CN102206330B - Bi-thiophene silole-containing conjugated polymer and preparation method and application thereof - Google Patents
Bi-thiophene silole-containing conjugated polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses bi-thiophene silole-containing conjugated polymer and a preparation method and application thereof. The bi-thiophene silole-containing conjugated polymer has a molecular structure general formula (I) shown in the specifications, wherein in the general formula, x and y is equal to 1, x is more than 0 and less than or equal to 0.5, and n is any one positive integer which is more than 1 and less than or equal to 150; R1 and R2 is C1 to C15 alkyl groups; and R3 and R4 are at least one of -H, C1 to C15 alkyl groups, C1 to C15 alkoxy, an alkyl group or/and alkyl group-containing thiophene group, an alkyl group-containing fluorene group, an alkyl group-containing carbazole group and an alkyl group-containing benzene ring group. The bi-thiophene silole-containing conjugated polymer has a low energy gap, expands light-absorbing bandwidths, enhances reduction potentials, improves an electric charge transmission property and has higher chemical and structural paintability. The preparation method for the polymer is simple, high in yield, easy to operate and control and suitable for fields of solar batteries and the like.
Description
Technical field
The invention belongs to the organic compound synthesis technical field, relate to a kind of two thiophene thiophenes that contain specifically and cough up class conjugated polymers and its preparation method and application.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is research focus and the difficult point in photovoltaic field always.Be used for the silicon solar cell on ground at present owing to complex manufacturing, cost height, its application is restricted.In order to reduce cost, expand range of application, people are seeking novel solar cell material always for a long time.Polymer solar battery receives much concern because of advantage such as mode large-area preparation such as cheap, the quality of cost of material is light, flexibility, simple, the available coating of production technique, printing, if its energy conversion efficiency can be brought up to the level near the commodity silicon solar cell, its market outlook will be very huge.From N.S.Sariciftci in 1992 etc. at SCIENCE report conjugated polymers and C
60Between photoinduction transfer transport phenomenon after, people have dropped into big quantity research aspect polymer solar battery, and have obtained development at full speed.At present, the research of polymer solar battery 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%, but it is 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 and solar radiation spectrum do not match, the red light district of high photon flux be not used effectively and the electrode collection effciency of current carrier low etc.In order to make polymer solar battery obtain actual application, the material of development of new increases substantially the top priority that its effciency of energy transfer is still this research field.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of two thiophene thiophenes that contain to cough up the class conjugated polymers, this polymkeric substance energy gap is low, increased carrier mobility, widened light absorbing bandwidth, strengthened reduction potential, improved the transport property of electric charge, stronger chemistry and structure modifiability have been arranged.
Another object of the present invention is to provide a kind of simple, productive rate is high, what be easy to operate and control contains the preparation method that two thiophene thiophenes are coughed up the class conjugated polymers.
Further aim of the present invention be to provide above-mentioned contain two thiophene thiophenes cough up the class conjugated polymers at organic photoelectrical material, polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or/and the organic laser Application for Field.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of two thiophene thiophenes that contain are coughed up the class conjugated polymers, and its general formula of molecular structure is following (I):
In the formula, arbitrary positive integer of x+y=1,0＜x≤0.5,1＜n≤150, R
1, R
2Be selected from C
1～C
15Alkyl, R
3, R
4Be selected from-H, C
1～C
15Alkyl, C
1～C
15Alkoxyl group, contain alkyl or/and the alkoxy thiophene group, contain the alkyl fluorene group, contain the alkyl carbazole group, contain at least a in the alkylbenzene cyclic group.
And a kind of two thiophene thiophenes that contain are coughed up the class method for preparing conjugated polymer, comprise the steps:
The compd A, B, the C that provide following structural formula to represent respectively,
Wherein, in the formula, arbitrary positive integer of x+y=1,0＜x≤0.5,1＜n≤150, R
1, R
2Be selected from C
1～C
15Alkyl, R
3, R
4Be selected from-H, C
1～C
15Alkyl, C
1～C
15Alkoxyl group, contain alkyl or/and the alkoxy thiophene group, contain the alkyl fluorene group, contain the alkyl carbazole group, contain at least a in the alkylbenzene cyclic group;
Compd A, B, C are carried out coupling reaction for m: p: q in molar ratio in organic solvent, obtain following general structure and be the polymkeric substance of (I) expression, wherein, m=p+q, and m＞p 〉=0,
General structure is in (I), arbitrary positive integer of x+y=1,0＜x≤0.5,1＜n≤150.
The present invention compared with prior art possesses following advantage at least:
1. containing two thiophene thiophenes coughs up two thiophene that contain in the class conjugated polymers molecule and has particular structure, two thiphene ring in its structural unit are on same plane, this structure can effectively prolong the conjugation performance of polymkeric substance, reduce the energy gap of polymkeric substance, make current carrier between two main chains, shift to become and be more prone to, increased carrier mobility; Two thiophene [3 that contain, 2-b:2 ', 3 '-d] to cough up the unit be with cyclopentadiene (2 to thiophene, 1-b:3,4-b ') the C atom in the structure of two thiophene converts the Si atom to, has improved the crystal property of this polymkeric substance, has improved the transport property of electric charge, it is compound to have weakened bimolecular, makes the carrier mobility that the carrier mobility of this polymkeric substance relatively only contains two thiophen polymers exceed an order of magnitude;
2. the thieno-[3 that also contains simultaneously, 4-b] pyrazine is a kind of good two dimensional structure that has, the body unit that is subjected to that contains a five-ring and six-ring skeleton, and have intramolecular charge and shift character, excellent electrochemical reduction character, make this polymkeric substance have stronger electron-withdrawing power, widened light absorbing bandwidth, strengthened reduction potential, this polymkeric substance also has stronger modifiability, can utilize easy method in this polymer molecule, to introduce electron-donating group and electron-accepting group, regulate its electrophilic performance;
3. the preparation method is simple, the productive rate height, and the reaction conditions gentleness is easy to operate and control, and is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the synoptic diagram that two thiophene thiophenes are coughed up class conjugated polymers general formula of molecular structure that contains of the embodiment of the invention;
Fig. 2 is that the polymkeric substance for preparing with embodiment 1 is the structural representation of the polymer solar cell device of active coating;
Fig. 3 is that the polymkeric substance for preparing with embodiment 1 is the structural representation of the organic electroluminescence device of active coating;
Fig. 4 is that the polymkeric substance for preparing with embodiment 1 is the structural representation of the organic field effect tube device of organic semiconductor layer.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
See also Fig. 1, show that the two thiophene thiophenes that contain of the embodiment of the invention are coughed up the class conjugated polymers, its general formula of molecular structure is following (I):
In the formula, arbitrary positive integer of x+y=1,0＜x≤0.5,1＜n≤150, R
1, R
2Be selected from C
1～C
15Alkyl, R
3, R
4Be selected from-H, C
1～C
15Alkyl, C
1～C
15Alkoxyl group, contain alkyl or/and the alkoxy thiophene group, contain the alkyl fluorene group, contain the alkyl carbazole group, contain at least a in the alkylbenzene cyclic group.
Above-mentioned contains alkyl or/and the alkoxy thiophene group is preferably any in the following general formula of molecular structure, in the formula, and R
5, R
6, R
7, R
8, R
9, R
10Be preferably C
1～C
15Alkyl is or/and C
1～C
15Alkoxyl group,
The above-mentioned alkyl fluorene group that contains is preferably following general formula of molecular structure, in the formula, and R
11, R
12Be preferably C
1～C
20Alkyl,
The above-mentioned alkyl carbazole group that contains is preferably following general formula of molecular structure, in the formula, and R
13Be preferably C
1～C
15Alkyl,
The above-mentioned alkylbenzene cyclic group that contains is preferably following general formula of molecular structure, in the formula, and R
14Be preferably C
1～C
15Alkyl,
The invention described above embodiment provides contains two thiophene thiophenes and coughs up two thiophene that contain in the class conjugated polymers molecule and have particular structure, two thiphene ring in its structural unit are on same plane, this structure can effectively prolong the conjugation performance of polymkeric substance, reduce the energy gap of polymkeric substance, make current carrier between two main chains, shift to become and be more prone to, increased carrier mobility; Two thiophene [3 that contain, 2-b:2 ', 3 '-d] to cough up the unit be with cyclopentadiene (2 to thiophene, 1-b:3,4-b ') the C atom in the structure of two thiophene converts the Si atom to, has improved the crystallinity of this polymkeric substance, has improved the transport property of electric charge, it is compound to have weakened bimolecular, makes the carrier mobility that the carrier mobility of this polymkeric substance relatively only contains two thiophen polymers exceed an order of magnitude.
This contains two thiophene thiophenes and coughs up the thieno-[3 that contains simultaneously in the class conjugated polymers molecule, 4-b] pyrazine is a kind of good two dimensional structure that has, the body unit that is subjected to that contains a five-ring and six-ring skeleton, and have intramolecular charge and shift character, excellent electrochemical reduction character, make this polymkeric substance have stronger electron-withdrawing power, widened light absorbing bandwidth, strengthened reduction potential, this polymkeric substance also has stronger modifiability, can utilize easy method in this polymer molecule, to introduce electron-donating group and electron-accepting group, regulate its electrophilic performance; Therefore, the embodiment of the invention contain two thiophene thiophenes cough up contain simultaneously in the class conjugated polymers molecule two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up unit and thieno-[3,4-b] polymkeric substance of pyrazine unit, enlarge this polymkeric substance in the range of application in fields such as polymer solar battery.
And the embodiment of the invention also provides this to contain two thiophene thiophenes and has coughed up the class method for preparing conjugated polymer, comprises following chemical equation:
The processing step that namely specifically comprises is:
(1) compd A, B, C, cyclohexadione compounds and 3,4-, the two amido thiophene hydrogenchloride that provide following structural formula to represent respectively,
In the formula, arbitrary positive integer of x+y=1,0＜x≤0.5,1＜n≤150, R
1, R
2Be selected from C
1～C
15Alkyl, R
3, R
4Be selected from-H, C
1～C
15Alkyl, C
1～C
15Alkoxyl group, contain alkyl or/and the alkoxy thiophene group, contain the alkyl fluorene group, contain the alkyl carbazole group, contain at least a in the alkylbenzene cyclic group;
(2) under weakly alkaline and 0～78 ℃, be 1: 0.1～10 to carry out dehydration reaction 1～24h in molar ratio with cyclohexadione compounds and 3,4-, two amido thiophene hydrogenchloride, make two replacement-thieno-[3, the 4-b] pyrazines of 2,3-;
(3) under 0～70 ℃, be 1: 0.1～10 to carry out bromination reaction 1～48h and make described Compound C in molar ratio with two replacement-thieno-[3, the 4-b] pyrazines of 2,3-and N-bromo-succinimide;
(4) compd A, B, C are carried out coupling reaction for m: p: q in molar ratio in organic solvent, obtain following general structure and be the polymkeric substance of (I) expression, wherein, m=p+q, and m＞p 〉=0,
General structure is in (I), arbitrary positive integer of x+y=1,0＜x≤0.5,1＜n≤150.
The solvent of dehydration reaction is preferably at least a in methyl alcohol, ethanol, the ethyl acetate and reaction solvent capacity in the above-mentioned steps (2); Weakly alkaline weak base is preferably at least a in triethylamine, the yellow soda ash, and described weak base consumption and cyclohexadione compounds consumption are preferably 2～50: 1 in molar ratio.This step is preferably carried out under the lucifuge condition, and this is because this reactant photosensitivity is strong, easily decomposes under illumination, thereby has reduced bromo thiophene class monomer yield.
The solvent of bromination reaction described in the above-mentioned steps (3) is preferably mixed solution, the N of tetrahydrofuran (THF), chloroform and acetic acid volume ratio 1: 0.1～10, at least a in the dinethylformamide, and reaction solvent capacity.
Further, above-mentioned steps (4) is that coupling reaction is the Stille coupling reaction, this Stille coupling reaction can also add catalyzer and improve the speed of this coupling reaction and contain the yield that two thiophene thiophenes are coughed up the class conjugated polymers, the addition of catalyzer is preferably 0.05%～50% of compd A molar percentage, and described catalyzer is preferably the mixture of organic palladium catalyzer or organic palladium catalyzer and organophosphorus ligand.Wherein, the organic palladium catalyzer is preferably Pd
2(dba)
3/ P (o-Tol)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2In at least a; When catalyzer is the mixture of organic palladium catalyzer and organophosphorus ligand, the mol ratio of this organic palladium catalyzer and organophosphorus ligand is preferably 1: 2～and 20.
The organic solvent of above-mentioned Stille coupling reaction is preferably one or more in tetrahydrofuran (THF), glycol dimethyl ether, benzene or the toluene, and the reaction solvent capacity; The temperature of reaction of coupling reaction is 40～120 ℃, and the time is 24～72 hours.
Above-mentioned Stille coupling reaction can carry out at aerobic environment or in oxygen-free environment.Preferably carry out in oxygen-free environment, oxygen-free environment can adopt vacuum or be full of rare gas element and realize, preferably is full of rare gas element and realizes oxygen-free environment, and this rare gas element is the art rare gas element commonly used, for example nitrogen, argon gas etc., preferred nitrogen.This is because carrying out improving in oxygen-free environment contains the yield that two thiophene thiophenes are coughed up the class conjugated polymers, because oxygen is a very active composition, energy and reactant reaction have disturbed successful reaction to carry out, thereby reduced efficiency of pcr product.
Contain two thiophene thiophenes at this and cough up in the class method for preparing conjugated polymer, only need that reactant is pressed ratio and add, need not special equipment and environmental requirement, its preparation method technology is simple, and productive rate height, and mild condition are easy to operate and control, and are suitable for suitability for industrialized production.
Because the present invention contains two thiophene thiophenes and coughs up the class conjugated polymers and have above-mentioned advantage, therefore, this contain two thiophene thiophenes cough up the class conjugated polymers can be at organic photoelectrical material, polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or/and use in the organic laser field.
Now in conjunction with the embodiments, the present invention is further elaborated.
Embodiment 1
Following structural formula P
1Synthesizing of polymkeric substance:
The preparation of two phenyl-thieno-[3, the 4-b] pyrazines of (1) 2,3-, its reaction is shown below:
The preparation detailed process is: with 3,4-two amido thiophene hydrogenchloride (1.0g, 5.34mmol) join and contain compound diphenylthanedione (1.12g, 5.34mmol) and dehydrated alcohol (100mL) solution of triethylamine (10.68mmol) in, then under the lucifuge condition, (1.15g, 11mmol) stirred 1 hour the back under 78 ℃ to add triethylamine.With the desolventizing of reaction solution rotary evaporation, column chromatography (methylene dichloride is as eluent) obtains solid behind the question response.MS(EI)m/z：288(M
+)。
(2) 5,7-dibromos 2, the preparation of two phenyl-thieno-[3, the 4-b] pyrazines of 3-, its reaction is shown below:
The preparation detailed process is: with NBS (0.72g, 4mmol) join and contain compound 2, two phenyl-the thieno-s [3 of 3-, 4-b] and pyrazine (0.49g, (v/v=1/1 is in solution 10mL) for chloroform/acetic acid 1.7mmol), and under ice bath, stir after 48 hours, reaction solution is joined in the saturated sodium carbonate solution, carry out chloroform extraction, water washing, anhydrous sodium sulfate drying more successively, revolve desolventizing, column chromatography gets yellow solid then.MS(EI)m/z：446(M
+)。
(3) polymer P
1Preparation, its reaction is shown below:
The preparation detailed process is: under nitrogen protection; toward containing compound 5,7-dibromo 2, the two phenyl-thieno-s [3 of 3-; 4-b] pyrazine (0.22g; 0.5mmol), 4,4-dioctyl-2, two tin trimethyl-two thiophene [3 of 6-; 2-b:2 '; 3 '-d] thiophene coughs up that (0.37g, toluene 0.5mmol) (30mL) solution continuous bubbling 0.5h removes the oxygen in the environment, adds Pd
2(dba)
3(0.14g, 0.015mol) and P (o-Tol)
3(0.0083g, 0.027mmol) after, continue bubbling 1h and remove residual oxygen, be heated to 90 ℃ then, reacted 72 hours.After reaction finishes mixed solution is added drop-wise to and carries out sedimentation in the methyl alcohol, carry out suction filtration, methanol wash, drying more successively, then with after the chlorobenzene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.The organic phase that obtains by behind the column chromatography of aluminum oxide, is carried out chloroform drip washing, decompression successively and removed organic solvent, methyl alcohol sedimentation, suction filtration and get solid.Use acetone Soxhlet extraction three days, methyl alcohol sedimentation, suction filtration to obtain product successively the gained solid.Molecular?weight(GPC，THF，R.I)：M
n＝61100，M
w/M
n＝2.3)。
Embodiment 2
Following structural formula P
2Synthesizing of polymkeric substance:
The preparation of two phenyl-thieno-[3, the 4-b] pyrazines of (1) 2,3-, its reaction is shown below:
The preparation detailed process is: with 3,4-two amido thiophene hydrogenchloride (5.34mmol) join in anhydrous ethyl acetate (100mL) solution of compound diphenylthanedione (0.534mmol) and yellow soda ash (26.7mmol), then under the lucifuge condition, add triethylamine (1.15g, 11mmol) back is stirred after 24 hours under ice bath, the rotary evaporation desolventizing, column chromatography (methylene dichloride is as eluent) obtains solid.MS(EI)m/z：288(M
+)。
(2) 5,7-dibromos 2, the preparation of two phenyl-thieno-[3, the 4-b] pyrazines of 3-, its reaction is shown below:
The preparation detailed process is: with NBS (0.72g, 4mmol) join and contain compound 2, two phenyl-the thieno-s [3 of 3-, 4-b] tetrahydrofuran (THF) (the THF)/N of pyrazine (0.4mmol), (v/v=1/2 is in solution 10mL) for dinethylformamide (DMF), and after stirring 1 hour under 70 ℃, reaction solution is joined in the saturated sodium carbonate solution, carry out chloroform extraction, water washing, anhydrous sodium sulfate drying more successively, revolve desolventizing, column chromatography gets yellow solid then.MS(EI)m/z：446(M
+)。
(3) polymer P
2Preparation, its reaction is shown below:
The preparation detailed process is: toward containing compound 5,7-dibromo 2, the two phenyl-thieno-s [3 of 3-, 4-b] and pyrazine (0.11g, 0.5mmol), 4,4-dioctyl-2,6-two bromo-two thiophene [3,2-b:2 ', 3 '-d] thiophene is coughed up (0.14g, 0.25mmol), 4,4-dioctyl-2, two tin trimethyl-two thiophene of 6-[3,2-b:2 ', 3 '-d] thiophene coughs up that (0.37g adds Pd (PPh in glycol dimethyl ether 0.5mmol) (30mL) solution
3)
4(0.035mmol), be heated to 120 ℃ then, reacted 24 hours.Reacted mixed solution is added drop-wise to carries out sedimentation in the methyl alcohol, carry out suction filtration, methanol wash, drying more successively, then with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ of stirrings and spends the night.The organic phase that obtains by behind the column chromatography of aluminum oxide, is carried out chloroform drip washing, decompression more successively and removed organic solvent, methyl alcohol sedimentation, suction filtration and get solid.After the gained solid extracted three days with the acetone Soxhlet, carry out the methyl alcohol sedimentation successively again, suction filtration obtains product.Molecular?weight(GPC，THF，R.I)：M
n＝48600，M
w/M
n＝1.7)。
Embodiment 3
Following structural formula P
3Synthesizing of polymkeric substance:
The preparation of (1) 5,7-dibromo 2-(3-(nitrogen hexyl carbazole) base)-3-phenyl-thieno-[3,4-b] pyrazine, its reaction is shown below:
The preparation detailed process is: with NBS (0.43g, 2.4mmol) join and contain compound 2-(3-(nitrogen hexyl carbazole) base)-3-phenyl-thieno-[3,4-b] pyrazine (0.50g, chloroform/acetic acid (v/v=1/1 1.1mmol), in solution 20mL), and after stirring 24 hours under 35 ℃.Reaction solution is joined in the saturated sodium carbonate solution, carry out chloroform extraction, water washing, anhydrous sodium sulfate drying more successively, revolve desolventizing, column chromatography gets yellow solid then.MS(MALDI)m/z：619(M
+)。
(2) polymer P
3Preparation, its reaction is shown below:
The preparation detailed process is: under nitrogen protection; toward containing compound 5; 7-dibromo 2-(3-(nitrogen hexyl carbazole) base)-3-phenyl-thieno-[3,4-b] pyrazine (0.32g, 0.5mmol), 4; 4-dioctyl-2; two tin trimethyl-two thiophene of 6-[3,2-b:2 ', 3 '-d] thiophene is coughed up (0.372g; 0.5mmol) toluene/benzene (v/v=4/1 altogether 30mL) solution in continuous bubbling 0.5h remove oxygen in the reaction environment, add Pd again
2(dba)
3(0.14g, 0.015mol) and P (o-Tol)
3(0.0083g, 0.027mmol) after, continue bubbling 1h and remove residual oxygen, be heated to 40 ℃ then, reacted 48 hours.After reaction finishes mixed solution is added drop-wise to and carries out sedimentation in the methyl alcohol, carry out suction filtration, methanol wash, drying more successively, then with after the chlorobenzene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.The organic phase that obtains by behind the column chromatography of aluminum oxide, is carried out chloroform drip washing, decompression successively and removed organic solvent, methyl alcohol sedimentation, suction filtration and get solid.Use acetone Soxhlet extraction three days, methyl alcohol sedimentation, suction filtration to obtain product successively the gained solid.Molecular?weight(GPC，THF，R.I)：M
n＝47100，M
w/M
n＝1.7；)。
Embodiment 4
Following structural formula P
4Synthesizing of polymkeric substance:
(1) 5,7-dibromo 2, the preparation of two (2-(9,9-dioctyl fluorene) base) thieno-[3, the 4-b] pyrazines of 3-, its reaction is shown below:
The preparation detailed process is: (0.25g 1.4mmol) joins and contains compound 2-(3-(nitrogen hexyl carbazole) base)-3-phenyl-thieno-[3,4-b] pyrazine (0.55g with NBS, 0.6mmol) chloroform/acetic acid (v/v=1/1, in solution 20mL), and after stirring 24 hours under 35 ℃.Reaction solution is joined in the saturated sodium carbonate solution, carry out chloroform extraction, water washing, anhydrous sodium sulfate drying more successively, revolve desolventizing, column chromatography gets solid then.MS(MALDI)m/z：1071(M
+)。
(2) polymer P
4Preparation, its reaction is shown below:
The preparation detailed process is: under nitrogen protection, toward containing compound 5,7-dibromo 2; 3-is two, and (2-(9; the 9-dioctyl fluorene) base) thieno-[3,4-b] pyrazine (0.54g, 0.5mmol), 4; 4-dioctyl-2; two tin trimethyl-two thiophene of 6-[3,2-b:2 ', 3 '-d] thiophene is coughed up (0.372g; 0.5mmol) toluene (30mL) solution in continuous bubbling 0.5h remove oxygen in the reaction environment, add Pd again
2(dba)
3(0.14g, 0.015mol) and P (o-Tol)
3(0.0083g 0.027mmol), continues bubbling 1h and removes residual oxygen, is heated to 80 ℃ then, reacts 96 hours.After reaction finishes mixed solution is added drop-wise to and carries out sedimentation in the methyl alcohol, carry out suction filtration, methanol wash, drying more successively, then with after the chlorobenzene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.The organic phase that obtains by behind the column chromatography of aluminum oxide, is carried out chloroform drip washing, decompression successively and removed organic solvent, methyl alcohol sedimentation, suction filtration and get solid.Use acetone Soxhlet extraction three days, methyl alcohol sedimentation, suction filtration to obtain product successively the gained solid.Molecular?weight(GPC，THF，R.I)：M
n＝13500，M
w/M
n＝2.1)。
Application Example 5
With the preparation as the solar cell device of active coating of the polymkeric substance of embodiment 1 preparation:
See also Fig. 2, this solar cell device comprises glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14, the negative electrode 15 that stacks gradually, middle supplementary layer 13 adopts polyethylene dioxy base thiophene: polystyrene-sulfonic acid matrix material (abbreviating PEDOT:PSS as), active coating 14 comprises electron donor material and electron acceptor material, electron donor material adopts the polymkeric substance of embodiment 1 preparation, electron acceptor material can be [6,6] phenyl-C
61-methyl-butyrate (abbreviating PCBM as).Transparent anode 12 can adopt tin indium oxide (abbreviating ITO as), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Negative electrode 15 can adopt aluminium electrode or double-metal layer electrode, for example Ca/Al or Ba/Al etc.Wherein, glass-base 11 can be used as bottom, during making, choose ito glass, and after ultrasonic cleaning, handle with oxygen-Plasma, supplementary layer 13 in the middle of ito glass applies on the supplementary layer 13, forms active coating 14 in the middle of the polymkeric substance of embodiment 1 preparation and electron acceptor material being coated on after by blend again, and then by vacuum evaporation technology deposition cathode 15 on active coating 14, obtain above-mentioned solar cell device.In a preferred embodiment, the thickness of transparent anode 12, middle supplementary layer 13, active coating 14, double-metal layer Ca and Al layer be respectively 170,40,150,70nm.
As shown in Figure 2, under illumination, light transmission glass-base 11 and ITO electrode 12, the polymkeric substance of embodiment 1 preparation in the active coating 14 absorbs luminous energy, and produces exciton, these excitons are moved to electron donor(ED)/acceptor material at the interface again, and give electron acceptor material with transfer transport, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to metallic cathode transmission and collected by negative electrode, freely the hole along electron donor material to ito anode transmission and collected by anode, thereby form photoelectric current and photovoltage, realize opto-electronic conversion, during external load 16, can power to it.In this process, the polymkeric substance of embodiment 1 preparation can utilize luminous energy more fully because it has very wide spectral response range, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, is convenient to large batch of preparation.
Application Example 6
The polymer organic electroluminescence preparation of devices that contains embodiment 1 preparation:
See also Fig. 3, show the polymer organic electroluminescence device that adopts embodiment 1 preparation, it comprises glass-base 21, transparent anode 22, luminescent layer 23, buffer layer 24, the negative electrode 25 that is cascading.Transparent anode 22 can adopt tin indium oxide (abbreviating ITO as), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Luminescent layer 23 comprises the polymkeric substance of embodiment 1 preparation.Buffer layer 24 can adopt LiF etc., but is not limited thereto.Negative electrode 25 can be but be not limited to metal A l etc.Thereby in a specific embodiment, the organic electroluminescence device structural table is shown: the polymkeric substance/LiF/Al of ITO/ embodiment 1 preparation.Each layer can adopt existing method to form, and the polymkeric substance of embodiment 1 preparation can be formed on the ITO by spin coating technique.On this luminescent layer, can adopt vacuum evaporation LiF buffer layer, on buffer layer, can adopt evaporation metal Al, as the negative electrode of device.
Application Example 7
Contain the preparation of the polymer organic field-effect transistor of poly-embodiment 1 preparation:
See also Fig. 4, this organic field effect tube comprises substrate 31, insulation layer 32, decorative layer 33, the organic semiconductor layer 34 that is cascading and is located at source electrode 35 and drain electrode 36 on the organic semiconductor layer 34.Wherein, substrate 31 can be but be not limited to highly doped silicon chip (Si) that insulation layer 32 can be but be not limited to micro-nano (as 400nm) thick SiO
2 Organic semiconductor layer 34 adopts the polymerised moiety of embodiment 1 preparation.Source electrode 35 and drain electrode 36 all can adopt but be not limited to gold.Decorative layer 33 can be but be not limited to octadecyl trichlorosilane (OTS).Substrate 31, insulation layer 32, decorative layer 33 and source electrode 35 and drain electrode 36 all can adopt existing method to form.Organic semiconductor layer 34 can be that the polymkeric substance that embodiment 1 prepares is spun on the insulation layer of being modified by decorative layer 33 32.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. one kind contains two thiophene thiophenes and coughs up the class conjugated polymers, and its general formula of molecular structure is following (I):
In the formula, arbitrary positive integer of x+y=1,0＜x≤0.5,1＜n≤150, R
1, R
2Be C
1～C
15Alkyl, R
3, R
4Be selected from and contain alkyl or/and the alkoxy thiophene group, contain the alkyl fluorene group, contain the alkyl carbazole group, contain at least a in the alkylbenzene cyclic group.
2. the two thiophene thiophenes that contain according to claim 1 are coughed up the class conjugated polymers, it is characterized in that:
Describedly contain alkyl or/and the alkoxy thiophene group is any in the following general formula of molecular structure, in the formula, R
5, R
6, R
7, R
8, R
9, R
10Be selected from C
1～C
15Alkyl or/and C
1～C
15Alkoxyl group,
It is described that to contain alkyl fluorene group general formula of molecular structure as follows, in the formula, and R
11, R
12Be selected from C
1～C
20Alkyl,
It is described that to contain alkyl carbazole group general formula of molecular structure as follows, in the formula, and R
13Be selected from C
1～C
15Alkyl,
It is described that to contain alkylbenzene cyclic group general formula of molecular structure as follows, in the formula, and R
14Be selected from C
1～C
15Alkyl,
3. one kind contains two thiophene thiophenes and coughs up the class method for preparing conjugated polymer, comprises the steps:
The compd A, B, the C that provide following structural formula to represent respectively,
Wherein, R
1, R
2Be selected from C
1～C
15Alkyl, R
3, R
4Be selected from and contain alkyl or/and the alkoxy thiophene group, contain the alkyl fluorene group, contain the alkyl carbazole group, contain at least a in the alkylbenzene cyclic group;
Compd A, B, C are carried out coupling reaction for m: p: q in molar ratio in organic solvent, obtain following general structure and be the polymkeric substance of (I) expression, wherein, m=p+q, and m＞p 〉=0; Described coupling reaction also is added with catalyzer, and its addition is 0.05%～50% of compd A molecular fraction, and described catalyzer is the mixture of organic palladium catalyzer or organic palladium catalyzer and organophosphorus ligand; Described organic solvent is one or more in tetrahydrofuran (THF), glycol dimethyl ether, benzene or the toluene; The temperature of reaction of described coupling reaction is 40～120 ℃, and the time is 24～72 hours;
General structure is in (I), arbitrary positive integer of x+y=1,0＜x≤0.5,1＜n≤150.
4. the two thiophene thiophenes that contain according to claim 3 are coughed up the class method for preparing conjugated polymer, and it is characterized in that: the preparation method of described Compound C comprises following steps:
Under 0～78 ℃, under the weak basic condition, be 1: 0.1～10 to carry out dehydration reaction 1～24h in molar ratio with cyclohexadione compounds and 3,4-, two amido thiophene hydrogenchloride, make two replacement-thieno-[3, the 4-b] pyrazines of 2,3-;
Under 0～70 ℃, be 1: 0.1～10 to carry out bromination reaction 1～48h in molar ratio with two replacement-thieno-[3, the 4-b] pyrazines of 2,3-and N-bromo-succinimide, make described Compound C.
5. the two thiophene thiophenes that contain according to claim 4 are coughed up the class method for preparing conjugated polymer, it is characterized in that: the solvent of described dehydration reaction is at least a in methyl alcohol, ethanol, the ethyl acetate;
Weakly alkaline weak base is at least a in triethylamine, the yellow soda ash in the described dehydration reaction, and described weak base consumption and cyclohexadione compounds consumption are 2～50: 1 in molar ratio;
The solvent of described bromination reaction is mixed solution, the N of tetrahydrofuran (THF), chloroform and acetic acid volume ratio 1: 0.1～10, at least a in the dinethylformamide.
6. the two thiophene thiophenes that contain according to claim 3 are coughed up the class method for preparing conjugated polymer, and it is characterized in that: described organic palladium catalyzer is Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2In at least a.
7. the two thiophene thiophenes that contain according to claim 3 are coughed up the class method for preparing conjugated polymer, and it is characterized in that: the mixture of described organic palladium catalyzer and organophosphorus ligand is Pd
2(dba)
3/ P (o-Tol)
3
The mol ratio of organic palladium catalyzer and organophosphorus ligand is 1: 2～20 in the mixture of described organic palladium catalyzer and organophosphorus ligand.
8. the two thiophene thiophenes that contain according to claim 3 are coughed up the class method for preparing conjugated polymer, and it is characterized in that: described coupling reaction is to carry out in oxygen-free environment.
According to claim 1 to 2 each described contain two thiophene thiophenes cough up the class conjugated polymers at organic photoelectrical material, polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or/and the organic laser Application for Field.
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| Synthesis and Characterization of Bridged Bithiophene-Based Conjugated Polymers for Photovoltaic Applications: Acceptor Strength and Ternary Blends";Chiu-Hsiang Chen, et al;《Macromolecules》;20091209;第43卷(第2期);第697-708页 * |
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