CN103626971A - Copolymer containing naphthalenetetracarboxylic diimide-cyclopentaphenanthrene, preparation method thereof and applications thereof - Google Patents

Copolymer containing naphthalenetetracarboxylic diimide-cyclopentaphenanthrene, preparation method thereof and applications thereof Download PDF

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CN103626971A
CN103626971A CN201210305677.7A CN201210305677A CN103626971A CN 103626971 A CN103626971 A CN 103626971A CN 201210305677 A CN201210305677 A CN 201210305677A CN 103626971 A CN103626971 A CN 103626971A
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multipolymer
preparation
compd
cyclopenta
bis
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周明杰
管榕
黄佳乐
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention belongs to the field of organic semiconductor materials, and discloses a copolymer containing naphthalenetetracarboxylic diimide-cyclopentaphenanthrene, a preparation method thereof and applications thereof. The copolymer has a general structure formula as follows, wherein n is an integer between 5 and 71; R1 and R2 are the same or different and are selected from hydrogen, phenyl, C1-C20 alkyl and C1-C20 alkoxybenzene; and R3 is C1-C20 alkyl. According to the copolymer, the cyclopenta[def]phenanthrene unit and the naphthalenetetracarboxylic diimide monomer are subjected to copolymerization to form an electron donor-receptor structure so as to adjust the bad gap of the polymer and to push the absorption band edge of the polymer to infrared and near infrared zones, thus increasing the sunlight utilization rate and further increasing the light conversion rate.

Description

Contain multipolymer of naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene and its preparation method and application
Technical field
The present invention relates to organic semiconductor material, relate in particular to a kind of multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene and its preparation method and application.
Background technology
Utilize cheap material preparation low cost, dynamical organic semiconductor device, as, organic solar batteries, organic electroluminescence device, organic field effect tube are study hotspot and the difficult points in photovoltaic field always.The current silicon solar cell for ground, because complex manufacturing, cost are high, is restricted its application.In order to reduce costs, expand range of application, people are finding novel solar cell material always for a long time.Organic semiconductor device receives much concern because the mode big area such as cheap, the quality of cost of material is light, flexibility, simple, the available coating of production technique, printing such as prepare at the advantage, if its energy conversion efficiency can be brought up to the level that approaches commodity silicon solar cell, its market outlook will be very huge.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C 60between Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect organic semiconductor device, and have obtained development at full speed.At present, the research of organic solar batteries mainly concentrates on to body, acceptor co-mixing system, adopts PTB7 and PC 71the energy conversion efficiency of BM co-mixing system has reached 7.4%(Y.Liang et al., Adv.Mater.; DOI:10.1002/adma.200903528), but still much lower than the efficiency of conversion of inorganic solar cell, the main restricting factor that limiting performance improves has: the carrier mobility that organic semiconductor device is relatively low, the spectral response of device is not mated with solar radiation spectrum, the red light district of high photon flux be not used effectively and the electrode collection effciency of current carrier low etc.For organic semiconductor device is on the actual application, the material of development of new, increases substantially the top priority that its effciency of energy transfer is still this research field.
Naphthalimide derivative is the important compound of material and supramolecular chemistry, and naphthalimide derivative has unique constructional feature and diversified performance, has N-shaped characteristic of semiconductor, in a lot of fields, all shows wide application prospect.
But, because naphthalimide and derivative thereof contain large planar conjugate system and good molecule coplanarity, the interaction of intermolecular large π key is very strong, there is larger lattice energy, thereby its solvability is poor, film forming processing characteristics is poor, causes the device of preparation to be easy to occur problem of phase separation, affect the efficiency of exciton diffusion, thereby cause the loss of energy.In addition, because the absorption spectrum of naphthalimide and derivative thereof mainly concentrates on visible region, absorption region is wide not enough, 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 semiconductor device.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene that can improve the photoelectric transformation efficiency of organic semiconductor device.
Technical scheme of the present invention is as follows:
A multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene, has following general structure:
Figure BDA00002056021300021
In formula: n is the integer between 5-71; R 1, R 2for identical or different be hydrogen, phenyl, C 1~ C 20alkyl, C 1~ C 20alkoxy benzene; R 3for C 1~ C 20alkyl.
Described multipolymer, wherein, preferably n is the integer between 11 ~ 62.
The preparation method who the invention provides the above-mentioned multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene, comprises the steps:
Under inert atmosphere, by structural formula, be
Figure BDA00002056021300031
compd A and structural formula be
Figure BDA00002056021300032
compd B according to the ratio of mol ratio 1:1 ~ 1:1.2, add in the solvent that catalyzer and alkaline solution exist, at 50 ~ 120 ℃, carry out Suzuki coupling reaction 24 ~ 72 hours, stopped reaction, makes structural formula and is
Figure BDA00002056021300033
containing the multipolymer of naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene;
In above-mentioned formula, n is the integer between 5-71; R 1, R 2for identical or different be hydrogen, phenyl, C 1~ C 20alkyl, C 1~ C 20alkoxy benzene; R 3for C 1~ C 20alkyl.
Described preparation method, wherein, preferably n is the integer between 11 ~ 62.
Described preparation method, wherein, after Suzuki coupling reaction finishes, also comprises described multipolymer is carried out to purification process process:
In the reaction solution that Suzuki coupling reaction is obtained, add in methyl alcohol and carry out sedimentation, suction filtration, washing, dry, obtain dry thing;
With toluene, dissolve dry thing, obtain solution, subsequently liquid is joined in the aqueous solution of Thiocarb, obtain mixing solutions; Then mixed solution is heated to 90 ℃ of stirrings and spends the night, obtain organic phase and the inorganic phase of layering;
By organic phase, by chromatography, drip washing, decompression are removed organic solvent, and again through sedimentation, suction filtration, are obtained screening; And extract screening by acetone Soxhlet, and then to the screening sedimentation of extracting, suction filtration, takes out and spends the night under vacuum pump, obtains the described multipolymer of purifying.
Described preparation method, wherein, described catalyzer is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; The mole dosage of described catalyzer is 0.01 ~ 20% of compd A and the total amount of compd B.
Described preparation method, wherein, described catalyzer is that mol ratio is three (dibenzalacetone) two palladiums of 1:2 ~ 20 and the mixture of three (o-methyl-phenyl-) phosphine or palladium that mol ratio is 1:2 ~ 20 and the mixture of tricyclohexyl phosphine; The mole dosage of described catalyzer is 0.01 ~ 20% of compd A and the total amount of compd B.
Described preparation method, wherein, described alkaline solution is the NaOH aqueous solution, Na 2cO 3the aqueous solution, NaHCO 3the aqueous solution or the tetraethyl ammonium hydroxide aqueous solution; In described alkaline solution, the mole dosage of alkali solute is compd A and the total amount of compd B 5 ~ 10 times.Described preparation method, wherein, described solvent is tetrahydrofuran (THF), dioxane, N, at least one in N-dimethyl amide, benzene and toluene.
The present invention also provides the application of above-mentioned multipolymer in organic solar batteries, organic electroluminescence device, organic field effect tube.
Multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene provided by the invention, the one, by introducing substituting group in its " bay " position, the 2nd, by naphthalenetetracarbacidic acidic diimide monomer and other monomer copolymerizations, improve its solvability.In addition, the luxuriant and rich with fragrance unit of cyclopenta [def] is the unit with good two dimensional structure that simultaneously contains the phenanthrene ring frame of a cyclopentadiene ring and three fused benzene rings, due to its good planeness and conjugation degree, its mobility is very high, and can introduce the modifications such as alkyl for 4 on cyclopenta [def] phenanthrene and improve its solvability, and improve its solution processable performance.Therefore, the luxuriant and rich with fragrance unit of cyclopenta [def] and naphthalenetetracarbacidic acidic diimide monomer copolymerization, form Electron donor acceptor structure, carrys out the band gap of telomerized polymer, and push its energy of absorption edge to infrared and near-infrared region.The solvability of the naphthalenetetracarbacidic acidic diimide monomer after modification is good, absorbancy is strong, absorption region is wide, may extend to near-infrared region, improved its utilization ratio to sunlight, and then improve light turnover ratio, and there is good charge transport properties, in the fields such as organic photovoltaic cell, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic solar batteries that makes of embodiment 8;
Fig. 2 is the structural representation of the organic electroluminescence device that makes of embodiment 9;
Fig. 3 is the structural representation of the organic field effect tube that makes of embodiment 10.
Embodiment
A kind of multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene provided by the invention, has following general structure:
Figure BDA00002056021300051
In formula: n is the integer between 5-71, preferably n is the integer between 11 ~ 62; R 1, R 2for identical or different be hydrogen, phenyl, C 1~ C 20alkyl, C 1~ C 20alkoxy benzene; R 3for C 1~ C 20alkyl.
The preparation method of the above-mentioned multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene, comprises the steps:
Under S1, inert atmosphere (comprising that nitrogen, argon gas or nitrogen and argon gas form the inert atmosphere that mixed gas forms), by structural formula, be
Figure BDA00002056021300052
compd A (naphthalenetetracarbacidic acidic diimide two bromo-derivatives) and structural formula be
Figure BDA00002056021300053
compd B (two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-bis-)-cyclopenta [def] phenanthrene derivative) according to the ratio of mol ratio 1:1 ~ 1:1.2, add in the solvent that catalyzer and alkaline solution exist, at 50 ~ 120 ℃, carry out Suzuki coupling reaction 24 ~ 72 hours, stopped reaction, makes and contains structural formula and be
Figure BDA00002056021300061
the reaction solution containing the multipolymer of naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene; Above-mentioned various in, n is the integer between 5-71; R 1, R 2for identical or different be hydrogen, phenyl, C 1~ C 20alkyl, C 1~ C 20alkoxy benzene; R 3for C 1~ C 20alkyl; Reaction formula is as follows:
Figure BDA00002056021300062
After S2, Suzuki coupling reaction finish, to making multipolymer in step S1, carry out purification process process:
The reaction solution that Suzuki coupling reaction is obtained is added drop-wise in methyl alcohol and carries out sedimentation, suction filtration, and methanol wash is dry; Then with toluene, dissolve, join in the aqueous solution of Thiocarb; Then mixed solution is heated to 90 ℃ of stirrings and spends the night, by organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing; Organic solvent, methyl alcohol sedimentation are removed in decompression; Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the multipolymer of purifying.
In above-mentioned preparation method, described catalyzer is tetrakis triphenylphosphine palladium (Pd (PPh 3) 4) or two (triphenylphosphine) palladium chloride (Pd (PPh 3) 2cl 2); Or described catalyzer is that mol ratio is three (dibenzalacetone) two palladium (Pd of 1:2 ~ 20 2(dba) 3) and three (o-methyl-phenyl-) phosphine (P (o-tol) 3) mixture or the mol ratio palladium (Pd (OAc) that is 1:2 ~ 20 2) and tricyclohexyl phosphine (PCy 3) mixture; The mole dosage of described catalyzer is 0.01 ~ 20% of compd A and the total amount of compd B.
In above-mentioned preparation method, described alkaline solution is the NaOH aqueous solution, Na 2cO 3the aqueous solution, NaHCO 3the aqueous solution or the tetraethyl ammonium hydroxide aqueous solution; In described alkaline solution, the mole dosage of alkali solute is compd A and the total amount of compd B 5 ~ 10 times.
In above-mentioned preparation method, described solvent is tetrahydrofuran (THF) (THF), dioxane, N, at least one in N-dimethyl amide (DMF), benzene and toluene.
The present invention also provides the application of above-mentioned multipolymer in organic solar batteries, organic electroluminescence device, organic field effect tube.
Multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene provided by the invention, the one, by introducing substituting group in its " bay " position, the 2nd, by naphthalenetetracarbacidic acidic diimide monomer and other monomer copolymerizations, improve its solvability.In addition, the luxuriant and rich with fragrance unit of cyclopenta [def] is the unit with good two dimensional structure that simultaneously contains the phenanthrene ring frame of a cyclopentadiene ring and three fused benzene rings, due to its good planeness and conjugation degree, its mobility is very high, and can introduce the modifications such as alkyl for 4 on cyclopenta [def] phenanthrene and improve its solvability, and improve its solution processable performance.Therefore, the luxuriant and rich with fragrance unit of cyclopenta [def] and naphthalenetetracarbacidic acidic diimide monomer copolymerization, form Electron donor acceptor structure, carrys out the band gap of telomerized polymer, and push its energy of absorption edge to infrared and near-infrared region.The solvability of the naphthalenetetracarbacidic acidic diimide monomer after modification is good, absorbancy is strong, absorption region is wide, may extend to near-infrared region, improved its utilization ratio to sunlight, and then improve light turnover ratio, and there is good charge transport properties, in the fields such as organic photovoltaic cell, have a good application prospect.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene of the present embodiment, gathers N, N '-bis--(2-octyl-decyl)-Isosorbide-5-Nitrae, and 5,8-benzene-naphthalene diimide-4,4-bis-(2-ethylhexyl)-cyclopenta [def] luxuriant and rich with fragrance (n=71):
Figure BDA00002056021300081
Under nitrogen protection, by N, N '-bis--(2-octyl-decyl)-2; the bromo-Isosorbide-5-Nitrae of 6-bis-, 5; 8-benzene-naphthalene diimide (0.5mmol), 4,4-bis-(2-ethylhexyl)-2; 6-bis-(4; 4,5,5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) the DMF solvent (18mL) of-cyclopenta [def] luxuriant and rich with fragrance (0.5mmol) dissolves.Continue to pass into nitrogen bubble 0.5h and remove residual oxygen.Then add Pd 2(dba) 3(0.014g, 0.015mol) and P (o-Tol) 3(0.0083g, 0.027mmol), adds 35% tetraethyl ammonium hydroxide aqueous solution 2ml, again continues to pass into nitrogen bubble 0.5h and removes residual oxygen, is then heated to 80 ℃ of reactions 48 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 90 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(2-octyl-decyl)-Isosorbide-5-Nitrae, 5,8-benzene-naphthalene diimide-4,4-bis-(2-ethylhexyl)-cyclopenta [def] phenanthrene.Molecular?weight(GPC,THF,R.I):M n=91,700,M w/M n=3.21.
Embodiment 2
The multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene of the present embodiment, gathers N, N '-bis--(2-hexyl octyl group)-Isosorbide-5-Nitrae, and 5,8-benzene-naphthalene diimide-4,4-dihexyl cyclopenta [def] luxuriant and rich with fragrance (n=29):
Figure BDA00002056021300082
Under argon shield, by N, N '-bis--(2-hexyl octyl group)-2; the bromo-Isosorbide-5-Nitrae of 6-bis-, 5; 8-benzene-naphthalene diimide (0.5mmol), 4,4-dihexyl-2; 6-bis-(4,4,5; 5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) the dioxane solvent (15mL) of cyclopenta [def] luxuriant and rich with fragrance (0.5mmol) dissolves, and continues to pass into argon gas bubbling 0.5h and removes residual oxygen.Then add Pd (PPh 3) 2cl 2(10mg, 0.014mmol), adds 35wt% tetraethyl ammonium hydroxide aqueous solution 3ml, and (asking contriver to provide mole number) again continued to pass into argon gas bubbling 0.5h and removed residual oxygen, is then heated to 120 ℃ of reactions 24 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 90 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(2-hexyl octyl group)-Isosorbide-5-Nitrae, 5,8-benzene-naphthalene diimide-4,4-dihexyl cyclopenta [def] phenanthrene.Molecular?weight(GPC,THF,R.I):M n=29,700,M w/M n=3.21。
Embodiment 3
The multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene of the present embodiment, gathers N, N '-bis--(2-methyl tetradecyl)-Isosorbide-5-Nitrae, and 5,8-benzene-naphthalene diimide-4,4-bis-(dodecyl) cyclopenta [def] luxuriant and rich with fragrance (n=23):
Figure BDA00002056021300091
Under nitrogen protection, by N, N '-bis--(2-methyl tetradecyl)-2; the bromo-Isosorbide-5-Nitrae of 6-bis-, 5; 8-benzene-naphthalene diimide (0.5mmol), 4,4-bis-(dodecyl)-2; 6-bis-(4,4,5; 5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) toluene and the THF mixed solvent (30mL) of-cyclopenta [def] luxuriant and rich with fragrance (0.6mmol) dissolve, and continue to pass into nitrogen bubble 0.5h and remove residual oxygen.Then add Pd (PPh 3) 4the Na of (8mg, 0.011mmol) and 2mol/l 2cO 3aqueous solution 4mml,, again continue to pass into nitrogen bubble 0.5h and remove residual oxygen, be then heated to 50 ℃ of reactions 72 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(2-methyl tetradecyl)-Isosorbide-5-Nitrae, 5,8-benzene-naphthalene diimide-4,4-bis-(dodecyl) cyclopenta [def] phenanthrene.Molecular?weight(GPC,THF,R.I):M n=27,930,M w/M n=2.77。
Embodiment 4
The multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene of the present embodiment, gathers N, N '-bis--docosyl-Isosorbide-5-Nitrae, and 5,8-benzene-naphthalene diimide-4,4-bis-(hexadecyl) cyclopenta [def] luxuriant and rich with fragrance (n=11):
Figure BDA00002056021300101
Under nitrogen protection, by N, N '-bis--docosyl-2; the bromo-Isosorbide-5-Nitrae of 6-bis-, 5; 8-benzene-naphthalene diimide (0.5mmol), 4,4-bis-(hexadecyl)-2; 6-bis-(4,4,5; 5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) benzene solvent (20mL) of-cyclopenta [def] luxuriant and rich with fragrance (0.52mmol) dissolves, and continues to pass into nitrogen bubble 0.5h and removes residual oxygen.Then add Pd (OAc) 2(4mg, 0.018mmol) and PCy 3(8mg, 0.028mmol), adds the NaHCO of 2mol/l 3aqueous solution 5mml, again continues to pass into nitrogen bubble 0.5h and removes residual oxygen, is then heated to 100 ℃ of reactions 56 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--docosyl-Isosorbide-5-Nitrae, 5,8-benzene-naphthalene diimide-4,4-bis-(hexadecyl) cyclopenta [def] phenanthrene.Molecular?weight(GPC,THF,R.I):M n=16,720,M w/M n=3.38。
Embodiment 5
The multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene of the present embodiment, gathers N, N '-bis--(2-phenyl-propyl group)-Isosorbide-5-Nitrae, and 5,8-benzene-naphthalene diimide-4,4-dimethyl cyclopenta [def] luxuriant and rich with fragrance (n=5):
Figure BDA00002056021300111
Under nitrogen protection, by N, N '-bis--(2-phenyl-propyl group)-2; the bromo-Isosorbide-5-Nitrae of 6-bis-, 5; 8-benzene-naphthalene diimide (0.5mmol), 4,4-dimethyl-2; 6-bis-(4,4,5; 5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) toluene and the DMF mixed solvent (25mL) of cyclopenta [def] luxuriant and rich with fragrance (0.51mmol), continue to pass into nitrogen bubble 0.5h and remove residual oxygen.Then add Pd (PPh 3) 4the NaOH aqueous solution 2.5mml of (10mg, 0.0087mmol) and 2mol/l, again continues to pass into nitrogen bubble 0.5h and removes residual oxygen, is then heated to 70 ℃ of reactions 40 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(2-phenyl-propyl group)-Isosorbide-5-Nitrae, 5,8-benzene-naphthalene diimide-4,4-dimethyl cyclopenta [def] phenanthrene.Molecular?weight(GPC,THF,R.I):M n=3,740,M w/M n=1.93。
Embodiment 6
The multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene of the present embodiment, gathers N, N '-bis--(2-is to eicosane oxygen base phenyl-docosyl)-1,4,5,8-benzene-naphthalene diimide-4,4-bis-(eicosyl) cyclopenta [def] luxuriant and rich with fragrance (n=36):
Figure BDA00002056021300121
Under argon shield, by N, N '-bis--(2-is to eicosane oxygen base phenyl-docosyl)-2; the bromo-Isosorbide-5-Nitrae of 6-bis-, 5; 8-benzene-naphthalene diimide (0.5mmol), 4,4-bis-(eicosyl)-2; 6-bis-(4,4,5; 5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) dioxane and the THF mixed solvent (18mL) of cyclopenta [def] luxuriant and rich with fragrance (0.5mmol) dissolve, and continue to pass into argon gas bubbling 0.5h and remove residual oxygen.Then add Pd (PPh 3) 2cl 2the Na of (8mg, 0.011mmmol) and 2mol/l 2cO 3aqueous solution 5ml, again continues to pass into argon gas bubbling 0.5h and removes residual oxygen, is then heated to 65 ℃ of reactions 72 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 90 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(2-is to eicosane oxygen base phenyl-docosyl)-Isosorbide-5-Nitrae, 5,8-benzene-naphthalene diimide-4,4-bis-(eicosyl) cyclopenta [def] phenanthrene.Molecular?weight(GPC,THF,R.I):M n=85,580,M w/M n=3.24。
Embodiment 7
The multipolymer containing naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene of the present embodiment, gathers N, N '-bis--(2-eicosyl docosyl)-Isosorbide-5-Nitrae, and 5,8-benzene-naphthalene diimide-4,4-dihexyl cyclopenta [def] luxuriant and rich with fragrance (n=62):
Figure BDA00002056021300131
Under nitrogen and the protection of argon gas gas mixture, by N, N '-bis--(2-eicosyl docosyl)-2; the bromo-Isosorbide-5-Nitrae of 6-bis-, 5; 8-benzene-naphthalene diimide (0.5mmol), 4,4-dihexyl-2; 6-bis-(4,4,5; 5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) DMF solvent (18mL) dissolving of cyclopenta [def] luxuriant and rich with fragrance (0.5mmol), continues to pass into nitrogen and argon gas gas mixture bubbling 0.5h removes residual oxygen.Then add Pd 2(dba) 3(0.015mol) and P (o-Tol) 3(0.03mmol), then add 2mol/lNaHCO 3aqueous solution 4ml, passes into nitrogen again and argon gas gas mixture bubbling 0.5h removes residual oxygen, is then heated to 85 ℃ of reactions 54 hours.Stopped reaction, is added drop-wise to reaction solution in methyl alcohol, to carry out sedimentation.Suction filtration, methanol wash, dry.Then with toluene, dissolve, join in the aqueous solution of Thiocarb, then mixed solution is heated to 90 ℃ of stirrings and spends the night.By organic phase by the column chromatography of aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days by acetone Soxhlet.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains the poly-N of purified product, N '-bis--(2-eicosyl docosyl)-Isosorbide-5-Nitrae, 5,8-benzene-naphthalene diimide-4,4-dihexyl cyclopenta [def] phenanthrene.Molecular?weight(GPC,THF,R.I):M n=113,300,M w/M n=2.94.
Embodiment 8
The present embodiment is organic solar batteries device, and it gather N with the multipolymer in embodiment 1, N '-bis--(2-octyl-decyl)-Isosorbide-5-Nitrae, 5,8-benzene-naphthalene diimide-4,4-bis-(2-ethylhexyl)-cyclopenta [def] luxuriant and rich with fragrance (being expressed as P1) is as active layer material.
An organic solar batteries device, its structure as shown in Figure 1.Wherein, the substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic solar batteries device is: glass 11/ITO layer 12/PEDOT:PSS layer 13/ active coating 14/Al layer 15; Wherein, the material of active coating is mixture, comprises electron donor material, and PCBM is electron acceptor material; The P1 that electron donor material be take in embodiment 1 is material, and electron acceptor material is [6,6] phenyl-C 61-methyl-butyrate (being called for short PCBM); ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is poly-(3,4-Ethylenedioxy Thiophene), and PSS is poly-(styrene sulfonic acid); Preferably square resistance is the ITO of 10 Ω/mouths.
The preparation process of this organic solar batteries device is:
Tin indium oxide (ITO) layer 12 that is 10-20 Ω/mouth at surface deposition one deck square resistance of glass substrate 11, forms the conductive layer as anode, and thickness is about 50-300nm;
Ito glass process ultrasonic cleaning, and after processing with oxygen-Plasma, on ITO surface, be coated with the PEDOT:PSS layer 13 that last layer plays modification, thickness is 50-300nm;
At poly-(3,4-Ethylenedioxy Thiophene): PSS, for gathering on (styrene sulfonic acid) layer, adopt spin coating technique to apply one deck active coating 14, thickness is 50-300nm, and the material of this active coating 14 is with the P1 in embodiment 1 and [6,6] phenyl-C 61the mixture of-methyl-butyrate (being called for short PCBM);
At the surface vacuum evaporation metal aluminium of active coating, form the metal aluminium lamination 15 as negative electrode, obtain organic solar batteries device;
Organic solar batteries device, with after epoxy encapsulation, is placed under 100 ° of C air tight conditions and is annealed 3 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 efficiency of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Preferably the thickness of ITO, PEDOT:PSS layer, active coating, Al layer is respectively 150nm, 50nm, 120nm, 100nm.
Embodiment 9
The present embodiment is organic electroluminescence device, and it gather N with the multipolymer in embodiment 2, N '-bis--(2-hexyl octyl group)-Isosorbide-5-Nitrae, and 5,8-benzene-naphthalene diimide-4,4-dihexyl cyclopenta [def] luxuriant and rich with fragrance (being expressed as P2) is as luminescent layer.
An organic electroluminescence device, its structure is as shown in Figure 2; Substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic electroluminescence device is: glass 21/ITO layer 22/ luminescent layer 23/LiF buffer layer 24/Al layer 25; Wherein: the P2 that luminescent layer 23 be take in embodiment 2 is material.
The preparation process of this organic electroluminescence device is:
Tin indium oxide (ITO) layer 22 that is 10-20 Ω/mouth at surface deposition one deck square resistance of glass substrate 21, forms the conductive layer as anode, and thickness is 50-300nm; Preferably square resistance is the ITO of 10 Ω/mouths.
The luminescent layer 23 that to prepare P2 that one deck take in embodiment 2 be material on ITO surface by spin coating technique, thickness is about 50-300nm;
Vacuum evaporation LiF on luminescent layer, as buffer layer 14, thickness is about 0.3-2nm;
Vacuum evaporation metallic aluminium on described luminescent layer, forms the metal aluminium lamination 25 as negative electrode, obtains described organic electroluminescence device.Accompanying drawing 1, represents that this polymkeric substance produces photoelectric current as the organic solar batteries of active coating under illumination effect, realizes opto-electronic conversion.
Embodiment 10
The present embodiment is organic field effect tube, and it gather N with the multipolymer containing in embodiment 3, N '-bis--(2-methyl tetradecyl)-Isosorbide-5-Nitrae, and 5,8-benzene-naphthalene diimide-4,4-bis-(dodecyl) cyclopenta [def] luxuriant and rich with fragrance (being expressed as P3) is material
An organic field effect tube, its structure is as shown in Figure 3; Substrate in the present embodiment adopts doped silicon wafer (Si) as substrate.
The structure of this organic field effect tube is: the SiO that Si31/450nm is thick 2insulation layer 32/ is for modifying SiO 2octadecyl trichlorosilane alkane (OTS) layer 33/ organic semiconductor layer 34/ take source electrode (S) 35 and the drain electrode (D) 36 that gold is material; Wherein, the P3 that organic semiconductor layer 34 be take in embodiment 3 is material; Wherein, source electrode (S) and drain electrode (D) material also can be selected copper material.
The preparation process of this organic field effect tube is:
First, on a surface cleaning doped silicon wafer 31 later, apply one deck SiO 2insulation layer 32; Secondly, at described SiO 2on insulation layer, apply the octadecyl trichlorosilane alkane layer 33 that one deck plays modification, thickness is 10-200nm; Then, the organic semiconductor layer 34 that the P1 that spin coating one deck be take in embodiment mono-on described octadecyl trichlorosilane alkane layer is material, thickness is about 50-300nm; Finally, on described organic semiconductor layer, be arranged at intervals with and take gold but be not limited only to source electrode (S) 35 and the drain electrode (D) 36 that gold is material, obtain described organic field effect tube.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.

Claims (10)

1. containing a multipolymer for naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene, it is characterized in that, this multipolymer has following general structure:
Figure FDA00002056021200011
In formula: n is the integer between 5-71; R 1, R 2for identical or different be hydrogen, phenyl, C 1~ C 20alkyl, C 1~ C 20alkoxy benzene; R 3for C 1~ C 20alkyl.
2. multipolymer according to claim 1, is characterized in that, n is the integer between 11 ~ 62.
3. contain a preparation method for the multipolymer of naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene, it is characterized in that, comprise the steps:
Under inert atmosphere, by structural formula, be compd A and structural formula be compd B according to mol ratio 1:1 ~ 1:1.2 ratio, add in the solvent that catalyzer and alkaline solution exist, at 50 ~ 120 ℃, carry out Suzuki coupling reaction 24 ~ 72 hours, stopped reaction, obtains structural formula and is containing the multipolymer of naphthalenetetracarbacidic acidic diimide-cyclopenta phenanthrene;
In above-mentioned formula, n is the integer between 5-71; R 1, R 2for identical or different be hydrogen, phenyl, C 1~ C 20alkyl, C 1~ C 20alkoxy benzene; R 3for C 1~ C 20alkyl.
4. preparation method according to claim 3, is characterized in that, n is the integer between 11 ~ 62.
5. preparation method according to claim 3, is characterized in that, after Suzuki coupling reaction finishes, also comprises described multipolymer is carried out to purification process process:
In the reaction solution that Suzuki coupling reaction is obtained, add in methyl alcohol and carry out sedimentation, suction filtration, washing, dry, obtain dry thing;
With toluene, dissolve dry thing, obtain solution, subsequently liquid is joined in the aqueous solution of Thiocarb, obtain mixing solutions; Then mixed solution is heated to 90 ℃ of stirrings and spends the night, obtain organic phase and the inorganic phase of layering;
By organic phase, by chromatography, drip washing, decompression are removed organic solvent, and again through sedimentation, suction filtration, are obtained screening; And extract screening by acetone Soxhlet, and then to the screening sedimentation of extracting, suction filtration, takes out and spends the night under vacuum pump, obtains the described multipolymer of purifying.
6. preparation method according to claim 3, is characterized in that, described catalyzer is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; The mole dosage of described catalyzer is 0.01 ~ 20% of compd A and the total amount of compd B.
7. preparation method according to claim 3, it is characterized in that, described catalyzer is that mol ratio is three (dibenzalacetone) two palladiums of 1:2 ~ 20 and the mixture of three (o-methyl-phenyl-) phosphine or palladium and tricyclohexyl phosphine mixture that mol ratio is 1:2 ~ 20; The mole dosage of described catalyzer is 0.01 ~ 20% of compd A and the total amount of compd B.
8. preparation method according to claim 3, is characterized in that, described solvent is tetrahydrofuran (THF), dioxane, N, at least one in N-dimethyl amide, benzene and toluene.
9. preparation method according to claim 3, is characterized in that, described alkaline solution is the NaOH aqueous solution, Na 2cO 3the aqueous solution, NaHCO 3the aqueous solution or the tetraethyl ammonium hydroxide aqueous solution; In described alkaline solution, the mole dosage of alkali solute is compd A and the total amount of compd B 5 ~ 10 times.
10. the application of multipolymer claimed in claim 1 in organic solar batteries, organic electroluminescence device, organic field effect tube.
CN201210305677.7A 2012-08-24 2012-08-24 Copolymer containing naphthalenetetracarboxylic diimide-cyclopentaphenanthrene, preparation method thereof and applications thereof Pending CN103626971A (en)

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