CN104045811B - A kind of containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers and preparation method and application - Google Patents
A kind of containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers and preparation method and application Download PDFInfo
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- 0 C*C1=CI(C)=CS1 Chemical compound C*C1=CI(C)=CS1 0.000 description 3
- RUNLZQAQXIXRQU-UAMSZSMSSA-N CC(S/C(/SC)=C(/C=C(C1)/C=C(\S)/[Sn](C)(C)C)\C=C1SC[Sn](C)(C)C)=C Chemical compound CC(S/C(/SC)=C(/C=C(C1)/C=C(\S)/[Sn](C)(C)C)\C=C1SC[Sn](C)(C)C)=C RUNLZQAQXIXRQU-UAMSZSMSSA-N 0.000 description 1
- AFDIYCXWQIGLFG-UHFFFAOYSA-N C[IH]1=CSCS1 Chemical compound C[IH]1=CSCS1 AFDIYCXWQIGLFG-UHFFFAOYSA-N 0.000 description 1
- QKZJQIHBRCFDGQ-UHFFFAOYSA-N Cc1c(C)[s]c(C)c1 Chemical compound Cc1c(C)[s]c(C)c1 QKZJQIHBRCFDGQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a kind of containing allene contracting thiourea-dithieno pyrroles-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-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～C12The alkyl of straight or branched, n is the integer between 5～60.Described contain 4 containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers, 8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants, dithieno pyrroles and allene contracting thiourea unit, high with the matching degree of solar spectrum, be planar conjugate structure simultaneously, carrier mobility speed is high, improves energy conversion efficiency.
Description
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of containing allene contracting thiourea-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.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 desirable to provide a kind of containing allene contracting thiourea-dithieno pyrroles-benzo
Two thiophene copolymers, containing 4 in this copolymer, 8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two
Thiophene derivants, dithieno pyrrole 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 with dithieno pyrroles's donor monomer as being polymerized owner
Chain, and using allene contracting Thiourea dyestuff as being articulated on side chain by body unit, given with side chain by main chain
Interaction this " push-pull electronics " in receptor, adds the two-dimentional conjugated system that master interchain is formed, with
Time reduce the energy gap of conjugated polymer, substantially increase the light abstraction width of material.The purpose of the present invention is also
It is the preparation method of above-mentioned allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers is provided and answers
With.
First aspect, the present invention provides a kind of containing allene contracting thiourea-dithieno pyrroles-benzene 1,4-Dithiapentalene copolymerization
Thing, for having the 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 dithieno pyrrole
Cough up donor monomer as main polymer chain, and allene contracting Thiourea dyestuff is articulated in side as by body unit
On chain, by main chain with side chain to the interaction of this in receptor " push-pull electronics ", add master interchain
The two-dimentional conjugated system formed, reduces the energy gap of conjugated polymer simultaneously, and the light substantially increasing material is inhaled
Receipts scope.
Second aspect, the present invention provides a kind of containing allene contracting thiourea-dithieno pyrroles-benzene 1,4-Dithiapentalene copolymerization
The preparation method of thing, including following operating procedure:
(1) polymer B is prepared;
Compound A and compound g 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 g that mol ratio is 1:1～1.5:1 is added first
Dissolving in organic solvent, be subsequently adding catalyst and form mixed solution, this mixed solution is carried out at 60～120 DEG C
Stille 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；
Offer structural formula isCompound h, R2For C1～C12The alkyl of straight or branched；
Mol ratio 1:20～the polymer B of 1:25 and compound h 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 organic phosphine.
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 (dibenzalacetone) two palladium with the mixture of organic phosphine
(Pd2(dba)3) and three (2-tolyl) phosphine (P (o-Tol)3) mixture；Described organic palladium mixes with organic phosphine
Pd in compound2(dba)3With 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 g mole dosage.
Preferably, described first organic solvent is oxolane, DMF or toluene.
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, 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 the column chromatography of aluminium oxide,
Chloroform drip washing.Distillation, removes organic solvent, and methanol settles, sucking filtration, gained solid acetone surname extraction
For several times, methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product night.
Preferably, 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, then filter, obtain crude product；After again crude product being dissolved with chloroform, through polytetrafluoroethyl-ne
After alkene filter membrane filters, rotation is steamed, and removes major part chloroform, then is slowly dropped in methanol and settles, takes out
Filter, 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
Being 1:2.0～1:2.5 with the mol ratio that mol ratio is 1:1～1.5:1, a and b of b, 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.
Preferably, described compound g can buy or prepared by following methods:
(1) magnesium rod, a small amount of iodine powder and 2～3 2-bromothiophenes are mixed to join in dry ether, at argon
Under gas shielded, heated and stirred to 40 DEG C refluxes.It is slowly added dropwise the diethyl ether solution into 2-bromothiophene again, drips
Bi Hou, continues back flow reaction 1h at 40 DEG C, cools down standby, obtain compound e；Then by compound e
It is slowly added dropwise into containing compound d, catalyst Pd (PPh3)2Cl2With in the reaction bulb of oxolane, stir and add
Back flow reaction 4h at hot to 60 DEG C, stopped reaction is also cooled to room temperature.Reactant liquor is poured into 50mL satisfy
And NH4In Cl aqueous solution, after ethyl acetate extracts, merge organic facies and use anhydrous Na2SO4It is dried overnight.
Filtering, after organic solvent is steamed in rotation, obtain product f through silica gel column chromatography separating purification, wherein, 2-bromothiophene exists
Concentration in ether is 0.9mol/L, and magnesium rod is 4:3 with the mol ratio of 2-bromothiophene, compound d and catalyst
Mol ratio be 1:0.03, eluant is normal hexane and dichloromethane is mixed to get for 9:1 by volume, reaction
Formula is:
(2) being dissolved in dry DMF by compound f, obtaining concentration is 0.233mol/L
DMF (DMF) solution, and be cooled to 0 DEG C, then by phosphorus oxychloride (POCl3)
Being slowly added dropwise in DMF solution, the mol ratio of phosphorus oxychloride and compound f is 30:1,
Drip complete, be warming up to 50 DEG C of stirring reaction 2h.It is cooled to room temperature, reactant liquor is poured in ice-water bath,
And it is the most neutral to add tune pH value in saturated sodium carbonate solution.After dichloromethane extracts, merge organic facies, use
After saturated common salt washing, use anhydrous MgSO4It is dried overnight.Filtering, solvent is steamed in rotation, divides through silica gel column chromatography
From obtaining product g, eluant is to obtain after petroleum ether and dichloromethane mix for 2:1 by volume, reaction equation
For:
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 h uses compound h1 respectively, and h2, h3 etc. represent, name is all with each reality
The title executed in example is as the criterion.
Owing to benzo [1,2-b:4,5-b '] two thiophene-based monomers have good symmetry and a flatness, therefore based on
Its 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, 8 introducings
1,3-bis-mercaptan-2-aldehyde derivative.1,3-bis-mercaptan-2-aldehyde derivative is as the good electron donor material of a class
Material, its introducing further enhance benzo [1,2-b:4,5-b '] two thiophene derivants to Electronic Performance.Cause
This, is just because of 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants tool itself
Some electronics and geometrical property, it will expand in polymer solar battery as excellent donor monomer
Application.
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 allene contracting Thiourea dyestuff is articulated in side as by body unit
On chain, by main chain with side chain to the interaction of this in receptor " push-pull electronics ", add master interchain
The two-dimentional conjugated system formed, reduces the energy gap of conjugated polymer simultaneously, and the light substantially increasing material is inhaled
Receipts scope.
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 containing allene contracting thiourea-dithieno pyrroles-benzene 1,4-Dithiapentalene copolymerization
The application of thing, described to be applied to preparation containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers poly-
Compound solaode active layer material, organic electroluminescence device emitting layer material and organic effect crystal
Pipe.Described containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers such as first aspect present invention institute
State.
The one that the present invention provides containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers and
Preparation method and application, have the advantages that
The present invention containing in allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers containing 4,8-bis-
(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants, dithieno pyrrole unit and third
Diene contracting thiourea unit, by 4,8-bis-(1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants
With dithieno pyrroles's donor monomer as main polymer chain, and using allene contracting Thiourea dyestuff as receptor
Unit is articulated on side chain, by main chain with side chain to the interaction of this in receptor " push-pull electronics ",
The two-dimentional conjugated system formed plus master interchain, reduces the energy gap of conjugated polymer simultaneously, is greatly improved
The light abstraction width of material, improves electricity conversion.
Containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers currently without document report and phase
Closing patent application publication, be a kind of new photoelectric material, energy conversion efficiency is high, and preparation method is simple, produces
Rate is high, mild condition, and product is easily controllable so that it is polymer solar battery, organic electroluminescent and
Having a extensive future of the field of photovoltaic materials such as organic field effect tube.
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-dithieno pyrroles-benzo two thiophene copolymers, 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-alkyl of straight or branched, n is the integer between 5～60.
Embodiment 1
A kind of containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 1
(n=10), structural 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 obtains after mixing for 3:1 with volume ratio for normal hexane and dichloromethane, productivity 51%, mass spectrometric measurement
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, 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:
(1) compound g, i.e. 5-(4-(2,6-dibromo dithieno [3,2-b:2 ', 3 '-d] pyrroles-4) phenyl) are prepared
Thiophene-2-formaldehyde；
A 0.29g (12.0mmol) magnesium rod, a small amount of iodine powder and 3 2-bromothiophenes are mixed to join 10mL by ()
In the ether being dried, under argon shield, heated and stirred to 40 DEG C refluxes.It is slowly added dropwise again into 2-bromothiophene
Diethyl ether solution (1.47g (9.0mmol) 2-bromothiophene in 10mL ether), after dropping, at 40 DEG C
Lower continuation back flow reaction 1h, cools down standby.Then the Grignard reagent of this just preparation is slowly added dropwise into containing 2.46
The bromo-4-(4-bromophenyl of g (5.0mmol) 2,6-bis-) and-4H-dithieno [3,2-b:2 ', 3 '-d] pyrroles (d) 0.11g
(0.15mmol)Pd(PPh3)2Cl2With in the reaction bulb of 40mL oxolane, it is stirred and heated at 60 DEG C
Back flow reaction 4h, stopped reaction is also cooled to room temperature.Reactant liquor is poured into the saturated NH of 50mL4Cl is water-soluble
In liquid, after ethyl acetate extracts, merge organic facies and use anhydrous Na2SO4It is dried overnight.Filtering, rotation is steamed
After organic solvent, obtain product f through silica gel column chromatography separating purification, eluant be normal hexane and dichloromethane by
Volume ratio is to obtain after 9:1 mixes, productivity 25%, MS (EI) m/z:495 (M+)；Its reaction equation is as follows:
B 3.47g (7.0mmol) compound f is dissolved in the N,N-dimethylformamide that 30mL is dried by ()
In, and it is cooled to 0 DEG C.Then 20.0mL (210.0mmol) phosphorus oxychloride is slowly added dropwise and mixes into reaction
In thing, drip complete, be warming up to 50 DEG C of stirring reaction 2h.It is cooled to room temperature, reactant liquor is poured into ice
In water-bath, and it is the most neutral to add tune pH value in saturated sodium carbonate solution.After dichloromethane extracts, it is associated with
Machine phase, after washing with saturated common salt, uses anhydrous MgSO4It is dried overnight.Filtering, solvent is steamed in rotation, through silica gel
Column chromatography for separation obtains product g, and eluant is to obtain after petroleum ether and dichloromethane mix for 2:1 by volume,
Productivity is 72%, MS (EI) m/z:523 (M+)；Its reaction equation is as follows:
(2) preparing polymer B 1, reaction equation is:
Under nitrogen protection, 1.8g (2.0mmol) A1 and 1.05g (2.0mmol) g 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.Productivity 62%, coagulates product B1
Glue penetration chromatograph (GPC) is tested, and number-average molecular weight ≈ 9380, monodispersity is 2.1.
Three, preparing copolymer p 1, reaction equation is as follows:
Thering is provided compound h1, structural formula is
164mg (0.175mmol) B1 and 0.7g (3.5mmol) h1 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, productivity 85%.
Copolymer p 1 after purifying carries out GPC test, number-average molecular weight Mn ≈ 11080, and polymer list divides
Scattered property is 2.02.
Embodiment 2
A kind of containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 2
(n=60), structural 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 after stirring reaction 3h,
The 10mL anhydrous tetrahydrofuran solution adding 0.44g (2.0mmol) a carries out Wittig-Horner reaction,
Return to room temperature after insulation reaction 0.5h, continue reaction 12h, stopped reaction.Rotation is steamed, and removes the anti-of excess
Answer liquid, the crude on silica gel column chromatographic isolation and purification obtained, obtain product c2；Eluant be normal hexane and
Dichloromethane is to obtain after 3:1 mixes according to volume ratio, productivity 53%, and 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:
(1) compound g is prepared；
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 2 is prepared；Reaction equation is:
Under nitrogen protection, 2.85g (2.2mmol) A2 and 1.05g (2.0mmol) g 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, productivity 58%.
Product B2 carries out GPC test, number-average molecular weight ≈ 79860, and monodispersity is 2.2.
Three, preparing copolymer p 2, reaction equation is as follows:
Thering is provided compound h2, structural formula is
266mg (0.2mmol) B2 and 774mg (4.5mmol) h2 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, productivity 82% night.
Copolymer p 2 after purifying carries out GPC test, number-average molecular weight Mn ≈ 88320, and polymer list divides
Scattered property is 1.8.
Embodiment 3
A kind of containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 3
(n=30), structural 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, it is slowly added to the cyclohexane solution (4.5mmol) of 3.0mL1.5M LDA, stirs at-78 DEG C
After reaction 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
Steam, remove the oxolane of excess, the crude on silica gel column chromatographic isolation and purification obtained, obtain product c3；
Eluant for being to obtain after 4:1 mixing for normal hexane and dichloromethane according to volume ratio, 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, it is slowly added to the hexane solution (5.0mmol) of 2.0mL2.5M n-BuLi, stirs at-78 DEG C
After reaction 3h, add the Me of 1.5mL (5.0mmol)3SnCl, returns to room after insulation reaction 1h
Temperature, continues reaction 23h, obtains product, i.e. A3, and mass spectrometric measurement result is MS (EI) m/z:1744 (M+)；
Two, preparation polymer B 3, structural formula is:
(1) compound g is prepared；
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 3 is prepared；Reaction equation is:
Under nitrogen protection, 4.36g (2.5mmol) A3 and 1.05g (2.0mmol) g 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, productivity 48%.
Product B3 carries out GPC test, number-average molecular weight ≈ 53400, and monodispersity is 1.9.
Three, preparing copolymer p 3, reaction equation is as follows:
Thering is provided compound h3, structural formula is
356mg (0.2mmol) B3 and 2.16mg (4.5mmol) h3 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, productivity 78%.
Copolymer p 3 after purifying carries out GPC test, number-average molecular weight Mn ≈ 66900, and polymer list divides
Scattered property is 1.78.
Embodiment 4
A kind of containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 4
(n=15), structural 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 cyclohexane solution ((6.0mmol), the stirring reaction at-78 DEG C of 2.0mL3M LDA
After 3h, 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) preparing compound A4, reaction equation is:
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:
(1) compound g is prepared；
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 4 is prepared；Reaction equation is:
Under nitrogen protection, 1.55g (2.0mmol) A4 and 1.05g (2.0mmol) g 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), bubbling 1h removes
Go the oxygen of residual, back flow reaction 30h at 80 DEG C, by mixed liquor decompression distillation, remove the N, N-of excess
Dimethylformamide, then be added drop-wise in methanol settle.Sucking filtration, methanol washs, and is dried.Then pass through
The column chromatography of aluminium oxide, chloroform drip washing.Distillation, removes organic solvent, and methanol settles.Sucking filtration, gained is solid
Body acetone surname extraction three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product B4, productivity night
60%。
Product B4 carries out GPC test, number-average molecular weight ≈ 12150, and monodispersity is 2.3.
Three, preparing copolymer p 4, reaction equation is as follows:
143mg (0.2mmol) B4 and 900mg (4.5mmol) h1 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, productivity 82%.
Copolymer p 4 after purifying carries out GPC test, number-average molecular weight Mn ≈ 14685, and polymer list divides
Scattered property is 1.9.
Embodiment 5
A kind of containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 5
(n=18), structural 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, finishes, at-78 DEG C
After lower stirring 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) preparing compound A-45, reaction equation is:
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:
(1) compound g is prepared；
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 5 is prepared；Reaction equation is:
Under nitrogen protection, 2.11g (2.0mmol) A5 and 1.05g (2.0mmol) g is joined 80mL
In dry toluene, bubbling 0.5h removes the oxygen of residual, then is rapidly added catalyst Pd2(dba)3(16.5mg,
0.018mmol) with P (o-Tol)3(54.8mg, 0.18mmol) forms mixed liquor, is removed by mixed liquor bubbling 1h
Go the oxygen of residual, back flow reaction 36h at 110 DEG C, after reaction terminates, by mixed liquor decompression distillation, remove
Remove the toluene of excess, then be added drop-wise in methanol settle.Sucking filtration, methanol washs, and is dried.Then pass through
The column chromatography of aluminium oxide, chloroform drip washing.Distillation, removes organic solvent, and methanol settles.Sucking filtration, gained is solid
Body acetone surname extraction three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product B5, productivity night
51%。
Product B5 carries out GPC test, number-average molecular weight ≈ 19638, and monodispersity is 2.0.
Three, preparing copolymer p 5, reaction equation is as follows:
218mg (0.2mmol) B5 and 900mg (4.5mmol) h1 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, productivity 81%.
Copolymer p 5 after purifying carries out GPC test, number-average molecular weight Mn ≈ 22914, and polymer list divides
Scattered property is 1.9.
Embodiment 6
A kind of containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 6
(n=20), structural 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, finishes, at-78 DEG C
After lower stirring reaction 2.5h, the 10mL anhydrous tetrahydrofuran solution adding 0.22g (1.0mmol) a enters
Row 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) preparing compound A6, reaction equation is:
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:
(1) compound g is prepared；
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 6 is prepared；Reaction equation is:
Under nitrogen protection, 4.845g (3.0mmol) A6 and 1.05g (2.0mmol) g is joined 80mL
In dry toluene, bubbling 0.5h removes the oxygen of residual, then is rapidly added catalyst Pd2(dba)3(0.1825
mg,2×10-4And P (o-Tol) mmol)3(0.1215mg, 4 × 10-4Mmol) mixed liquor is formed, will mixing
Liquid bubbling 1h removes the oxygen of residual, and back flow reaction 30h at 110 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, dry
Dry.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, productivity 45%.
Product B6 carries out GPC test, number-average molecular weight ≈ 33040, and monodispersity is 2.2.
Three, preparing copolymer p 6, reaction equation is as follows:
330mg (0.2mmol) B6 and 1.0g (5mmol) h1 is joined in 15mL chloroform, then drips
Enter 0.6mL pyridine, stirring reaction 24h under the conditions of 40 DEG C of lucifuges.After reaction stops, partial solvent is steamed in rotation,
Again residual reaction liquid is poured in 50mL methanol, generates a large amount of precipitation, filter, obtain crude product.Again will
After crude product dissolves with 15mL chloroform, after the Teflon filtration membrane filtration of 0.45 μm, rotation is steamed, and removes
Remove major part chloroform, then be slowly dropped in methanol and settle, sucking filtration, it is pumped through under vacuum pump and is produced night
Thing P6, productivity 76%.
Copolymer p 6 after purifying carries out GPC test, number-average molecular weight Mn ≈ 36680, and polymer list divides
Scattered property is 2.12.
Embodiment 7
A kind of containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers, it is designated as copolymer p 7
(n=5), structural 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, finishes, at-78 DEG C
After lower stirring 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) 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, 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:
(1) compound g is prepared；
Concrete operations are with (1) step of embodiment 1 step 2.
(2) polymer B 7 is prepared；Reaction equation is:
Under nitrogen protection, 1.44g (2.0mmol) A7 and 1.05g (2.0mmol) g 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, productivity 59%.
Product B7 carries out GPC test, number-average molecular weight ≈ 3770, and monodispersity is 2.3.
Three, preparing copolymer p 7, reaction equation is as follows:
151mg (0.2mmol) B7 and 900mg (4.5mmol) h1 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 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, productivity 79%.
Copolymer p 7 after purifying carries out GPC test, number-average molecular weight ≈ 5765, and monodispersity is 2.14.
Embodiment 8
With the embodiment of the present invention 2 preparation containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers
P2 is active layer, prepares organic solar batteries device, including the substrate of glass 1 stacked gradually, and anode 2,
Middle auxiliary layer 3, active layer 4 and negative electrode 5, this device architecture specifically can be briefly described as: substrate of glass/
Anode/centre auxiliary layer/active layer/negative electrode, is shown in Fig. 1.Wherein, anode 2 is ITO(tin indium oxide), in
Between auxiliary layer 3 material use poly-(3,4-Ethylenedioxy Thiophene) (PEDOT) and polystyrolsulfon acid (PSS)
The composite formed, is called for short PEDOT:PSS；Active layer 4 includes electron donor material and electron acceptor material
Material, the material of electron donor be the embodiment of the present invention prepare containing allene contracting thiourea-dithieno pyrroles-benzo
Two thiophene copolymers, the material of electron acceptor is [6,6] phenyl-C61-methyl butyrate (being called for short PCBM)；Negative electrode
The material of 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 P2 and PCBM with mass ratio be
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.
With making containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers P2 of embodiment 2 preparation
Material for active layer 4 prepares organic solar batteries device, obtains device, and all preparation process are all carrying
For carrying out in the glove box of nitrogen inert atmosphere.
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 with the present invention containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers P2 as activity
The performance data of the organic solar batteries device of layer preparation
As seen from the data in Table 1, being total to containing allene contracting thiourea-dithieno pyrroles-benzene 1,4-Dithiapentalene by the present invention
The energy conversion efficiency of the organic solar batteries device that polymers P2 is prepared as active layer is 1.58%.Show
The present invention's contains 4,8-bis-(1,3-bis-mercaptan-2-containing allene contracting thiourea-dithieno pyrroles-benzene 1,4-Dithiapentalene
Aldehyde) benzo [1,2-b:4,5-b '] two thiophene derivants, dithieno pyrrole 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 dithieno pyrroles
Donor monomer is as main polymer chain, and as by body unit, allene contracting Thiourea dyestuff is articulated in side chain
On, by main chain with side chain to the interaction of this in receptor " push-pull electronics ", add master interchain shape
The two-dimentional conjugated system become, reduces the energy gap of conjugated polymer simultaneously, and the light substantially increasing material absorbs
Scope.
Embodiment 9
With prepared by embodiment 3 containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers P3 it is
Luminescent layer, prepares 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: glass base
The end/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.Its
In, transparent anode 02 material is tin indium oxide (ITO), and luminescent layer 03 material is that the embodiment of the present invention 3 is made
Standby copolymer, uses spin coating technique to prepare luminescent layer on ITO, and the material of cathode buffer layer 04 is fluorination
Lithium (LiF), the material of negative electrode 05 is metallic aluminium, and the preparation method of each layer is carried out by existing preparation method,
Obtain organic 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 2.3cd/A, and high-high brightness is 1375cd/m2。
Embodiment 10
With embodiment 6 preparation copolymer p 6 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 of the embodiment of the present invention 6 preparation, source electrode (S) 005 He
Drain electrode (D) 006 all uses gold as electrode.
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 6 of the embodiment of the present invention 6 preparation is
1.25×10-4m2/ Vs, show prepared by the present invention containing allene contracting thiourea-dithieno pyrroles-benzene 1,4-Dithiapentalene
Polymer has good 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 contains allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers, it is characterised in that
For having the 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.
2. the preparation method containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers, its
It is characterised by, including following operating procedure:
(1) polymer B is prepared；
Compound A and compound g 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 g 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, n is the integer between 5～60；
Reaction equation is:
(2) copolymer p is prepared；
The compound h that following structural formula represents is provided:
R2For C1～C12The alkyl of straight or branched；
Mol ratio 1:20～the polymer B of 1:25 and compound h 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. as claimed in claim 2 containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers
Preparation method, it is characterised in that described catalyst is the mixture of organic palladium or organic palladium and organic phosphine.
4. as claimed in claim 3 containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers
Preparation method, it is characterised in that described organic palladium is double (triphenylphosphine) palladium chloride or four (triphenylphosphines)
Palladium, described organic palladium is three (dibenzalacetone) two palladium and three (2-tolyl) phosphine with the mixture of organic phosphine
Mixture；
Three (dibenzalacetone) two palladium and three (2-tolyl) phosphine in the mixture of described organic palladium and organic phosphine
Mol ratio is 1:2～1:20.
5. as claimed in claim 3 containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers
Preparation method, it is characterised in that the mole dosage of described organic palladium is compound g mole dosage
0.01%～5%.
6. as claimed in claim 2 containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers
Preparation method, it is characterised in that described first organic solvent is oxolane, DMF
Or toluene；Described second organic solvent is chloroform.
7. as claimed in claim 2 containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers
Preparation method, it is characterised in that step (1) described isolation and purification method is:
After the completion of reaction, the decompression of polymer B reactant liquor is distilled off 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 after,
Again with methanol settles, and sucking filtration is pumped through under vacuum pump and obtains product night.
8. as claimed in claim 2 containing allene contracting thiourea-dithieno pyrroles-benzene 1,4-Dithiapentalene copolymerization
The preparation method of thing, 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, then filter, obtain crude product；After again crude product being dissolved with chloroform, through polytetrafluoroethyl-ne
After alkene filter membrane filters, rotation is steamed, and removes major part chloroform, then is slowly dropped in methanol and settles, takes out
Filter, is pumped through under vacuum pump and obtains product night.
9. as claimed in claim 2 containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers
Preparation 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
Add the cyclohexane solution of lithium diisopropyl amido, at-78 DEG C after stirring reaction 2～3h, add chemical combination
The tetrahydrofuran solution of thing a, carries out Wittig-Horner reaction, returns to room after insulation reaction 0.5～1h
Temperature, continues reaction 12～15h, obtains product, i.e. compound c；Wherein, lithium diisopropyl amido and b
Mol ratio 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,
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. as claimed in claim 1 containing allene contracting thiourea-dithieno pyrroles-benzo two thiophene copolymers
Application in polymer solar battery, organic electroluminescence device and organic field effect tube.
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