CN102329417B - Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof - Google Patents
Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a copolymer containing carbazole porphyrin-benzene, which has a structural formula shown as below, wherein n is an integer from 1 to 100, and R1 and R2 are hydrogen or C1-C32 alkyl. The copolymer containing carbazole porphyrin-benzene has good solubility, a broader spectral absorption range and higher energy conversion efficiency and can be used as an organic semiconductor material in solar cells, organic electroluminescent devices, organic field effect transistors and other fields.
Description
[technical field]
The present invention relates to the organic semiconductor material field, relate in particular to a kind of carbazolyl porphyrin-benzene multipolymer and its preparation method and application that contains.
[background technology]
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.Polymer materials on the one hand good due to the environmental stability of organic materials, 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 relatively simple, but cold operation, and the element manufacturing cost is the advantage such as lower and receiving much concern also, becomes cheap and attractive solar cell material.
Porphyrin Molecule is the general name that is connected with a substituent class macrocylc compound on porphin ring, and porphines is the large ring delocalizedπelectron of the two dimensional structure conjugated system that is replaced by the Dan Shuanjian that four pyrrole rings and four methyne bridgings get up.The quantum yield of their charge transfer and energy transfer reaction is higher, has good electronics resiliency and photoelectric magnetic property, good hard and soft property and better thermostability and environmental stability.Therefore, the porphyrin organic semiconductor material is a up-and-coming material of class, and its application in the photovoltaic field has obtained broad research.
Carbazole is the good hole mobile material of a class: on the one hand, due to the pi-conjugated effect of p-, the N atom on carbazole not shared electron is supplied with two keys, makes two key electron riches; On the other hand, the N atom of parent electricity absorbs electronics on pair keys by inductive effect again, and wherein conjugative effect is greater than inductive effect, so carbazole has very strong cavity transmission ability, and this just makes it that very large potential using value is arranged aspect organic semiconductor material.
Yet the effciency of energy transfer of traditional organic semiconductor material that contains carbazole or porphyrin is lower, has greatly limited the range of application of this class material.
[summary of the invention]
Based on this, be necessary to provide a kind of energy conversion efficiency higher contain carbazolyl porphyrin-benzene multipolymer.
A kind of carbazolyl porphyrin-benzene multipolymer that contains has following structural formula (III):
Wherein, n is the integer between 1-100; R
1And R
2Be hydrogen or C
1～C
32Alkyl.
Increase the group of solubility by introducing, for example alkyl, can improve solubility and the film-forming properties of polymer materials, and can regulate and control the extinction scope of carbazolyl porphyrin.Therefore, the above-mentioned carbazolyl porphyrin-benzene multipolymer that contains has good solubility, lower energy gap, wider spectral absorption scope, is conducive to current carrier and more effectively transmits in active layer material inside, and photoelectric transformation efficiency is high.
A kind of preparation method who contains carbazolyl porphyrin-benzene multipolymer, in oxygen-free environment, with 5,15-two bromo-10,20-alkyl carbazole porphyrin or derivatives thereof (I) is carrying out the Suzuki coupling reaction with two boric acid ester benzene (II) under the catalysts and solvents existence condition, obtain containing carbazolyl porphyrin-benzene multipolymer (III), reaction formula is as follows:
Wherein, n is the integer between 1-100; R
1And R
2Identical or not identical, be hydrogen or C
1～C
32Alkyl.
Wherein, 5,15-, two bromo-10,20-alkyl carbazole porphyrin is 1: 1.5～1.5: 1 with the mol ratio of two boric acid ester benzene; Temperature of reaction is 50-120 ℃, and the reaction times is 24～72 hours.
Wherein, catalyzer is the mixture for organic palladium or organic palladium and organophosphor ligand.Wherein, organic palladium is Pd
2(dba)
3, Pd (OAc)
2, Pd (PPh
3)
4Or Pd (PPh
3)
2Cl
2In at least a; Organophosphor ligand is tricyclohexyl phosphine or P (o-Tol)
3In at least a; The mol ratio of organic palladium and organophosphor ligand is 1: 2～1: 20.
Wherein, the molar weight of catalyzer be two boric acid ester benzene (II) molar weight 0.05%～20%.
Wherein, solvent is at least a in benzene, toluene, glycol dimethyl ether, tetrahydrofuran (THF).
Above-mentioned preparation method utilizes the Suzuki reaction principle, and technique is simple, low for equipment requirements.
A kind of organic solar batteries device, comprise successively glass baseplate, be located at conductive layer on glass baseplate, be coated in poly-(3 on conductive layer, the 4-Ethylenedioxy Thiophene), poly-(styrene sulfonic acid) layer, be coated in active coating on poly-(3,4-Ethylenedioxy Thiophene), poly-(styrene sulfonic acid) layer, be deposited on active coating metal Al layer and for the epoxy resin that encapsulates above-mentioned each layer.Active coating comprises electron donor material and electron acceptor material, and electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate.Electron donor material is the aforesaid carbazolyl porphyrin-benzene multipolymer that contains.
A kind of organic electroluminescence device comprises successively glass baseplate, is located at conductive layer on glass baseplate, is coated in luminescent layer on conductive layer, evaporation is at the LiF buffer layer on luminescent layer and be deposited on metal Al layer on the LiF buffer layer.Wherein, luminescent layer is the aforesaid carbazolyl porphyrin-benzene multipolymer that contains.
A kind of organic field effect tube device comprises successively the doped silicon wafer base material, is located at the SiO of doped silicon wafer substrate surface
2Insulation layer, be coated in SiO
2The octadecyl trichlorosilane alkane decorative layer on surface, be coated in the organic semiconductor layer on octadecyl trichlorosilane alkane decorative layer and source electrode and the drain electrode of organic semiconductor layer surface are set.Wherein, organic semiconductor layer is the aforesaid carbazolyl porphyrin-benzene multipolymer that contains.
Above-mentioned polymer materials is high, easy to utilize as the photoelectric transformation efficiency of polymer solar cell device, organic electroluminescent device and the organic field effect tube device of active material preparation.
[description of drawings]
Fig. 1 is the structural representation of the organic solar batteries device that contains carbazolyl porphyrin-benzene multipolymer of an embodiment.
Fig. 2 be an embodiment contain carbazolyl porphyrin-benzene multipolymer as the structural representation of the organic electroluminescence device of luminescent layer.
Fig. 3 be an embodiment contain carbazolyl porphyrin-benzene multipolymer as the structural representation of the organic field effect tube of organic semiconductor layer.
[embodiment]
The below mainly is further described the above-mentioned carbazolyl porphyrin-benzene multipolymer and its preparation method and application that contains with embodiment by reference to the accompanying drawings.
Carbazolyl porphyrin-benzene the multipolymer that contains of present embodiment has following structural formula (III):
Wherein, n is the integer between 1-100; R
1And R
2Be hydrogen or C
1-C
32Alkyl.
Increase the group of solubility by introducing, for example alkyl, can improve solubility and the film-forming properties of polymer materials, and can regulate and control the extinction scope of carbazolyl porphyrin.Therefore, the above-mentioned carbazolyl porphyrin-benzene multipolymer that contains has good solubility, lower energy gap, wider spectral absorption scope, is conducive to current carrier and more effectively transmits in active layer material inside, and photoelectric transformation efficiency is high.
The above-mentioned preparation process that contains carbazolyl porphyrin-benzene multipolymer comprises the steps:
Step S1: following structural formula (I) and raw materials of compound (II) are provided:
Wherein, R
1And R
2Be hydrogen or C
1-C
32Alkyl;
Step S2: in oxygen-free environment (oxygen-free environment of the present invention is comprised of nitrogen and/or rare gas element), with structural formula (I) and (II) compound be that the ratio of 1: 1.5～1.5: 1 is carried out the Suzuki coupling reaction in molar ratio at raw material under the catalysts and solvents existence condition under 50～120 ℃ of conditions, react obtained having structural formula in 24～72 hours multipolymer of (III);
Reaction formula is:
Catalyzer can be the mixture of organic palladium or organic palladium and organophosphorus ligand.The consumption of catalyzer be structural formula (II) the compound molar weight 0.05%～20%.Wherein, organic palladium is Pd
2(dba)
3, Pd (OAc)
2, Pd (PPh
3)
4Or Pd (PPh
3)
2Cl
2Organophosphorus ligand is tricyclohexyl phosphine or P (o-Tol)
3In at least a.When catalyzer was the mixture of organic palladium and organophosphorus ligand, the mol ratio of organic palladium and organophosphorus ligand was 1: 2～20.
Preferably, solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene.
After the crude product in solution that obtains the Suzuki coupled reaction, also need crude product in solution is carried out sedimentation, drying treatment: at first, solution is added drop-wise in methyl alcohol, carries out sedimentation and process, suction filtration then, methanol wash, drying must contain assorted copolymer colloid; With the toluene dissolving, get the toluene solution of multipolymer subsequently; Then, this toluene solution is joined in the aqueous solution of Thiocarb, 90 ℃ of heated and stirred mixed solutions with the column chromatography of mixed solution by aluminum oxide, are isolated multipolymer, then chlorobenzene drip washing, and organic solvent is removed in decompression subsequently; Repeat the above-mentioned the first step, and extract multipolymer with the acetone Soxhlet, obtain copolymer solids.
Above-mentioned preparation method utilizes the Suzuki reaction principle, and technique is simple, low for equipment requirements.
Further illustrate the above-mentioned carbazolyl porphyrin-benzene multipolymer and its preparation method and application that contains below by specific embodiment.
Embodiment 1
. the present embodiment disclose a kind of structure following 10,20-two (9-octyl group carbazole) porphyrin-benzene multipolymer:
The preparation process of above-mentioned multipolymer is as follows:
Step S11, synthetic Isosorbide-5-Nitrae-to two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two), reaction formula is as follows:
Under the protection of nitrogen, add paradibromobenzene (4.8g, 0.02mol) in there-necked flask; the tetrahydrofuran solvent that adds 100ml slowly injects n-Butyl Lithium (16.8mL, 0.04mol) with syringe again under-78 ℃ of conditions; continue stirring reaction 2h, inject 2-isopropoxy-4,4 with syringe under-78 ℃ of conditions; 5; 5-tetramethyl--1,3, the assorted oxygen pentaborane (8.7mL of 2-two; 0.04mol), stir under room temperature and spend the night.Add 30ml saturated sodium-chloride water solution termination reaction, use chloroform extraction, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve and evaporate solvent.At last crude product is separated for leacheate carries out silica gel column chromatography with petrol ether/ethyl acetate (15/1), obtain product, productive rate 94.6%.
Step S12, synthetic 5,15-two (9-octyl group carbazole) porphyrin, reaction formula is as follows:
put up the anhydrous and oxygen-free device, take intermediate 2-aldehyde-9-octyl group carbazole (0.31g, 1mmol) with dipyrrylmethanes (0.15g, 1mmol), be dissolved in the 250ml methylene dichloride, pass into nitrogen 30min, syringe adds propionic acid 1ml, stir 24h under 20 ℃, then add DDQ (DDQ) (0.91g, 4mmol), continue at room temperature to stir 30min, then add 1ml triethylamine cancellation reaction, concentrated solvent, filter, collect filtrate and be spin-dried for solvent, with methylene dichloride drip washing fast on silicagel column, be spin-dried for solvent, arrive product with ether/recrystallizing methanol, productive rate is about 86.4%.
Step S13, synthetic 5,15-, two bromo-10,20-two (9-octyl group carbazole) porphyrin, reaction formula is as follows:
Put up the anhydrous and oxygen-free device, take 10,20-two (9-octyl group carbazole) porphyrin (0.17g, 0.2mmol) be dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃, add N-bromo-succinimide (0.07g, 0.4mmol), after stirring 72h, mixture returns to room temperature, then continue to stir 4h, add 5ml acetone termination reaction, desolventizing, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 88.2%.
Step S14, synthetic 10,20-two (9-octyl group carbazole) porphyrin-benzene multipolymer, reaction formula is as follows:
Under nitrogen protection, add Isosorbide-5-Nitrae-two (4; 4,5,5-tetramethyl--1; 3; the assorted oxygen pentaborane of 2-two) benzene (66mg, 0.2mmol), 5,15-two bromo-10; 20-two (9-octyl group carbazole) porphyrin (205mg; 0.2mmol) and toluene solvant 50ml, vacuumize deoxygenation and be filled with nitrogen, then add 5mg Pd (PPh
3)
2Cl
2, be heated to 100 ℃ of reaction 56h.Be cooled to mixed solution to be added drop-wise to after room temperature and carry out sedimentation in 300ml methyl alcohol.Suction filtration, methanol wash, drying.Then with the toluene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone apparatus,Soxhlet's.The methyl alcohol sedimentation, suction filtration.Taking out under vacuum pump spends the night obtains product, productive rate 80.9%, molecular weight (GPC, THF, R.I): M
n=34600, M
w/ M
n=3.28).
Embodiment 2
The present embodiment discloses the following 10-of a kind of structure (9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin-benzene multipolymer:
The preparation process of above-mentioned multipolymer is as follows:
Step S21, synthetic Isosorbide-5-Nitrae-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-two) benzene.
Its preparation method is with the step S11 of embodiment 1.
Step S22, synthetic 5-(9-methyl carbazole)-10-(9-dotriacontyl carbazole) porphyrin, reaction formula is as follows:
put up the anhydrous and oxygen-free device, take intermediate 2-aldehyde-9-methyl carbazole (0.21g, 1mmol), 2-aldehyde-9-dotriacontyl carbazole (0.65g, 1mmol), dipyrrylmethanes (0.30g, 2mmol), be dissolved in the 250ml methylene dichloride, pass into nitrogen 30min, syringe adds trifluoroacetic acid 2ml, stir 1h under 100 ℃, then add DDQ (DDQ) (1.82g, 8mmol), continue at room temperature to stir 30min, then add 2ml pyridine cancellation reaction, concentrated solvent, filter, collect filtrate and be spin-dried for solvent, with methylene dichloride drip washing fast on silicagel column, be spin-dried for solvent, arrive product with ether/recrystallizing methanol, productive rate is about 74.3%.
Step S23, synthetic 5,15-, two bromo-10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin, reaction formula is as follows:
Put up the anhydrous and oxygen-free device, take 10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin (0.22g, 0.2mmol) and be dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃, add N-bromo-succinimide (0.07g, 0.4mmol), after stirring 0.5h, mixture is warming up to 120 ℃, after then continuing to stir 1h, add 5ml acetone termination reaction, desolventizing is carried out recrystallization with ether/methyl alcohol and is obtained product, productive rate 83.3%.
Step S24, synthetic 10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin-benzene multipolymer, reaction formula is as follows:
Nitrogen and argon gas mixed gas protected under, add Isosorbide-5-Nitrae-two (4; 4; 5,5-tetramethyl--1,3; the assorted oxygen pentaborane of 2-two) benzene (66mg; 0.2mmol), 5,15-two bromo-10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin (253mg, 0.2mmol) and toluene solvant 120ml; vacuumize deoxygenation and be filled with nitrogen and the argon gas mixed gas, then add Pd (OAc)
2(2.5mg)/tricyclohexyl phosphine (6.5mg) and 2ml 20% (wt) Et
4NOH solution is heated to 120 ℃ of reaction 24h.Be cooled to mixed solution to be added drop-wise to after room temperature and carry out sedimentation in 200ml methyl alcohol.Suction filtration, methanol wash, drying.Then with the toluene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet.The methyl alcohol sedimentation, suction filtration.Taking out under vacuum pump spends the night obtains product, productive rate 79.8%, molecular weight (GPC, THF, R.I): M
n=36400, M
w/ M
n=3.57).
Embodiment 3
The present embodiment discloses the following 10-carbazole-20-of a kind of structure (9-hexadecyl carbazole) porphyrin-benzene multipolymer:
The preparation process of above-mentioned multipolymer is as follows:
Step S31, synthetic Isosorbide-5-Nitrae-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-two) benzene.
Its preparation is with embodiment 1 step S11.
Step S32, synthetic 10-carbazole-20-(9-hexadecyl carbazole) porphyrin, reaction formula is as follows:
put up the anhydrous and oxygen-free device, take intermediate 2-aldehyde carbazole (0.20g, 1mmol), 2 aldehyde-9-hexadecyl carbazole (0.42g, 1mmol), dipyrrylmethanes (0.30g, 2mmol), be dissolved in the 300ml methylene dichloride, pass into nitrogen 30min, syringe adds trifluoroacetic acid 2ml, stir 3h under room temperature, then add DDQ (DDQ) (1.82g, 8mmol), continue at room temperature to stir 30min, then add 2ml triethylamine cancellation reaction, concentrated solvent, filter, collect filtrate and be spin-dried for solvent, with methylene dichloride drip washing fast on silicagel column, be spin-dried for solvent, arrive product with ether/recrystallizing methanol, productive rate is about 86.8%.
Step S33, synthetic 5,15-, two bromo-10-carbazole-20-(9-hexadecyl carbazole) porphyrin, reaction formula is as follows:
Put up the anhydrous and oxygen-free device, take 10-carbazole-20-(9-hexadecyl carbazole) porphyrin (0.17g, 0.2mmol) and be dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃, add N-bromo-succinimide (0.07g, 0.4mmol), after stirring 0.5h, mixture is warming up to 30 ℃, then continues to stir 48h, add 5ml acetone termination reaction, desolventizing is carried out recrystallization with ether/methyl alcohol and is obtained product, productive rate 78.2%.
Step S34, synthetic 10-carbazole-20-(9-hexadecyl carbazole) porphyrin-benzene multipolymer, reaction formula is as follows:
Under argon shield, add Isosorbide-5-Nitrae-two (4; 4; 5,5-tetramethyl--1,3; the assorted oxygen pentaborane of 2-two) benzene (66mg; 0.2mmol), 5,15-two bromo-10-carbazole-20-(9-hexadecyl carbazole) porphyrin (205mg, 0.2mmol) and toluene solvant 100ml; vacuumize deoxygenation and be filled with argon gas, then add 10mg Pd (PPh
3)
4, be heated to 50 ℃ of reaction 72h.Be cooled to mixed solution to be added drop-wise to after room temperature and carry out sedimentation in 300ml methyl alcohol.Suction filtration, methanol wash, drying.Then with the toluene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet.The methyl alcohol sedimentation, suction filtration.Taking out under vacuum pump spends the night obtains product, productive rate 84.1%.Molecular weight (GPC, THF, R.I): M
n=38700, M
w/ M
n=3.29).
Embodiment 4
With 10 of embodiment 1,20-two (9-octyl group carbazole) porphyrin-benzene multipolymer is as the organic solar batteries device of active layer material, and its structure as shown in Figure 1.
Active layer material comprises above-mentioned multipolymer 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/, PEDOT is poly-(3, the 4-Ethylenedioxy Thiophene), PSS is poly-(styrene sulfonic acid); Ito glass is through after ultrasonic cleaning, process 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, be placed under 110 ℃ of air tight conditions annealing 4 hours, then drop to room temperature.Due to device annealed after, the chemical structure of material is more regular in order, has improved transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Embodiment 5
With 10 of embodiment 1,20-two (9-octyl group carbazole) porphyrin-benzene multipolymer is as the organic electroluminescence device of the material of luminescent layer, and its structure as shown in Figure 2.
This device is followed successively by ITO/P1/LiF/Al, namely 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, prepare one deck P1 material by spin coating technique as luminescent layer on ITO, vacuum evaporation LiF on this luminescent layer again, as buffer layer, adopt at last vacuum coating technology metal refining Al on buffer layer, as the negative electrode of device.
Embodiment 6
Containing 10 of embodiment 1, the organic field effect tube of 20-two (9-octyl group carbazole) porphyrin-benzene multipolymer, 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, also can adopt copper to make electrode, and P1 is spun to SiO after octadecyl trichlorosilane alkane (OTS) is modified as organic semiconductor layer
2On, thereby make the organic field effect tube that contains 10,20-two (9-octyl group carbazole) porphyrin-benzene multipolymer.
High, easy to utilize as the photoelectric transformation efficiency of polymer solar cell device, organic electroluminescent device and the organic field effect tube device of active material preparation with above-mentioned polymer materials.
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 the scope of the claims 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. a multipolymer that contains carbazolyl porphyrin-benzene, is characterized in that, has following structural formula (III):
Wherein, n is the integer between 1-100; R
1And R
2Be hydrogen or C
1~ C
32Alkyl.
2. preparation method who contains the multipolymer of carbazolyl porphyrin-benzene, it is characterized in that, in oxygen-free environment, with 5,15-two bromo-10,20-alkyl carbazole porphyrin or derivatives thereof (I) and the Suzuki coupling reaction that two boric acid ester benzene (II) carry out under the catalysts and solvents existence condition obtain containing the multipolymer (III) of carbazolyl porphyrin-benzene, and reaction formula is as follows:
Wherein, n is the integer between 1-100; R
1And R
2Be hydrogen or C
1~ C
32Alkyl.
3. the preparation method who contains the multipolymer of carbazolyl porphyrin-benzene according to claim 2, it is characterized in that: described 5,15-two bromo-10,20-alkyl carbazole porphyrin (I) is 1:1.5 ~ 1.5:1 with the mol ratio of described pair of boric acid ester benzene (II), temperature of reaction is 50-120 ℃, and the reaction times is 24 ~ 72 hours.
4. the preparation method who contains the multipolymer of carbazolyl porphyrin-benzene according to claim 2, it is characterized in that: described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand.
5. the preparation method who contains the multipolymer of carbazolyl porphyrin-benzene according to claim 4, it is characterized in that: described organic palladium is Pd
2(dba)
3, Pd (OAc)
2, Pd (PPh
3)
4Or Pd (PPh
3)
2Cl
2In at least a; Described organophosphor ligand is tricyclohexyl phosphine or P (o-Tol)
3In at least a; The mol ratio of described organic palladium and described organophosphor ligand is 1:2 ~ 1:20.
6. according to claim 2 or 4 or 5 described preparation methods that contain the multipolymer of carbazolyl porphyrin-benzene is characterized in that: the molar weight of described catalyzer be described pair of boric acid ester benzene (II) molar weight 0.05% ~ 20%.
7. the preparation method who contains the multipolymer of carbazolyl porphyrin-benzene according to claim 2 is characterized in that: described solvent is at least a in benzene, toluene, glycol dimethyl ether, tetrahydrofuran (THF).
8. organic solar batteries device, comprise successively glass baseplate, be located at conductive layer on described glass baseplate, be coated in poly-(3 on described conductive layer, the 4-Ethylenedioxy Thiophene), poly-(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 described active coating metal Al layer and for the epoxy resin that encapsulates 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 is for having the multipolymer that contains carbazolyl porphyrin-benzene of structural formula (III):
Wherein, n is the integer between 1-100; R
1And R
2Be hydrogen or C
1~ C
32Alkyl.
9. organic electroluminescence device, comprise successively glass baseplate, be located at conductive layer on described glass baseplate, be coated in luminescent layer on described conductive layer, evaporation is at the LiF buffer layer on described luminescent layer and be deposited on metal Al layer on described LiF buffer layer, it is characterized in that, the material of described luminescent layer has the multipolymer that contains carbazolyl porphyrin-benzene of structural formula (III):
Wherein, n is the integer between 1-100; R
1And R
2Be hydrogen or C
1~ C
32Alkyl.
10. organic field effect tube device comprises successively the doped silicon wafer base material, is located at the SiO of described doped silicon wafer substrate surface
2Insulation layer, be coated in described SiO
2The octadecyl trichlorosilane alkane decorative layer on surface, be coated in the organic semiconductor layer on described octadecyl trichlorosilane alkane decorative layer and be arranged on source electrode and the drain electrode on organic semiconductor layer surface, it is characterized in that, the material of described organic semiconductor layer has the multipolymer that contains carbazolyl porphyrin-benzene of structural formula (III):
Wherein, n is the integer between 1-100; R
1And R
2Be hydrogen or C
1~ C
32Alkyl.
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| CN 201010226125 CN102329417B (en) | 2010-07-13 | 2010-07-13 | Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof |
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| CN 201010226125 CN102329417B (en) | 2010-07-13 | 2010-07-13 | Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof |
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| CN102329417B true CN102329417B (en) | 2013-06-05 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631890A (en) * | 2004-12-10 | 2005-06-29 | 吉林大学 | Tetraphenyl porphyrin derivative and its application in organic electroluminescent device |
| FR2892723A1 (en) * | 2005-11-03 | 2007-05-04 | Biomerieux Sa | New electropolymerizable monomer, useful for detecting a target ligand in a biological sample, comprises an electropolymerizable unit e.g. acetylene and metallo-porphyrin substituted by ionized/ionizable entities |
-
2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631890A (en) * | 2004-12-10 | 2005-06-29 | 吉林大学 | Tetraphenyl porphyrin derivative and its application in organic electroluminescent device |
| FR2892723A1 (en) * | 2005-11-03 | 2007-05-04 | Biomerieux Sa | New electropolymerizable monomer, useful for detecting a target ligand in a biological sample, comprises an electropolymerizable unit e.g. acetylene and metallo-porphyrin substituted by ionized/ionizable entities |
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