CN102276803A - Polymeric material containing anthracene and pyrrole-pyrrole-dione unit, preparation method thereof and application thereof - Google Patents
Polymeric material containing anthracene and pyrrole-pyrrole-dione unit, preparation method thereof and application thereof Download PDFInfo
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Abstract
The invention relates to a polymeric material containing anthracene and a pyrrole-pyrrole-dione unit, a preparation method thereof and an application thereof. The polymeric material which has a structural formula (III) shown in the specification is copolymerized from anthracene, and pyrrole-pyrrole-dione or derivatives thereof. In the invention, groups for improving the solubility are introduced into pyrrole-pyrrole-dione at the second position and the fifth position to improve the solubility and the film forming ability of the polymeric material, and substituents at third and the sixth position of pyrrole-pyrrole are changed to regulate light absorption range of pyrrole-pyrrole-dione. So the obtained polymeric material containing anthracene and the pyrrole-pyrrole-dione unit has the advantages of good dissolvability, wide spectrum absorption range, and high energy conversion efficiency, can be applied to the organic solar cell field, the organic electroluminescent field, the organic field effect transistor field, the organic optical storage field, the organic non-linear material field, the organic laser field and the like as organic semiconductor materials.
Description
[technical field]
The present invention relates to the organic semiconductor material field, relate in particular to a kind of anthracene and unitary organic semiconductor of pyrrolopyrrole diketone and its production and application of containing.
[background technology]
Utilize cheap material preparation low cost, dynamical solar cell is the research focus and the difficult point in photovoltaic field always.Polymer materials is on the one hand because the environmental stability of organic materials is good, preparation cost is low, function is easy to modulation, snappiness and good film-forming property; On the other hand because the organic solar batteries course of processing is simple relatively, but cold operation, and advantage such as the element manufacturing cost is also lower and receiving much concern becomes cheap and attractive solar cell material.
Pyrrolopyrrole diketone or derivatives thereof has high stability to light, heat and different climatopes, but because stronger π-pi-conjugated and molecule hydrogen bond is arranged in the molecular structure, its solvability is relatively poor, thereby the film forming processing characteristics is relatively poor, the device that causes preparing is easy to take place problem of phase separation, influence the efficient of exciton diffusion, the loss of energy is higher.Simultaneously, the absorption spectrum of pyrrolopyrrole or derivatives thereof is narrow, and is high not enough with the emmission spectrum matching degree of sunlight, can not effectively utilize sunlight, also can reduce the photoelectric transformation efficiency of organic solar batteries.
[summary of the invention]
Based on this, be necessary to provide that a kind of solvability is good, light abstraction width is wide contains anthracene and the unitary polymer materials of pyrrolopyrrole diketone.
A kind of anthracene and unitary polymer materials of pyrrolopyrrole diketone of containing has following structure formula III:
Wherein, n is 1～200 natural number; R
1, R
2Be hydrogen, halogen, cyano group, C
1～C
40Alkyl, aryl or heteroaryl; R
3Be hydrogen or C
1～C
40Alkyl; R
4Be hydrogen, C
1～C
40Alkyl, C
1～C
40Alkoxyl group, C
6～C
40Aryl, C
6～C
40Aralkyl or C
6～C
40Alkoxy aryl.
Simultaneously, also be necessary to provide a kind of its preparation method at above-mentioned polymer materials.
The above-mentioned preparation method who contains anthracene and the unitary polymer materials of pyrrolopyrrole diketone, under oxygen free condition, with 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene or derivatives thereof (I) and 2,5-dialkyl group-3,6-two (5-bromo-di-thiophene or derivatives thereof) base-pyrrolopyrrole diketone (II) carried out the Suzuki reaction in 1: 1 in molar ratio～1: 4 in catalyzer, alkaline solution and solvent, obtain containing anthracene and the unitary polymkeric substance of pyrrolopyrrole diketone (III), reaction formula is as follows:
Wherein, n is 1～200 natural number, R
1, R
2For being selected from hydrogen, halogen, cyano group, C
1～C
40Alkyl, aryl or heteroaryl; R
3For being selected from hydrogen or C
1～C
40Alkyl; R
4For being selected from hydrogen, C
1～C
40Alkyl, C
1～C
40Alkoxyl group, C
6～C
40Aryl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
Preferably, described catalyzer is Pd (PPh
3)
4, Pd
2(dba)
3/ P (o-Tol)
3Or Pd (PPh
3)
2Cl
2In a kind of; Catalyst consumption is 9,0.5%～10% of 10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene or derivatives thereof (I) molar weight; Described alkaline solution is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3At least a in the aqueous solution or the tetraethyl ammonium hydroxide aqueous solution; The consumption of alkali is 9 in the alkaline solution, 5～10 times of 10-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic anthracene or derivatives thereof (I) molar weight; Described solvent is at least a in toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate.
Preferably, the temperature of reaction of described Suzuki reaction is 60 ℃-100 ℃, and the reaction times is 12h～72h.
Preferably, also comprise describedly 9,10-two (4,4,5,5-tetramethyl--1,3, assorted oxygen pentaboranes of 2-two) preparation method of basic anthracene or derivatives thereof (I): under the anhydrous and oxygen-free reaction conditions, with 9,10-dibromoanthracene or derivatives thereof (IV) is dissolved in the organic solvent under-70 ℃～-85 ℃ temperature with n-Butyl Lithium (V), adds 2-isopropoxy-4,4 then, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes (VI), temperature of reaction system is adjusted to 10-40 ℃ and keep this temperature, and reaction 12h～48h promptly gets 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene or derivatives thereof (I); The reaction formula of this step is expressed as:
Preferably, described 9, the mol ratio of 10-dibromoanthracene or derivatives thereof (IV) and n-Butyl Lithium (V) is 1: 2～1: 4; Described organic solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; The mole dosage of described organic solvent is 9,2.0～4.0 times of 10-dibromoanthracene or derivatives thereof.
Preferably, after the described Suzuki reaction, also comprise following purification step: add deionized water and toluene extraction in anthracene and the unitary polymers soln of pyrrolopyrrole diketone toward containing, get underpressure distillation after the organic phase, product after will distilling again splashes into to anhydrous methanol and stirs, with the solid process suction filtration of separating out, obtain pressed powder after the oven dry, again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, revolve again to steam and splash into to methanol solvate and stir 1～10h, at last polymer collection is dried, use the Soxhlet extractor extracting, what promptly obtain purifying contains anthracene and the unitary polymkeric substance of pyrrolopyrrole diketone (III).
Above-mentioned make contain anthracene and the unitary polymer materials of pyrrolopyrrole diketone, can be used as organic semiconductor material and be applied in the fields such as machine solar cell, organic field effect tube, organic electroluminescent, organic optical storage, organic non-linear optical properties or organic laser.
As a kind of organic solar batteries device, comprise glass baseplate successively, be located at conductive layer on the described glass baseplate, be coated in poly-(3 on the described conductive layer, the 4-Ethylenedioxy Thiophene): gather (styrene sulfonic acid) layer, be coated in described poly-(3, the 4-Ethylenedioxy Thiophene): the active coating on poly-(styrene sulfonic acid) layer, be deposited on the metal Al layer on the described active coating and be used to encapsulate the Resins, epoxy of above-mentioned each layer, described active coating comprises electron donor material and electron acceptor material, described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate, described electron donor material are above-mentioned anthracene and the unitary polymer materials of pyrrolopyrrole diketone of containing.
A kind of organic electroluminescence device, comprise glass baseplate successively, be located at conductive layer on the described glass baseplate, be coated in luminescent layer on the described conductive layer, evaporation is at the LiF buffer layer on the described luminescent layer and be deposited on metal Al layer on the described LiF buffer layer, wherein, the luminescent layer material is above-mentioned anthracene and the unitary polymer materials of pyrrolopyrrole diketone of containing.
A kind of organic field effect tube device comprises the doped silicon wafer base material successively, is located at the SiO of described doped silicon wafer substrate surface
2Insulation layer, be coated in described SiO
2The octadecyl trichlorosilane decorative layer on surface, be coated in the organic semiconductor layer on the described octadecyl trichlorosilane decorative layer and the source electrode and the drain electrode of organic semiconductor layer surface are set, wherein, described organic semiconductor layer is above-mentioned anthracene and the unitary polymer materials of pyrrolopyrrole diketone of containing.
By introduce to increase the group of solubility on 2,5 of pyrrolopyrrole diketone, alkyl for example improves the solubility and the film-forming properties of polymer materials, and regulates and control the extinction scope of pyrrolopyrrole diketone by the substituting group that changes 3,6.Therefore, contain anthracene and the unitary polymer materials of pyrrolopyrrole diketone and have good solubility, lower energy gap, the spectral absorption scope of broad, and this polymer materials helps current carrier and more effectively transmits in active layer material inside, the photoelectric transformation efficiency height.
Utilize the Suzuki reaction principle in the above-mentioned preparation process, technology is simple, low for equipment requirements.
With polymer solar cell device, organic electroluminescent device and the organic field effect tube device of the above-mentioned polymer materials that obtains as the active material preparation, the photoelectric transformation efficiency height, easy to utilize.
[description of drawings]
Fig. 1 is to contain anthracene and the unitary polymer materials of the pyrrolopyrrole diketone structural representation as the organic solar batteries device of active coating electron donor material for Fig. 1.
Fig. 2 is to contain anthracene and the unitary polymer materials of the pyrrolopyrrole diketone structural representation as the organic electroluminescence device of luminescent layer.
Fig. 3 is to contain anthracene and the unitary polymer materials of the pyrrolopyrrole diketone structural representation as the organic field effect tube device of organic semiconductor layer.
[embodiment]
By with anthracene and the copolymerization of pyrrolopyrrole diketone or derivatives thereof, on 2,5 of pyrrolopyrrole diketone, introduce solubility and the film-forming properties that the group that increases solubility improves polymer materials, and regulate and control the extinction scope of pyrrolopyrrole diketone by the substituting group that changes 3,6 of pyrrolopyrroles, obtain contain anthracene and the unitary polymer materials of pyrrolopyrrole diketone has the spectral absorption scope of good solubility, broad and higher effciency of energy transfer.
The above-mentioned polymkeric substance that obtains can be used as organic semiconductor material and is applied in the fields such as organic photovoltaic cell, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties and organic laser, and its structural formula is:
Wherein, n is 1～200 natural number; R
1, R
2Be hydrogen, halogen, cyano group, C
1～C
40Alkyl, aryl or heteroaryl; R
3Be hydrogen or C
1～C
40Alkyl; R
4Be hydrogen, C
1～C
40Alkyl, C
1～C
40Alkoxyl group, C
6～C
40Aryl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
The above-mentioned preparation process that contains anthracene and the unitary polymer materials of pyrrolopyrrole diketone specifically comprises the steps:
At first, under the anhydrous and oxygen-free reaction conditions, with 9,10-dibromoanthracene or derivatives thereof and n-Butyl Lithium were added in the organic solvent with mol ratio under-70 ℃～-85 ℃ in 1.0: 2.0～1.0: 4.0, added 2-isopropoxy-4 then, 4,5,5-tetramethyl--1,3, (its mole dosage is 9 to 2-two assorted oxygen pentaboranes (or two tetramethyl ethylene ketone closes two boron), 2.0～4.0 times of 10-dibromoanthracene or derivatives thereof), reacted 12～48 hours, promptly obtain 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene or derivatives thereof;
Wherein, solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate;
Its reaction formula is as follows:
Secondly, under oxygen free condition, with 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene or derivatives thereof, 2,5-dialkyl group-3,6-two (5-bromo-di-thiophene or derivatives thereof) base-pyrrolopyrrole diketone 1: 1 in molar ratio～1: 4 carries out Suzuki reaction 12～72 hours under 60～100 ℃, catalyzer, alkaline solution and solvent, obtain polymer materials;
Wherein, catalyzer is Pd (PPh
3)
4, Pd
2(dba)
3/ P (o-Tol)
3Or Pd (PPh
3)
2Cl
2In at least a, alkali is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3At least a in the aqueous solution or the tetraethyl ammonium hydroxide aqueous solution, solvent are at least a in toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate, and catalyst consumption is 9,10-two (4,4,5,5-tetramethyl--1,3, assorted oxygen pentaboranes of 2-two) 0.5%～10% of basic anthracene or derivatives thereof molar weight, the consumption of alkali is 9, and 10-two (4,4,5,5-tetramethyl--1,3, assorted oxygen pentaboranes of 2-two) 5～10 times of basic anthracene or derivatives thereof molar weight; Reaction formula is as follows:
At last, add deionized water and toluene extraction in anthracene and the unitary polymers soln of pyrrolopyrrole diketone toward containing, get underpressure distillation after the organic phase, product after will distilling again splashes into to anhydrous methanol and stirs, with the solid process suction filtration of separating out, obtain pressed powder after the oven dry, again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, revolve again to steam and splash into to methanol solvate and stir 1～10h, with polymer collection oven dry, use the Soxhlet extractor extracting at last, what promptly obtain purifying contains anthracene and the unitary polymkeric substance of pyrrolopyrrole diketone.
Mainly reaching accompanying drawing below in conjunction with specific embodiments is further described containing anthracene and the unitary polymer materials of pyrrolopyrrole diketone and its production and application.
The open following polymer P 1 of structure of embodiment 1 present embodiment:
The preparation process of P1 is as follows:
Step 1,9, the preparation of the basic anthracene of 10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes):
Put up tetrahydrofuran (THF) (THF) water distilling apparatus, the tetrahydrofuran solvent with KOH dry a couple of days is joined in the 1000ml single port bottle, cut into the sodium piece again and add benzophenone, constantly stir and the system of being back to is intense violet color, it is stand-by to steam purified THF.
Put up the anhydrous and oxygen-free reaction unit, under the protection of continuous stirring and N2, in there-necked flask, add 9 of light yellow crystal shape, 10-dibromoanthracene 9.0mmol, inject the above-mentioned purified tetrahydrofuran solvent of 150ml with syringe, slowly inject 27.0mmol n-BuLi with syringe again under-75 ℃ of conditions, system is gradually by the faint yellow orange that becomes, stirring reaction 2 hours; React after 2 hours, under-75 ℃ of conditions, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes, system is become faint yellow by orange, be warmed up to room temperature reaction and spend the night.
After reaction finishes, add the saturated NaCl aqueous solution, chloroform extraction, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve and steam solvent.At last with the crude product sherwood oil: ethyl acetate (v/v=15: 1) separate, obtain pulverulent solids, productive rate 58% for leacheate carries out silica gel column chromatography.GC-MS(EI-m/z)：430(M
+)。
Step 2,3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Under the protection of argon gas, in reaction flask, behind the adding 35.7mmol potassium tert.-butoxide, 30mmol 2-cyano thiophene is dissolved in 25ml tertiary amyl alcohol solvent and with syringe it is added to reaction flask, be warming up to 110 ℃.Dropwise join in the reaction system after again the 10mmol dimethyl succinate being dissolved in 8ml tertiary amyl alcohol solvent, keep dropping and kept thermotonus again 1.5 hours after 1 hour.Continue reaction 2 hours after then by-product carbinol being distilled again.Reaction system is reduced to 65 ℃ at last, with the dilution of 50ml methyl alcohol, in the acetic acid and after, 10min again refluxes.Obtain black solid behind the suction filtration, the methyl alcohol of reusable heat and deionized water respectively wash 2 times, obtain product 3 after the vacuum-drying, and 6-dithienyl-pyrrolopyrrole diketone can directly enter next step reaction, productive rate 78% after purifying.GC-MS(EI-m/z)：300(M
+)。
Step 3,2,5-dioctyl-3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
With 3,6-dithienyl-pyrrolopyrrole diketone 43.3mmol and Anhydrous potassium carbonate 24g are dissolved in 250ml N, and the dinethylformamide solvent joins it two mouthfuls of reaction flask post-heating to 140 ℃ under the protection of argon gas.Added 1-bromooctane 200mmol stirring reaction 16 hours with syringe again.Be cooled to room temperature then, there is solid to separate out after pouring reactant into the 500ml frozen water, filter, thing be will leach and deionized water and washed with methanol used for several times, be after washing fluid carries out silica gel column chromatography, to obtain solid powdery product 2,5-dioctyl-3 with methylene dichloride after the vacuum-drying, 6-dithienyl-pyrrolopyrrole diketone, productive rate 71%.GC-MS(EI-m/z)：525(M
+)。
Step 4,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
With 2; 5-dioctyl-3; 6-dithienyl-pyrrolopyrrole diketone 8.6mmol and N-bromo-succinimide (NBS) 17.6mmol are dissolved in the 200ml chloroform solvent, are added in two mouthfuls of reaction flasks of argon shield and constantly to stir, and the lucifuge reaction is 50 hours at ambient temperature.Product after the reaction end is joined in the 200ml methanol solvate, there is solid to separate out, filter, thing hot washed with methanol 2 times will be leached, carry out silica gel column chromatography after the vacuum-drying and purify, obtain solid powdery product 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone, productive rate 75%.GC-MS(EI-m/z)：682(M
+)。
Step 5,2,5-dioctyl-3, the preparation of 6-two (di-thiophene) base-pyrrolopyrrole diketone:
With 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 1mmol and 2-tributyl tinbase thiophene 2.2mmol are dissolved in the dry toluene solvent, add tetra-triphenylphosphine palladium 0.03mmol again, and back flow reaction is spent the night under protection of nitrogen gas.Cooling back sedimentation in methanol solvate is through obtaining 2,5-dioctyl-3,6-two (di-thiophene) base-pyrrolopyrrole diketone, productive rate 68% after the silicagel column purification.GC-MS(EI-m/z)：689(M
+)。
Step 6,2,5-dioctyl-3, the preparation of 6-two (5-bromo-di-thiophene) base-pyrrolopyrrole diketone:
With 2; 5-dioctyl-3; 6-two (di-thiophene) base-pyrrolopyrrole diketone 1mmol and N-bromo-succinimide (NBS) 2.3mmol are dissolved in the 200ml chloroform solvent, are added in two mouthfuls of reaction flasks of argon shield and constantly to stir, and the lucifuge reaction is 50 hours at ambient temperature.Product after the reaction end is joined in the 200ml methanol solvate, there is solid to separate out, filter, thing hot washed with methanol 2 times will be leached, carry out silica gel column chromatography after the vacuum-drying and purify, obtain solid powdery product 2,5-dioctyl-3,6-two (5-bromo-di-thiophene) base-pyrrolopyrrole diketone, productive rate 72%.GC-MS(EI-m/z)：847(M
+)。
The preparation of step 7, P1:
In reactor, add 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene 1mmol, 2,5-dioctyl-3, the Na of 6-two (5-bromo-di-thiophene) base-pyrrolopyrrole diketone 1mmol, tetra-triphenylphosphine palladium 0.02mmol, 2mol/L
2CO
3Aqueous solution 10ml and toluene solvant 30ml are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 90 ℃ of conditions, react 72h.
Behind the reaction 72h, in the product reaction flask, add deionized water and toluene extraction, get organic phase, with underpressure distillation with polymkeric substance/toluene solution evaporate to dryness to the 5ml, it is splashed into constantly stirring in the 300ml anhydrous methanol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column, remove the catalyzer tetra-triphenylphosphine palladium, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 1 is collected oven dry with neutral alumina.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymer P 1 after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 51000, the polymkeric substance monodispersity is 2.25.
The open following polymer P 2 of structure of embodiment 2 present embodiments:
The preparation process of P2 is as follows:
Step 1,9, the preparation of the basic anthracene of 10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes):
Its preparation sees the step 1 among the embodiment 1 for details.
Step 2,3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Its preparation sees the step 2 among the embodiment 1 for details.
Step 3,2,5-dioctyl-3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Its preparation sees the step 3 among the embodiment 1 for details.
Step 4,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation sees the step 4 among the embodiment 1 for details.
Step 5,2,5-dioctyl-3, the preparation of 6-two (4-dodecyl di-thiophene) base-pyrrolopyrrole diketone:
With 2; 5-dioctyl-3; 6-two (5-bromothiophene) base-pyrrolopyrrole diketone 1mmol and 4-dodecyl-2-tributyl tinbase thiophene 2.3mmol is dissolved in the dry toluene solvent, adds tetra-triphenylphosphine palladium 0.04mmol again, and back flow reaction is spent the night under protection of nitrogen gas.Cooling back sedimentation in methanol solvate is through obtaining 2,5-dioctyl-3,6-two (4-dodecyl di-thiophene) base-pyrrolopyrrole diketone, productive rate 77% after the silicagel column purification.GC-MS(EI-m/z)：1026(M
+)。
Step 6,2,5-dioctyl-3, the preparation of 6-two (5-bromo-4-dodecyl di-thiophene) base-pyrrolopyrrole diketone:
With 2; 5-dioctyl-3; 6-two (4-dodecyl di-thiophene) base-pyrrolopyrrole diketone 1mmol and N-bromo-succinimide (NBS) 2.3mmol are dissolved in the 200ml chloroform solvent, are added in two mouthfuls of reaction flasks of argon shield and constantly to stir, and the lucifuge reaction is 40 hours at ambient temperature.Product after the reaction end is joined in the 200ml methanol solvate, there is solid to separate out, filter, thing hot washed with methanol 2 times will be leached, carry out silica gel column chromatography after the vacuum-drying and purify, obtain solid powdery product 2,5-dioctyl-3,6-two (5-bromo-4-dodecyl di-thiophene) base-pyrrolopyrrole diketone, productive rate 75%.GC-MS(EI-m/z)：1183(M
+)。
The preparation of step 7, P2:
Add 9 in reactor, 10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene 1mmol, 2,5-dioctyl-3, the Na of 6-two (5-bromo-4-dodecyl di-thiophene) base-pyrrolopyrrole diketone 1mmol, tetra-triphenylphosphine palladium 0.04mmol, 2mol/L
2CO
3Aqueous solution 10ml and toluene solvant 40ml are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 85 ℃ of conditions, react 70h.
Behind the reaction 70h, add deionized water in the product reaction flask and toluene extracts, get organic phase, with underpressure distillation with polymkeric substance/toluene solution evaporate to dryness to about 5ml, it is splashed into constantly stirring in the 300ml anhydrous methanol, there is solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column, remove the catalyzer tetra-triphenylphosphine palladium, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 2 is collected oven dry with neutral alumina.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymer P 2 after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 37500, the polymkeric substance monodispersity is 2.14.
The open following polymer P 3 of structure of embodiment 3 present embodiments:
The preparation process of P3 is as follows:
Step 1,9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-2, the preparation of 6-two (2-octyl-decyl) anthracene:
Put up the anhydrous and oxygen-free reaction unit, under the protection of continuous stirring and N2, in there-necked flask, add 9,10-two bromo-2, (the synthetic method of this compound is referring to people's such as Klaus Mullen Macromol.Chem.Phys.2006,207 for 6-two (2-octyl-decyl) anthracene 5mmol, 1107-1115), inject 150ml purified tetrahydrofuran solvent with syringe, under-80 ℃ of conditions, slowly inject 15mmol n-BuLi with syringe again, stirring reaction 2 hours; React after 2 hours, under-80 ℃ of conditions, inject 15mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.
After reaction finishes, add saturated sodium-chloride water solution, chloroform extraction, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve and steam solvent.Be that leacheate carries out the silica gel column chromatography separation with crude product with suitable solvent at last, obtain pulverulent solids, productive rate 61%.GC-MS(EI-m/z)：935(M+)。
Step 2,2,5-dioctyl-3, the preparation of 6-two (5-bromo-4-dodecyl di-thiophene) base-pyrrolopyrrole diketone:
Its preparation sees step 2 among the embodiment 2 for details to step 6.
The preparation of step 3, P3:
In reactor, add 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-2,6-two (2-octyl-decyl) anthracene 1mmol, 2,5-dioctyl-3, the Na of 6-two (5-bromo-4-dodecyl di-thiophene) base-pyrrolopyrrole diketone 1mmol, tetra-triphenylphosphine palladium 0.03mmol, 2mol/L
2CO
3Aqueous solution 8ml and toluene solvant 40ml are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 85 ℃ of conditions, react 48h.
Behind the reaction 48h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, with the method for underpressure distillation with polymkeric substance/toluene solution evaporate to dryness to about 5ml, it is splashed into constantly stirring in the 500ml anhydrous methanol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column, remove the catalyzer tetra-triphenylphosphine palladium, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 3 is collected oven dry with neutral alumina.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymer P 3 after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 52900, the polymkeric substance monodispersity is 2.31.
Embodiment 4 is with the organic solar batteries preparation of devices of polymer P 1 as active layer material, and its structure as shown in Figure 1.
Active layer material comprises above-mentioned P1 as electron donor material, [6,6] phenyl-C
61-methyl-butyrate (being called for short PCBM) is as electron acceptor material, be that device architecture is glass/ITO/PEDOT:PSS/ active coating/Al, wherein ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is poly-(3, the 4-Ethylenedioxy Thiophene), PSS is poly-(styrene sulfonic acid); Ito glass is through after the ultrasonic cleaning, handle with oxygen-Plasma, coat PEDOT:PSS on ITO, active coating adopts spin coating technique as electron donor material and PCBM as electron acceptor material with P1, metal aluminium electrode prepares by vacuum evaporation technology, obtains the organic solar batteries device.With device with epoxy encapsulation after, place under 110 ℃ of air tight conditions annealing 4 hours, drop to room temperature again.Because after device was annealed, the chemical structure of material was more regular in order, has improved the transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Embodiment 5 is with the preparation of P1 as the luminescent layer organic electroluminescence device, its structure as shown in Figure 2:
This device is followed successively by ITO/P1/LiF/Al, promptly deposition one deck square resistance is that the tin indium oxide (ITO) of 10-20 Ω/mouth is as transparent anode on a glass substrate, on ITO, prepare one deck P1 material as luminescent layer by spin coating technique, vacuum evaporation LiF on this luminescent layer again, as buffer layer, on buffer layer, adopt vacuum coating technology metal refining Al at last, as the negative electrode of device.
Embodiment 6 is with the preparation of the organic field effect tube that contains P1, its structure as shown in Figure 3:
Adopt highly doped silicon chip (Si) as substrate, the SiO that 450nm is thick
2As insulation layer, source electrode (S) and drain electrode (D) all adopt gold as electrode, and P1 is spun to SiO after octadecyl trichlorosilane (OTS) is modified as organic semiconductor layer
2On, thereby make the organic field effect tube that contains P1.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. one kind contains anthracene and the unitary polymer materials of pyrrolopyrrole diketone, it is characterized in that having following structure formula III:
Wherein, n is 1～200 natural number;
R
1, R
2Be hydrogen, halogen, cyano group, C
1～C
40Alkyl, aryl or heteroaryl;
R
3Be hydrogen or C
1～C
40Alkyl;
R
4Be hydrogen, C
1～C
40Alkyl, C
1～C
40Alkoxyl group, C
6～C
40Aryl, C
6～C
40Aralkyl or C
6～C
40Alkoxy aryl.
2. preparation method who contains anthracene and the unitary polymer materials of pyrrolopyrrole diketone, under oxygen free condition, with 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene or derivatives thereof (I) and 2,5-dialkyl group-3,6-two (5-bromo-di-thiophene or derivatives thereof) base-pyrrolopyrrole diketone (II) carried out the Suzuki reaction in 1: 1 in molar ratio～1: 4 in catalyzer, alkaline solution and solvent, obtain containing anthracene and the unitary polymkeric substance of pyrrolopyrrole diketone (III), reaction formula is as follows:
Wherein, n is 1～200 natural number,
R
1, R
2For being selected from hydrogen, halogen, cyano group, C
1～C
40Alkyl, aryl or heteroaryl;
R
3For being selected from hydrogen or C
1～C
40Alkyl;
R
4For being selected from hydrogen, C
1～C
40Alkyl, C
1～C
40Alkoxyl group, C
6～C
40Aryl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
3. the preparation method who contains anthracene and the unitary polymer materials of pyrrolopyrrole diketone as claimed in claim 2 is characterized in that described catalyzer is Pd (PPh
3)
4, Pd
2(dba)
3/ P (o-Tol)
3Or Pd (PPh
3)
2C1
2In a kind of; Catalyst consumption is 9,0.5%～10% of 10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene or derivatives thereof (I) molar weight;
Described alkaline solution is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3At least a in the aqueous solution or the tetraethyl ammonium hydroxide aqueous solution; The consumption of alkali is 9 in the alkaline solution, 5～10 times of 10-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic anthracene or derivatives thereof (I) molar weight;
Described solvent is at least a in toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate.
4. the preparation method who contains anthracene and the unitary polymer materials of pyrrolopyrrole diketone as claimed in claim 2 is characterized in that, the temperature of reaction of described Suzuki reaction is 60 ℃-100 ℃, and the reaction times is 12h～72h.
5. the preparation method who contains anthracene and the unitary polymer materials of pyrrolopyrrole diketone as claimed in claim 2 is characterized in that, also comprises described 9,10-two (4,4,5,5-tetramethyl--1,3, assorted oxygen pentaboranes of 2-two) preparation method of basic anthracene or derivatives thereof (I):
Under the anhydrous and oxygen-free reaction conditions, with 9,10-dibromoanthracene or derivatives thereof (IV) is dissolved in the organic solvent under-70 ℃～-85 ℃ temperature with n-Butyl Lithium (V), add 2-isopropoxy-4,4 then, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes (VI), temperature of reaction system is adjusted to 10-40 ℃ and keep this temperature, and reaction 12h～48h promptly gets 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene or derivatives thereof (I); The reaction formula of this step is expressed as:
6. the preparation method who contains anthracene and the unitary polymer materials of pyrrolopyrrole diketone as claimed in claim 5 is characterized in that, and is described 9, and the mol ratio of 10-dibromoanthracene or derivatives thereof (IV) and n-Butyl Lithium (V) is 1: 2～1: 4;
Described organic solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate;
The mole dosage of described organic solvent is 9,2.0～4.0 times of 10-dibromoanthracene or derivatives thereof (IV).
7. the preparation method who contains anthracene and the unitary polymer materials of pyrrolopyrrole diketone as claimed in claim 2 is characterized in that, after the described Suzuki reaction, also comprises following purification step:
Add deionized water and toluene extraction in anthracene and the unitary polymers soln of pyrrolopyrrole diketone toward containing, get underpressure distillation after the organic phase, product after will distilling again splashes into to anhydrous methanol and stirs, the solid of separating out is obtained pressed powder after through suction filtration, oven dry, again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, revolve again to steam and splash into to methanol solvate and stir 1～10h, at last polymer collection is dried, use the Soxhlet extractor extracting, what promptly obtain purifying contains anthracene and the unitary polymkeric substance of pyrrolopyrrole diketone (III).
8. organic solar batteries device, comprise glass baseplate successively, be located at conductive layer on the described glass baseplate, be coated in poly-(3 on the described conductive layer, the 4-Ethylenedioxy Thiophene): gather (styrene sulfonic acid) layer, be coated in described poly-(3, the 4-Ethylenedioxy Thiophene): the active coating on poly-(styrene sulfonic acid) layer, be deposited on the metal Al layer on the described active coating and be used to encapsulate the Resins, epoxy of above-mentioned each layer, described active coating comprises electron donor material and electron acceptor material, described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate is characterized in that, described electron donor material has following structure formula III for containing anthracene and the unitary polymer materials of pyrrolopyrrole diketone:
Wherein, n is 1～200 natural number;
R
1, R
2Be hydrogen, halogen, cyano group, C
1～C
40Alkyl, aryl or heteroaryl;
R
3Be hydrogen or C
1～C
40Alkyl;
R
4Be hydrogen, C
1～C
40Alkyl, C
1～C
40Alkoxyl group, C
6～C
40Aryl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
9. organic electroluminescence device, comprise glass baseplate successively, be located at conductive layer on the described glass baseplate, be coated in luminescent layer on the described conductive layer, evaporation is at the LiF buffer layer on the described luminescent layer and be deposited on metal Al layer on the described LiF buffer layer, it is characterized in that, the luminescent layer material has following structure formula III for containing anthracene and the unitary polymer materials of pyrrolopyrrole diketone:
Wherein, n is 1～200 natural number;
R
1, R
2Be hydrogen, halogen, cyano group, C
1～C
40Alkyl, aryl or heteroaryl;
R
3Be hydrogen or C
1～C
40Alkyl;
R
4Be hydrogen, C
1～C
40Alkyl, C
1～C
40Alkoxyl group, C
6～C
40Aryl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
10. organic field effect tube device comprises the doped silicon wafer base material successively, is located at the SiO of described doped silicon wafer substrate surface
2Insulation layer, be coated in described SiO
2The octadecyl trichlorosilane decorative layer on surface, be coated in the organic semiconductor layer on the described octadecyl trichlorosilane decorative layer and the source electrode and the drain electrode of organic semiconductor layer surface are set, it is characterized in that, described organic semiconductor layer has following structure formula III for containing anthracene and the unitary polymer materials of pyrrolopyrrole diketone:
Wherein, n is 1～200 natural number;
R
1, R
2Be hydrogen, halogen, cyano group, C
1～C
40Alkyl, aryl or heteroaryl;
R
3Be hydrogen or C
1～C
40Alkyl;
R
4Be hydrogen, C
1～C
40Alkyl, C
1～C
40Alkoxyl group, C
6～C
40Aryl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102976986A (en) * | 2012-11-20 | 2013-03-20 | 溧阳市生产力促进中心 | Method for manufacturing polymer used as electron transfer layer of solar cell |
| CN102993068A (en) * | 2012-11-20 | 2013-03-27 | 溧阳市生产力促进中心 | Electronic transmission layer polymer for solar cell |
| CN103030581A (en) * | 2012-11-20 | 2013-04-10 | 溧阳市生产力促进中心 | Method for manufacturing electron transfer layer in solar cell |
| CN105218791A (en) * | 2015-10-28 | 2016-01-06 | 武汉理工大学 | Containing 2-(4-thiophene-2-phenyl) polymkeric substance of thiophene and its preparation method and application |
| CN106632410A (en) * | 2016-12-20 | 2017-05-10 | 中国科学院化学研究所 | Pyridine-thiophene-based diketopyrrolopyrrole and polymer thereof |
| CN111423426A (en) * | 2019-12-26 | 2020-07-17 | 江西科技师范大学 | Asymmetric 9- (N-tert-butyloxycarbonyl-2-pyrrolyl) -10-five-membered heterocyclic anthracene compound and application thereof |
| CN111574539A (en) * | 2020-05-14 | 2020-08-25 | Tcl华星光电技术有限公司 | Active layer material, preparation method of active layer material and transistor |
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| CN102976986A (en) * | 2012-11-20 | 2013-03-20 | 溧阳市生产力促进中心 | Method for manufacturing polymer used as electron transfer layer of solar cell |
| CN102993068A (en) * | 2012-11-20 | 2013-03-27 | 溧阳市生产力促进中心 | Electronic transmission layer polymer for solar cell |
| CN103030581A (en) * | 2012-11-20 | 2013-04-10 | 溧阳市生产力促进中心 | Method for manufacturing electron transfer layer in solar cell |
| CN102976986B (en) * | 2012-11-20 | 2014-12-10 | 溧阳市生产力促进中心 | Method for manufacturing polymer used as electron transfer layer of solar cell |
| CN103030581B (en) * | 2012-11-20 | 2015-02-25 | 溧阳市生产力促进中心 | Method for manufacturing electron transfer layer in solar cell |
| CN105218791A (en) * | 2015-10-28 | 2016-01-06 | 武汉理工大学 | Containing 2-(4-thiophene-2-phenyl) polymkeric substance of thiophene and its preparation method and application |
| CN106632410A (en) * | 2016-12-20 | 2017-05-10 | 中国科学院化学研究所 | Pyridine-thiophene-based diketopyrrolopyrrole and polymer thereof |
| CN106632410B (en) * | 2016-12-20 | 2019-04-23 | 中国科学院化学研究所 | Pyrido thienyl pyrrolo-pyrrole-dione and its polymer |
| CN111423426A (en) * | 2019-12-26 | 2020-07-17 | 江西科技师范大学 | Asymmetric 9- (N-tert-butyloxycarbonyl-2-pyrrolyl) -10-five-membered heterocyclic anthracene compound and application thereof |
| CN111574539A (en) * | 2020-05-14 | 2020-08-25 | Tcl华星光电技术有限公司 | Active layer material, preparation method of active layer material and transistor |
| CN111574539B (en) * | 2020-05-14 | 2021-07-06 | Tcl华星光电技术有限公司 | Active layer material, preparation method of active layer material and transistor |
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