer p 7, reaction equation is as follows:
Compound e1 is provided；
132mg (0.2mmol) B7 and 1000mg (5mmol) e1 is joined in 15mL chloroform, then drips
Add 0.6mL pyridine, stirring reaction 24h under the conditions of 40 DEG C of lucifuges.After reaction stops, it is molten that part is steamed in rotation
Agent, then residual reaction liquid is poured in 50mL methanol, generate a large amount of precipitation, filter, obtain crude product.
After again crude product being dissolved with 15mL chloroform, after the Teflon filtration membrane filtration of 0.45 μm, rotation
Steam, remove major part chloroform, then be slowly dropped in methanol and settle, sucking filtration, it is pumped through night under vacuum pump
Obtain product P7.
Copolymer p 7 after purifying carries out GPC test, number-average molecular weight ≈ 4210, and monodispersity is 2.0.
Embodiment 8
With the embodiment of the present invention 3 preparation containing allene contracting thiourea-carbazole-benzo two thiophene copolymers P3 as work
Property layer, prepare organic solar batteries device, including the substrate of glass 1 stacked gradually, anode 2, middle auxiliary
Helping layer 3, active layer 4 and negative electrode 5, this device architecture specifically can be briefly described as: substrate of glass/anode/in
Between auxiliary layer/active layer/negative electrode, see Fig. 1.Wherein, anode 2 is ITO(tin indium oxide), middle auxiliary layer
The material of 3 uses poly-(3,4-Ethylenedioxy Thiophene) (PEDOT) and polystyrolsulfon acid (PSS) to be formed
Composite, is called for short PEDOT:PSS；Active layer 4 includes electron donor material and electron acceptor material, electricity
The material of sub-donor be the embodiment of the present invention 3 preparation containing allene contracting thiourea-carbazole-benzo two thiophene copolymers
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, choose during making ito glass (with anode ITO layer, can
Buy), after ultrasonic waves for cleaning, process with oxygen plasma (oxygen-Plasma), to improve its work function；
Then the middle auxiliary layer 3PEDOT:PSS of coating on ito glass；By P3 and PCBM with mass ratio it is
After 1:1 mixing, it is spun on PEDOT:PSS film layer, obtains active layer 4；Evaporation cathode under vacuum
Metallic aluminium 5, obtains organic solar batteries device.
By the I-E characteristic of Keithley236 current/voltage source-measurement system test device, obtain device
The performance data of part is shown in Table 1.
Table 1 preparing for active layer containing allene contracting thiourea-carbazole-benzo two thiophene copolymers P3 with the present invention
The performance data of organic solar batteries device
| Copolymer | Short circuit current (mA/cm2) | Open-circuit voltage (V) | Fill factor, curve factor (%) | Energy conversion efficiency (%) |
| P3 | 7.30 | 0.62 | 0.33 | 1.49 |
As seen from the data in Table 1, making containing allene contracting thiourea-carbazole-benzo two thiophene copolymers P3 by the present invention
The energy conversion efficiency of the organic solar batteries device prepared for active layer is 1.49%.Show containing of the present invention
Allene contracting thiourea-carbazole-benzene 1,4-Dithiapentalene contains 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b ']
Two thiophene derivants, carbazole unit and allene contracting thiourea unit, by 4,8-bis-(1,3-bis-mercaptan-2-aldehyde)
Benzo [1,2-b:4,5-b '] two thiophene derivants and carbazole donor monomer are as main polymer chain, and by allene
Contracting Thiourea dyestuff is articulated on side chain as by body unit, by main chain and side chain to this in receptor " push away-
Draw electronics " interaction, add the two-dimentional conjugated system that master interchain is formed, reduce conjugation poly-simultaneously
The energy gap of compound, substantially increases the light abstraction width of material, improves electricity conversion.
Embodiment 9
With embodiment 2 preparation containing allene contracting thiourea-carbazole-benzo two thiophene copolymers P2 as luminescent layer,
Prepare organic electroluminescence device, including the glass substrate 01 stacked gradually, transparent anode 02, luminescent layer 03,
Cathode buffer layer 04 and negative electrode 05, this device architecture specifically can be briefly described as: substrate of glass/transparent anode/
Luminescent layer/cathode buffer layer/negative electrode, is shown in Fig. 2, but the structure of practical devices is not limited to this.Wherein, transparent sun
Pole 02 material is tin indium oxide (ITO), and luminescent layer 03 material is the copolymer of the embodiment of the present invention 2 preparation
P2, uses spin coating technique to prepare luminescent layer on ITO, and the material of cathode buffer layer 04 is lithium fluoride (LiF),
The material of negative electrode 05 is metallic aluminium, and the preparation method of each layer is carried out by existing spin coating method, obtains Organic Electricity
Electroluminescence device.
Tested above-mentioned organic electroluminescence by Keithley source measurement system (Keithley2400Sourcemeter) to send out
Current versus brightness-the voltage characteristic of optical device, with its electricity of JY company of France SPEX CCD3000 spectrometer measurement
Photoluminescence spectrum, all measurements all complete in atmosphere at room temperature, record the most light of organic electroluminescence device
Degree efficiency is 1.83cd/A, and high-high brightness is 1086cd/m2。
Embodiment 10
With embodiment 5 preparation copolymer p 5 as organic semiconductor layer, prepare organic field effect tube, its
Substrate 001 that structure as it is shown on figure 3, include stacks gradually, insulating barrier 002, decorative layer 003, You Jiban
Conductor layer 004, source electrode (S) 005 and drain electrode (D) 006.This device architecture specifically can briefly describe
For: substrate/insulating barrier/decorative layer/organic semiconductor layer/source/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 can be but not limited to thickness and be
The SiO of 450nm2, 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 p 5 of the embodiment of the present invention 5 preparation, source electrode (S) 005
All use gold as electrode with drain electrode (D) 006.
By time-of-flight method (Time of Flight, TOF), 7.0 × 105Vcm-1Electric field in test and contain
The mean void mobility of the organic field effect tube of the copolymer p 5 of the embodiment of the present invention 5 preparation is
1.52×10-4m2/ Vs, show prepared by the present invention containing allene contracting thiourea-carbazole-benzo two thiophen polymer
Hole transport performance.
The above is the preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, this
A little improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. one kind contain allene contracting thiourea-carbazole-benzo two thiophene copolymers, it is characterised in that for have as
The copolymer p of lower structural formula:
In formula, R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl of straight or branched
Sulfydryl, R2For C1～C12The alkyl of straight or branched, n is the integer between 5～60.
2. the preparation method containing allene contracting thiourea-carbazole-benzo two thiophene copolymers, it is characterised in that
Including following operating procedure:
(1) polymer B is prepared；
Compound A and compound d that following structural formula represents be provided respectively:
In atmosphere of inert gases, compound A and the compound d that mol ratio is 1:1～1.5:1 is added first
Dissolving in organic solvent, be subsequently adding catalyst and form mixed liquor, this mixed liquor carries out Stille at 60～120 DEG C
Coupled reaction 24～72 hours, after stopped reaction, the isolated and purified polymer B that obtains, structural formula is as follows:
In formula, R1For H, C1～C16The alkyl of straight or branched or C1～C16The alkyl of straight or branched
Sulfydryl, n is the integer between 5～60；
Reaction equation is:
(2) copolymer p is prepared；
The compound e that following structural formula represents is provided:
R in formula2For C1～C12The alkyl of straight or branched；
Mol ratio 1:20～the polymer B of 1:25 and compound e are joined in the second organic solvent, drips pyrrole
After pyridine, 30～40 DEG C of stirring reactions 20～24h, after stopped reaction, isolated and purified obtain copolymer p, instead
Ying Shiwei:
3. the preparation side containing allene contracting thiourea-carbazole-benzo two thiophene copolymers as claimed in claim 2
Method, it is characterised in that described catalyst is the mixture of organic palladium or organic palladium and organophosphorus ligand.
4. the preparation side containing allene contracting thiourea-carbazole-benzo two thiophene copolymers as claimed in claim 3
Method, it is characterised in that described organic palladium is double (triphenylphosphine) palladium chloride or tetrakis triphenylphosphine palladium, described
Organic palladium is three (dibenzalacetone) two palladium and the mixing of three (2-tolyl) phosphine with the mixture of organophosphorus ligand
Thing；
Described organic palladium and three (dibenzalacetone) two palladium and three (2-tolyls) in the mixture of organophosphorus ligand
The mol ratio of phosphine is 1:2～1:20.
5. the preparation side containing allene contracting thiourea-carbazole-benzo two thiophene copolymers as claimed in claim 3
Method, it is characterised in that the mole dosage of described organic palladium is the 0.01%～5% of compound d mole dosage.
6. the preparation side containing allene contracting thiourea-carbazole-benzo two thiophene copolymers as claimed in claim 2
Method, it is characterised in that described first organic solvent is oxolane, DMF or toluene；
Described second organic solvent is chloroform.
7. the preparation side containing allene contracting thiourea-carbazole-benzo two thiophene copolymers as claimed in claim 2
Method, it is characterised in that step (1) described isolation and purification method is:
After the completion of reaction, by the decompression distillation of polymer B reactant liquor, remove the first organic solvent of excess,
Being added drop-wise to settle in methanol, sucking filtration, methanol washs again, and is dried；Then by column chromatography, chloroform drenches
Wash, distillation, remove organic solvent, methanol settle, sucking filtration, gained solid with acetone surname extraction for several times,
Methanol settles, and sucking filtration is pumped through under vacuum pump and obtains product night.
8. the preparation containing allene contracting thiourea-carbazole-benzo two thiophene copolymers as claimed in claim 2
Method, it is characterised in that step (2) described isolation and purification method is:
By the decompression distillation of copolymer p reactant liquor, remove the second organic solvent of excess, then pour in methanol,
Generate a large amount of precipitation, filter, obtain crude product；After again crude product being dissolved with chloroform, through politef mistake
After membrane filtration, rotation is steamed, and removes major part chloroform, then is slowly dropped in methanol and settles, sucking filtration,
It is pumped through under vacuum pump and obtains product night.
9. the preparation side containing allene contracting thiourea-carbazole-benzo two thiophene copolymers as claimed in claim 2
Method, it is characterised in that 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, slowly adds
Enter the cyclohexane solution of lithium diisopropyl amido, at-78 DEG C after stirring reaction 2～3h, add compound a
Tetrahydrofuran solution, carry out Wittig-Horner reaction, after insulation reaction 0.5～1h, return to room temperature,
Continue reaction 12～15h, obtain product, i.e. compound c；Wherein, lithium diisopropyl amido and b mole
Than being 1:2.0～1:2.5 for 1:1～1.5:1, a and b mol ratio, 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,
It is slowly added to the hexane solution of n-BuLi, then stirring reaction 2～3h at-78 DEG C, adds trimethyl
Stannic chloride reagent, returns to room temperature after insulation reaction 0.5～1h, continue reaction 20～24h, obtain product,
I.e. compound A；Wherein, n-BuLi is 2.2:1～2.5:1 with the mol ratio of c, and trimethyltin chloride is with c's
Mol ratio is 2.0:1～2.5:1, and its reaction equation is as follows:
10. allene contracting thiourea-carbazole-benzo two thiophene copolymers that contains as claimed in claim 1 is at polymer
Application in solaode, organic electroluminescence device and organic field effect tube.
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