CN102453236A - Naphthalenetetracarboxylic acid diimide copolymer containing benzothiophene, and preparation method and application thereof - Google Patents

Naphthalenetetracarboxylic acid diimide copolymer containing benzothiophene, and preparation method and application thereof Download PDF

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CN102453236A
CN102453236A CN2010105253855A CN201010525385A CN102453236A CN 102453236 A CN102453236 A CN 102453236A CN 2010105253855 A CN2010105253855 A CN 2010105253855A CN 201010525385 A CN201010525385 A CN 201010525385A CN 102453236 A CN102453236 A CN 102453236A
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naphthalenetetracarbacidic acidic
acidic diimide
thionaphthene
structural formula
thiophene
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CN102453236B (en
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周明杰
黄杰
管榕
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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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Abstract

The invention is applicable to the technical field of organic semiconductor materials, and provides a naphthalenetetracarboxylic acid diimide copolymer containing benzothiophene unit, and a preparation method and application thereof. The copolymer has the following structural formula. The benzothiophene unit and the naphthalenetetracarboxylic acid diimide unit are polymerized, so that the copolymer provided by the invention has the advantages of high solubility, strong absorbance, wide light absorption range and the like; the light absorption range can be extended to the near infrared region, so that the sunlight utilization ratio is enhanced; and meanwhile, the naphthalenetetracarboxylic acid diimide copolymer containing benzothiophene has excellent stability and charge transmission performance.

Description

Contain thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer, its preparation method and application
Technical field
The invention belongs to the organic semiconductor material technical field, relate in particular to a kind of contain thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer, its preparation method and application.
Background technology
The polymer organic semiconductor material is applied to solar cell and receives much concern because of advantage such as mode large-area preparation such as cheap, the light weight of cost of material, flexibility, simple, the available coating of production technique, printing; But polymer organic semiconductor material in the prior art is because relatively low carrier mobility; Spectral response and solar radiation spectrum do not match; Reason such as the red light district of high photon flux is not used effectively and the electrode collection effciency of current carrier is low; Make that the photoelectric transformation efficiency of polymer organic semiconductor material is low, become the obstacle that influences its application.
Summary of the invention
In view of this, the embodiment of the invention provides a kind of thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer that contains, and solves the low technical problem of organic semiconductor material photoelectric transformation efficiency in the prior art.
The embodiment of the invention is achieved in that
A kind of thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer that contains has following structural formula:
Figure BDA0000030125260000021
Wherein, n is arbitrary natural number of 1-100, R 1, R 2For identical or different, be selected from hydrogen, alkyl, alkoxyl group, phenyl or alkoxy benzene, R 3, R 4For identical or different, be selected from hydrogen, alkoxyl group.
The embodiment of the invention further provides a kind of thionaphthene naphthalenetetracarbacidic acidic diimide copolymer method that contains, and comprises the steps:
Provide respectively the naphthalenetetracarbacidic acidic diimide dibromo of structural formula (I) derive and structural formula (II) 2, two tributyl tin-benzo [1,2-b:4,5-b '] two thiophene derivants of 6-;
Under the oxygen free condition, 1-2 in molar ratio: 1 with 2 of naphthalenetetracarbacidic acidic diimide two br-derivatives of this structural formula (I) and structural formula (II), the two tributyl tin-benzos [1 of 6-; 2-b:4; 5-b '] two thiophene derivants are dissolved in the solvent, under 50-120 ℃ of temperature and catalyzer condition, carry out the Stille coupling reaction 24-72 hour; Obtain containing thiophene and cough up unit naphthalenetetracarbacidic acidic diimide multipolymer, this reaction formula is expressed as:
Figure BDA0000030125260000022
I II
Wherein, n is arbitrary natural number of 1-100, R 1, R 2For identical or different, be selected from hydrogen, alkyl, alkoxyl group, phenyl or alkoxy benzene, R 3, R 4For identical or different, and be selected from hydrogen, alkoxyl group.
The embodiment of the invention further provides the above-mentioned application of thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer in organic photoelectrical material, organic solar batteries, organic electroluminescence display device and method of manufacturing same, organic field effect tube, organic light storage device or organic non-linear optical properties that contain.
Embodiment of the invention multipolymer; Through polymerization thionaphthene unit and naphthalenetetracarbacidic acidic diimide unit, it is good to make that embodiment of the invention multipolymer has solvability, and absorbancy is strong; The wide advantage of light abstraction width; Photoabsorption may extend to the near-infrared region, has improved its utilization ratio to sunshine, also has advantages of excellent stability and charge transport properties.
Description of drawings
Fig. 1 be the embodiment of the invention provide with the structure iron of copolymer p 1 as the organic solar batteries device of active layer material;
Fig. 2 show that the embodiment of the invention provides with the structure iron of copolymer p 1 as the organic electroluminescence device of luminescent layer;
Fig. 3 show that the embodiment of the invention provides with the structure iron of copolymer p 1 as the organic field effect tube of organic semiconductor layer.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with accompanying drawing and embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The embodiment of the invention provides a kind of thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer that contains, and this copolymer structure formula is following:
Wherein, n is arbitrary natural number of 1-100, the preferred arbitrary natural number of 9-76, R 1, R 2For identical or different, be selected from hydrogen, alkyl, alkoxyl group, phenyl or alkoxy benzene etc., be preferably C 1～C 20Alkyl, C 1～C 20Alkoxyl group, phenyl or C 1～C 20Alkoxy benzene etc.; For example, 2-octyl-decyl, 2-hexyl octyl group, 2-eicosyl-docosyl, eicosane oxygen base phenyl-docosane, 2-are to eicosane oxygen base phenyl-docosyl, 2-two-p-methoxyphenyl-ethyl, 2-phenyl-propyl group, docosyl, 2-methyl tetradecyl etc.; R 3, R 4For identical or different, and be selected from hydrogen, alkoxyl group, be preferably C 1～C 20Alkoxyl group, for example, methoxyl group, second alkoxyl group, third alkoxyl group, penta alkoxyl group, hot alkoxyl group, eicosane oxygen base.
The embodiment of the invention contains thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer and is polymerized by thionaphthene unit and naphthalenetetracarbacidic acidic diimide unit.This naphthalenetetracarbacidic acidic diimide unit has excellent n N-type semiconductorN characteristic, belongs to the electronic semicoductor material, has excellent carrier mobility speed.Thiophene unit has moderate energy gap and wide region spectral absorption scope and excellent stability.The thionaphthene unit has the unit with good two dimensional structure of two five-rings and a six-ring skeleton; Have good planeness and conjugation degree; Lower energy gap can improve the energy gap of polymkeric substance, and its absorption band is extended to the infrared light district; Increased the spectral absorption scope of multipolymer greatly; Simultaneously, thionaphthene is incorporated into to form in the naphthalenetetracarbacidic acidic diimide unit of electron deficiency has the unitary polymkeric substance of electron donor(ED)-receptor structure, has increased multipolymer current carrier transfer rate greatly; Thionaphthene can also increase the solubility property of multipolymer greatly, has improved its processability.In addition, the stability of thiophene unit has also increased the stabilization energy of multipolymer greatly.Therefore, it is good that embodiment of the invention multipolymer has solvability, and absorbancy is strong, and absorption region is wide, may extend to the near-infrared region, improved its utilization ratio to sunshine, has advantages of excellent stability and charge transport properties.
The embodiment of the invention also provides a kind of thionaphthene naphthalenetetracarbacidic acidic diimide copolymer method that contains, and comprises the steps:
Provide respectively the naphthalenetetracarbacidic acidic diimide dibromo of structural formula (I) derive and structural formula (II) 2, two tributyl tin-benzo [1,2-b:4,5-b '] two thiophene derivants of 6-;
Under the oxygen free condition, 1-2 in molar ratio: 1 with 2 of naphthalenetetracarbacidic acidic diimide two br-derivatives of this structural formula (I) and structural formula (II), the two tributyl tin-benzos [1 of 6-; 2-b:4; 5-b '] two thiophene derivants are dissolved in the solvent, under 50-120 ℃ of temperature and catalyzer condition, carry out the Stille coupling reaction 24-72 hour; Obtain containing thiophene and cough up unit naphthalenetetracarbacidic acidic diimide multipolymer, this reaction formula is expressed as:
Figure BDA0000030125260000051
Wherein, wherein, n, R 1, R 2, R 3, R 4Value with aforementioned identical, do not set forth in detail at this.
Particularly, among the embodiment of the invention preparation method, solvent is not restriction, preferred organic solvent, for example, THF, glycol dimethyl ether, dioxane, N, one or more of dinethylformamide, chlorobenzene, benzene or toluene; Catalyzer is that organic palladium or mol ratio are 1: the organic palladium of 1-20 and the mixture of organophosphor ligand, for example, Pd 2(dba) 3/ P (o-Tol) 3, Pd (PPh 3) 4Or Pd (PPh 3) 2Cl 2, the add-on of catalyzer is for being the 0.01-30% of total reactant molar weight, 2 of naphthalenetetracarbacidic acidic diimide two br-derivatives of structural formula I and structural formula II; Two tributyl tin-the benzos [1 of 6-; 2-b:4,5-b '] two thiophene derivant mol ratios are 1-2: 1, preferred 1-1.5: 1.
Wherein, among the embodiment of the invention preparation method, the preparation method of naphthalenetetracarbacidic acidic diimide two br-derivatives of structural formula (I) is following:
With 2; 6 two bromo-1,4,5; 8-naphthalene tetracid acid anhydride and primary amine join in the solvent (be selected from third quinoline, imidazoles, butanols, N-N-methyl-2-2-pyrrolidone N-or the propionic acid one or more); Reaction is 1-24 hour under 50-150 ℃ of condition, obtains naphthalenetetracarbacidic acidic diimide dibrominated thing, and reaction formula is expressed as:
Figure BDA0000030125260000061
R 1, R 2Value with aforementioned identical, do not set forth in detail at this;
With N, N '-two-(2-octyl-decyl)-2,6-two bromo-1,4,5, the 8-benzene-naphthalene diimide be prepared as example explanation:
The preparation process is described below:
Under nitrogen protection, with 2-octyl-decyl amine (0.30g 1mmol) joins and contains 2,6-two bromo-1,4,5,8-naphthalene dianhydride (0.43g, in propionic acid 0.1mmol0) (15mL) solution, spend the night by backflow.Be chilled to room temperature, reaction solution poured in the aqueous sodium hydroxide solution into chloroform extraction.Remove organic solvent, ETHYLE ACETATE washing, dissolved in chloroform, column chromatography (aluminum oxide chromatographic column) then.Removing desolvates obtains solid productive rate 52%.MS (MALDI) m/z:984 (M +), reaction formula is expressed as:
Figure BDA0000030125260000071
2 of structural formula (II), the preparation method of two tributyl tin-benzo [1,2-b:4,5-b '] two thiophene derivants of 6-is following:
1, with 4,8-dihydrobenzo [1,2-b:4,5-b '] two thiophene-4,8-diketone, zinc powder, sodium hydroxide and four butyl bromation amine reaction obtain 4, and the 8-disubstituted benzenes is [1,2-b:4,5-b '] two thiophene also.(reference: Macromolecules, 2008,41,6012);
2, with obtain in the step 14, the 8-disubstituted benzenes is [1,2-b:4,5-b '] two thiophene and liquid bromine reaction also, obtains 2,6-two bromo-(4,8-two replace) benzo [1,2-b:4,5-b '] two thiophene.(reference: Macromolecules, 2008,41,6012);
3, with step 2 obtain 2,6-two bromo-(4,8-two replace) benzo [1,2-b:4; 5-b '] in the adding reaction flask, reaction flask places liquid nitrogen-acetone bath of-78 ℃ to cool off, and adds n-Butyl Lithium then under nitrogen protection for two thiophene and solvent (like THF, ether etc.); Dropwise afterreaction liquid and stirred 0.5-3 hour down at-78 ℃, add tributyltin chloride again, stirring at room reaction 0.5-5 hour is through aftertreatment; Obtain 2, the two tributyl tins of 6--(4,8-two replaces) benzo [1; 2-b:4,5-b '] two thiophene, reaction formula is expressed as:
Figure BDA0000030125260000081
Wherein, R 3, R 4Value with aforementioned identical, do not set forth in detail at this;
With 1,1,3,4-tetramethyl--2, two (4-tributyl tin-phenyl) thiophenes of 5-are coughed up is prepared as example explanation:
The preparation process is described below:
With 4,8-dihydrobenzo [1,2-b:4,5-b '] two thiophene-4; The 8-diketone (4.4g, 20mmol), (2.86g 44mmol) adds in the 250ml flask with 60ml water zinc powder; Add 12g sodium hydroxide then, mixed solution fully stirs post-heating and refluxed 1 hour, and the reaction solution color is after redness becomes orange at last from xanthochromia by the time, adds hexyl bromide 1 bromohexane (9.9g; 60mmol), add four butyl bromation amine, the 2 hours reaction solutions that reflux are that yellow perhaps orange continued refluxed 6 hours.Finish the reaction back and pours reaction solution in the cold water into, with 200ml extracted with diethyl ether 2 times, ether is used anhydrous magnesium sulfate drying mutually, remove by filter solvent after crude product obtain 42 times with ethyl alcohol recrystallization, 8-two-hexyloxy benzo [1,2-b:4,5-b '] two thiophene.MS(EI)m/z：390(M +)；
With 4, and 8-two-hexyloxy benzo [1,2-b:4; 5-b '] two thiophene (3.9g; 10mmol) be dissolved in the 100ml methylene dichloride, reaction flask places ice-water bath, with bromine (3.2g; 20mmol) be dissolved in the 60ml methylene dichloride back and slowly drip, dropwise the back room temperature and continue reaction 4-6 hour and finish up to the bromine reaction.Remove the back normal hexane recrystallization that desolvates and obtain 21 time, 6-two bromo-(4,8-two-hexyloxy) benzos [1,2-b:4,5-b '] two thiophene, productive rate 89%.MS(EI)m/z：548(M +)；
Again with 2, and 6-two bromo-(4,8-two-hexyloxy) benzo [1,2-b:4; 5-b '] two thiophene (2.5mmol, 1.37g) with the anhydrous THF of 100ml under nitrogen protection in the adding reaction flask, reaction flask places liquid nitrogen-acetone bath of-78 ℃ to cool off, and drips (4.7mL then; 1.6mol/L 7.5mmol) n-Butyl Lithium dropwises afterreaction liquid and stirred 1 hour down at-78 ℃, again property adding tributyltin chloride (2.44g; 7.5mmol) after, to shift out low temperature and bathe, the stirring at room reaction was poured reaction solution in the cold water into after 2 hours, with extracted with diethyl ether 3 times; Organic phase is used anhydrous magnesium sulfate drying after washing 2 times, filter, and obtains 2 except that after desolvating, the two tributyl tins-(4 of 6-; 8-two-hexyloxy) benzo [1,2-b:4,5-b '] two thiophene 1.40g, productive rate 58%.MS (EI) m/z:968 (M +), reaction formula is expressed as:
Figure BDA0000030125260000091
Oxygen free condition among the embodiment of the invention preparation method comprises various oxygen free conditions, for example can be environment such as 100% nitrogen, argon gas, carbonic acid gas, and the preparation method of oxygen free condition also can comprise the whole bag of tricks; But preferably vacuumize through oil pump; Feed nitrogen again, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of nitrogen gas; When reaction system adds reactant, keep this protection of nitrogen gas simultaneously.
Among the embodiment of the invention preparation method, contain the separation and purification process that thiophene is coughed up unit naphthalenetetracarbacidic acidic diimide multipolymer:
The thiophene that contains that embodiment of the invention preparation method obtains is coughed up the mixed solution of unit naphthalenetetracarbacidic acidic diimide multipolymer and is added drop-wise to and carries out sedimentation in the methyl alcohol; Suction filtration; Methanol wash, drying is dissolved with toluene then; Join in the aqueous solution of Thiocarb, then mixed solution is heated to 90 ℃ of stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product.
The embodiment of the invention also provides the above-mentioned thiophene that contains to cough up the application of unit naphthalenetetracarbacidic acidic diimide multipolymer in organic solar batteries, organic electroluminescence display device and method of manufacturing same, organic field effect tube, organic light storage device and organic non-linear optical properties.
Embodiment of the invention preparation method, simple, convenient, with low cost, be suitable for suitability for industrialized production.
Below in conjunction with specific embodiment preparation method of the present invention and performance are specifically set forth.
Embodiment one
The embodiment of the invention is gathered N, N '-two-(2-octyl-decyl)-1,4,5, and 8-benzene-naphthalene diimide-2,6-(4,8-two-hexyloxy) benzo [1,2-b:4,5-b '] two thiophene (P1) have following structural formula:
Figure BDA0000030125260000101
Wherein, n is 22;
Its preparation method is following:
Under nitrogen protection, with the N of 0.5mmol, N '-two-(2-octyl-decyl)-2,6-two bromo-1; 4,5,8-benzene-naphthalene diimide, 0.5mmol 2, the two tributyl tins-(4 of 6-; 8-two-hexyloxy) benzo [1,2-b:4,5-b '] two thiophene are added among the DMF (18mL); Bubbling 0.5h removes residual oxygen, adds (0.014g, Pd 0.015mmol) then 2(dba) 3(0.0083g, P 0.027mmol) (o-Tol) 3, continue bubbling 0.5h and remove residual oxygen, be heated to 80 ℃ of reactions 48 hours then, obtain containing and gather N; N '-two-(2-octyl-decyl)-1,4,5,8-benzene-naphthalene diimide-2; The mixing solutions of 6-(4,8-two-hexyloxy) benzo [1,2-b:4,5-b '] two thiophene.This mixed solution is added drop-wise to carries out sedimentation in the methyl alcohol, suction filtration, methanol wash, drying with the toluene dissolving, joins in the aqueous solution of Thiocarb then, then mixed solution is heated to 90 ℃ of stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product.Molecular?weight(GPC，THF，R.I)：M n＝27,600，M w/M n＝2.53。Embodiment of the invention preparing method's reaction formula is expressed as:
Figure BDA0000030125260000111
Embodiment two
The embodiment of the invention is gathered N, N '-two-(2-hexyl octyl group)-1,4,5, and 8-benzene-naphthalene diimide-2,6-(4,8-two-octyloxy) benzo [1,2-b:4,5-b '] two thiophene (P2) have following structural formula:
Figure BDA0000030125260000112
Wherein, n is 29;
Its preparation method is following:
Under nitrogen protection, with the N of 0.5mmol, N '-two-(2-hexyl octyl group)-2,6-two bromo-1; 4,5,2 of 8-benzene-naphthalene diimide, 0.5mmol; The two tributyl tins of 6--(4,8-two-octyloxy) benzo [1,2-b:4; 5-b '] two thiophene are added in the dioxane (15mL), and bubbling 0.5h removes residual oxygen, adds Pd (PPh then 3) 2Cl 210mg, bubbling 0.5h removes residual oxygen, is heated to 85 ℃ of reactions 36 hours then, obtains containing and gathers N; N '-two-(2-hexyl octyl group)-1,4,5,8-benzene-naphthalene diimide-2; The mixing solutions of 6-(4,8-two-octyloxy) benzo [1,2-b:4,5-b '] two thiophene.This mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol.With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 90 ℃ of stirred overnight.With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product.Molecularweight(GPC，THF，R.I)：M n＝33,100，M w/M n＝2.89。Embodiment of the invention preparing method's reaction formula is expressed as:
Figure BDA0000030125260000121
Embodiment three
The embodiment of the invention is gathered N, N '-two-(2-eicosyl-docosyl)-2, and 6-(4,8-two-eicosane oxygen base) benzo [1,2-b:4,5-b '] two thiophene (P3) have following structural formula:
Figure BDA0000030125260000131
Wherein, n is 100;
Its preparation method is following:
Under nitrogen protection, with the N of 0.5mmol, N '-two-(2-eicosyl-docosyl)-2,6-two bromo-1; 4,5,8-benzene-naphthalene diimide, 2 of 0.5mmol; The two tributyl tins of 6--(4,8-two-eicosane oxygen base) benzo [1,2-b:4; 5-b '] two thiophene are added among toluene/THF (30mL), and bubbling 0.5h removes residual oxygen, adds Pd (PPh then 3) 48mg, bubbling 0.5h removes residual oxygen, is heated to 80 ℃ of reactions 72 hours then, obtains containing and gathers N, N '-two-(2-eicosyl-docosyl)-2, the mixing solutions of 6-(4,8-two-eicosane oxygen base) benzo [1,2-b:4,5-b '] two thiophene.This mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash in the methyl alcohol; Drying with the toluene dissolving, joins in the aqueous solution of Thiocarb then; Then mixed solution is heated to 80 ℃ of stirred overnight, with the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product.Molecular?weight(GPC，THF，R.I)：M n＝203,300，M w/M n＝3.74。Embodiment of the invention preparing method's reaction formula is expressed as:
Figure BDA0000030125260000141
Embodiment four
The embodiment of the invention is gathered N, N '-two-(2-is to eicosane oxygen base phenyl-docosyl)-1,4,5, and 8-benzene-naphthalene diimide-2,6-(4,8-two-dodecyloxy) benzo [1,2-b:4,5-b '] two thiophene (P4) have following structural formula:
Figure BDA0000030125260000142
Wherein, n is 37;
Its preparation method is following:
Under nitrogen protection, with the N of 0.52mmol, N '-two-(2-is to eicosane oxygen base phenyl-docosyl)-2,6-two bromo-1; 4,5,8-benzene-naphthalene diimide, 2 of 0.5mmol; The two tributyl tins of 6--(4,8-two-dodecyloxy) benzo [1,2-b:4; 5-b '] two thiophene are added in the benzene (20mL), and bubbling 0.5h removes residual oxygen, adds Pd (PPh then 3) 2Cl 25mg, bubbling 0.5h removes residual oxygen, is heated to 120 ℃ of reactions 24 hours then; Obtain containing and gather N, N '-two-(2-is to eicosane oxygen base phenyl-docosyl)-1,4; 5,8-benzene-naphthalene diimide-2,6-(4; 8-two-dodecyloxy) mixing solutions of benzo [1,2-b:4,5-b '] two thiophene.This mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirred overnight; With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing, organic solvent is removed in decompression; The methyl alcohol sedimentation, suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product.Molecular?weight(GPC，THF，R.I)：M n＝83,800，M w/M n＝3.57。Embodiment of the invention preparing method's reaction formula is expressed as:
Embodiment five
The embodiment of the invention is gathered N, N '-two-(2-two-p-methoxyphenyl-ethyl)-1,4,5, and 8-benzene-naphthalene diimide-2,6-(4-dodecyloxy-8-eicosane oxygen base) benzo [1,2-b:4,5-b '] two thiophene (P5) have following structural formula:
Wherein, n is 76;
Its preparation method is following:
Under nitrogen protection, with the N of 0.51mmol, N '-two-(2-two-p-methoxyphenyl-ethyl)-2,6-two bromo-1; 4,5, the 8-benzene-naphthalene diimide; 0.5mmol 2, the two tributyl tins of 6--(4-dodecyloxy-8-eicosane oxygen base) benzo [1,2-b:4; 5-b '] two thiophene are added among toluene/DMF (25mL), and bubbling 0.5h removes residual oxygen, adds Pd (PPh then 3) 410mg, bubbling 0.5h removes residual oxygen, is heated to 70 ℃ of reactions 40 hours then; Obtain containing and gather N, N '-two-(2-two-p-methoxyphenyl-ethyl)-1,4; 5,8-benzene-naphthalene diimide-2,6-(4-dodecyloxy-8-eicosane oxygen base) benzo [1; 2-b:4,5-b '] mixing solutions of two thiophene.This mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash in the methyl alcohol; Drying with the toluene dissolving, joins in the aqueous solution of Thiocarb then; Then mixed solution is heated to 80 ℃ of stirred overnight, with the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing; Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product.Molecularweight(GPC，THF，R.I)：M n＝110,400，M w/M n＝3.58。Embodiment of the invention preparing method's reaction formula is expressed as:
Figure BDA0000030125260000171
Embodiment six
The embodiment of the invention is gathered N, N '-two-(2-phenyl-propyl group)-1,4,5, and 8-benzene-naphthalene diimide-2,6-(4-methoxyl group) benzo [1,2-b:4,5-b '] two thiophene (P6) have following structural formula:
Figure BDA0000030125260000172
Wherein, n is 9;
Its preparation method is following:
Under nitrogen protection, with the N of 0.75mmol, N '-two-(2-phenyl-propyl group)-2,6-two bromo-1; 4,5, the 8-benzene-naphthalene diimide; 0.5mmol 2, the two tributyl tins of 6--(4-methoxyl group) benzo [1,2-b:4; 5-b '] two thiophene are added among dioxane/THF (18mL), and bubbling 0.5h removes residual oxygen, adds Pd (PPh then 3) 2Cl 28mg, bubbling 0.5h removes residual oxygen, is heated to 50 ℃ of reactions 72 hours then, obtains containing and gathers N, N '-two-(2-phenyl-propyl group)-1,4,5,8-benzene-naphthalene diimide-2, the mixing solutions of 6-(4-methoxyl group) benzo [1,2-b:4,5-b '] two thiophene.This mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash in the methyl alcohol; Drying with the toluene dissolving, joins in the aqueous solution of Thiocarb then; Then mixed solution is heated to 90 ℃ of stirred overnight, with the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing; Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product.Molecularweight(GPC，THF，R.I)：M n＝6,740，M w/M n＝2.98。Embodiment of the invention preparing method's reaction formula is expressed as:
Embodiment seven
The embodiment of the invention is gathered N, N '-two-docosyl-1,4,5, and 8-benzene-naphthalene diimide-2,6-(4,8-two-methoxyl group) benzo [1,2-b:4,5-b '] two thiophene (P7) have following structural formula:
Figure BDA0000030125260000191
Wherein, n is 16;
Its preparation method is following:
Under nitrogen protection, with the N of 0.65mmol, N '-two-docosyl-2,6-two bromo-1; 4,5,2 of 8-benzene-naphthalene diimide, 0.5mmol; The two tributyl tins of 6--(4,8-two-methoxyl group) benzo [1,2-b:4; 5-b '] two thiophene are added among dioxane/THF (20mL), and bubbling 0.5h removes residual oxygen, adds Pd (PPh then 3) 2Cl 29mg, bubbling 0.5h removes residual oxygen, is heated to 75 ℃ of reactions 72 hours then, obtains containing and gathers N, N '-two-docosyl-1,4,5,8-benzene-naphthalene diimide-2, the mixing solutions of 6-(4,8-two-methoxyl group) benzo [1,2-b:4,5-b '] two thiophene.This mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 90 ℃ of stirred overnight; With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing, organic solvent is removed in decompression; The methyl alcohol sedimentation, suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product.Molecularweight(GPC，THF，R.I)：M n＝18,700，M w/M n＝2.74。Embodiment of the invention preparing method's reaction formula is expressed as:
Figure BDA0000030125260000201
Embodiment eight
The embodiment of the invention is gathered N, N '-two-(2-methyl tetradecyl)-1,4,5, and 8-benzene-naphthalene diimide-2,6-(the hot alkoxyl group of 4--8-eicosane oxygen base) benzo [1,2-b:4,5-b '] two thiophene (P8) have following structural formula
Figure BDA0000030125260000202
Wherein, n is 57;
Its preparation method is following:
Under nitrogen protection, with the N of 0.5mmol, N '-two-(2-methyl tetradecyl)-2; 6-two bromo-1,4,5; 2 of 8-benzene-naphthalene diimide, 0.5mmol, and the two tributyl tins of 6--(the hot alkoxyl group of 4--8-eicosane oxygen base) benzo [1,2-b:4; 5-b '] two thiophene are added among toluene/THF (30mL), and bubbling 0.5h removes residual oxygen, adds Pd (PPh then 3) 48mg, bubbling 0.5h removes residual oxygen, is heated to 80 ℃ of reactions 72 hours then, obtains containing and gathers N; N '-two-(2-methyl tetradecyl)-1,4,5,8-benzene-naphthalene diimide-2; The mixing solutions of 6-(the hot alkoxyl group of 4--8-eicosane oxygen base) benzo [1,2-b:4,5-b '] two thiophene.This mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the toluene dissolving, join in the aqueous solution of Thiocarb then, then mixed solution is heated to 80 ℃ of stirred overnight; With the column chromatography of organic phase through aluminum oxide, chlorobenzene drip washing, organic solvent is removed in decompression; The methyl alcohol sedimentation, suction filtration, the gained solid extracted three days with acetone Suo Shi.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains the 0.20g product.Molecular?weight(GPC，THF，R。I)：M n＝76,100，M w/M n＝3.53。Embodiment of the invention preparing method's reaction formula is expressed as:
Figure BDA0000030125260000211
Application examples one
Fig. 1 shows with the multipolymer (P1) of top embodiment 1 structure iron as the organic solar batteries device 40 of active layer material; This organic solar batteries device architecture is: glass-base 41, transparent anode 42, middle supplementary layer 43, active coating 44, negative electrode 45; Wherein, Glass-base 41 can comprise various glass, to not restriction of material, but can not hinder sun optical transmission.Transparent anode 42 can for but be not limited to the tin indium oxide that square resistance is 10-20 Ω/mouth, i.e. ITO.Middle supplementary layer 43 can for but be not limited to PEDOT:PSS, PEDOT is for gathering (3, the 4-Ethylenedioxy Thiophene), PSS is for gathering (styrene sulfonic acid), active coating 44 is a copolymer p 1.In the organic solar batteries device 40 of the embodiment of the invention, glass-base 41/ transparent anode 42 is an integral unit, is also referred to as ito glass, can buy from market.
Above-mentioned organic solar batteries preparation of devices method is following,
It is that 15mg/ml is dissolved in the chloroform that embodiment multipolymer (P1) is dissolved in concentration, stirs.With above-mentioned ito glass with ultrasonic cleaning after, middle supplementary layer 43 is applied on the transparent anode 42 through spin coating method.Above-mentioned multipolymer (P1) solution is passed through spin coating method; Be applied to the upper surface of the middle supplementary layer 43 of above-mentioned ito glass, form active coating, pass through vacuum deposition method again; Negative electrode 45 is plated on above-mentioned active coating 44, obtains the prefabrication of organic solar batteries device 40.These organic solar batteries device 40 prefabrications are used epoxy encapsulation, under 110 ℃ of temperature, annealed 4 hours in the closed environment, reduce to room temperature again, obtain the organic solar batteries device 40 of the embodiment of the invention.
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.
Application examples two
Fig. 2 shows that this device 50 comprises glass 51 basic units, transparent anode 52, luminescent layer 53, impact plies 54, negative electrode 55, wherein with the multipolymer (P1) of embodiment 1 organic electroluminescence device 50 as luminescent layer; Glass 51 can be various glass; To not restriction of material, but can not hinder the transmission of light, transparent anode 52 can for but to be not limited to square resistance be that the tin indium oxide of 10-20 Ω/mouth is ITO; Luminescent layer 53 with embodiment 1 multipolymer (P1) as luminescent material; Adopt spin coating method to be applied on the transparent anode 52, the material of impact plies 54 can for but be not limited to LiF, LiF adopts vacuum deposition method to be plated on the luminescent layer 53; Negative electrode 55 can for but be not limited to the metallic aluminium material, be deposited on the impact plies 54 through vacuum coating method.
Application examples three
Fig. 3 shows multipolymer (P1) with embodiment 1 as organic semiconductor layer organic field effect tube 60, and this transistor 60 comprises substrate 61, insulation layer 62, decorative layer 63, organic semiconductor layer 64, source electrode 65 and drain electrode 66.
The material that substrate 61 uses can for but be not limited to elementary silicon/silicon chip; The material of insulation layer 62 can for but be not limited to silicon-dioxide; Thickness is 500mm; The material of decorative layer 63 can for but to be not limited to the octadecyl trichlorosilane be OTS, the multipolymer of embodiment 1 (P1) adopts spin coating method to be applied to form on the decorative layer 63 organic semiconductor layer 64, the material of source electrode 65 and drain electrode 66 can for but be not limited to gold.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. one kind contains thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer, has following structural formula:
Figure FDA0000030125250000011
Wherein, n is arbitrary natural number of 1-100, R 1, R 2For identical or different, be selected from hydrogen, alkyl, alkoxyl group, phenyl or alkoxy benzene, R 3, R 4For identical or different, be selected from hydrogen or alkoxyl group.
2. the thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer that contains as claimed in claim 1 is characterized in that n is arbitrary natural number of 9-76.
3. the thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer that contains as claimed in claim 1 is characterized in that R 1, R 2Be selected from C 1～C 20Alkyl, C 1～C 20Alkoxyl group, phenyl or C 1～C 20Alkoxy benzene.
4. the thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer that contains as claimed in claim 1 is characterized in that R 3, R 4Be selected from C 1～C 20Alkoxyl group.
5. one kind contains thionaphthene naphthalenetetracarbacidic acidic diimide copolymer method, comprises the steps:
Provide respectively following structural formula I naphthalenetetracarbacidic acidic diimide two br-derivatives and structural formula II 2, two tributyl tin-benzo [1,2-b:4,5-b '] two thiophene derivants of 6-;
Under the oxygen free condition, 1-2 in molar ratio: 1 with 2 of naphthalenetetracarbacidic acidic diimide two br-derivatives of said structural formula I and structural formula II, the two tributyl tin-benzos [1 of 6-; 2-b:4; 5-b '] two thiophene derivants are dissolved in the solvent, under 50-120 ℃ of temperature and catalyzer condition, carry out the Stille coupling reaction 24-72 hour; Obtain containing thiophene and cough up unit naphthalenetetracarbacidic acidic diimide multipolymer, its reaction formula is expressed as:
Figure FDA0000030125250000021
Wherein, n is the natural number of 1-100, R 1, R 2For identical or different, be selected from hydrogen, alkyl, alkoxyl group, phenyl or alkoxy benzene, R 3, R 4For identical or different, be selected from hydrogen or alkoxyl group.
6. like the said thionaphthene naphthalenetetracarbacidic acidic diimide copolymer method that contains of claim 5; It is characterized in that; 2 of naphthalenetetracarbacidic acidic diimide two br-derivatives of said structural formula I and structural formula II; Two tributyl tin-benzo [1,2-b:4,5-b '] the two thiophene derivant mol ratios of 6-are 1-1.5: 1.
7. like the said thionaphthene naphthalenetetracarbacidic acidic diimide copolymer method that contains of claim 5, it is characterized in that said catalyzer is that organic palladium or mol ratio are 1: the organic palladium of 1-20 and the mixture of organophosphor ligand.
8. like the said thionaphthene naphthalenetetracarbacidic acidic diimide copolymer method that contains of claim 5; It is characterized in that; 2 of naphthalenetetracarbacidic acidic diimide two br-derivatives that said catalyzer add-on is said structural formula I and structural formula II; The 0.01-30% of two tributyl tin-benzo [1,2-b:4,5-b '] the two thiophene derivant integral molar quantities of 6-.
9. like the said thionaphthene naphthalenetetracarbacidic acidic diimide copolymer method that contains of claim 5, it is characterized in that said solvent is THF, glycol dimethyl ether, dioxane, N, one or more of dinethylformamide, chlorobenzene, benzene or toluene.
10. each describedly contains the application of thionaphthene naphthalenetetracarbacidic acidic diimide multipolymer in organic photoelectrical material, organic solar batteries, organic electroluminescence display device and method of manufacturing same, organic field effect tube, organic light storage device or organic non-linear optical properties like claim 1-4.
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CN105218558A (en) * 2015-09-30 2016-01-06 国家纳米科学中心 A kind of benzo two thiophene-based organic photoelectric compound and its preparation method and application

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WO2013053204A1 (en) * 2011-10-11 2013-04-18 中国科学院化学研究所 Conjugated aramid polymer, preparation method for same, and application thereof in organic optoelectronic device
CN103172837A (en) * 2013-03-05 2013-06-26 合肥工业大学 Semiconductor conjugated polymer based on benzodithiophene and benzotrithiophene, and preparation method thereof
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