CN103408731A - Semiconductor conjugated polymer based on isoindigo and trans-1,2-bis(2-thienyl) ethylene and preparation method of semiconductor conjugated polymer - Google Patents
Semiconductor conjugated polymer based on isoindigo and trans-1,2-bis(2-thienyl) ethylene and preparation method of semiconductor conjugated polymer Download PDFInfo
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Abstract
The invention discloses a novel conjugated polymer based on isoindigo and trans-1,2-bis(2-thienyl) ethylene and a preparation method of novel conjugated polymer. The conjugated polymer has a structural formula shown in the specification, wherein R is a C12-C24 alkane chain, and n is more than or equal to 1. According to the preparation method, a trans-1,2-bis(2-thienyl) ethylene dual-tin monomer and an isoindigo dual-bromine monomer are in Stille cross coupling reaction to prepare the conjugated polymer. Based on the advantages of the isoindigo and the trans-1,2-bis(2-thienyl) ethylene are combined together, the invention provides a novel and solution-processable semiconductor conjugated polymer. The semiconductor conjugated polymer disclosed by the invention is reasonable in molecular design, has a good molecular arrangement, has a strong absorption peak in a whole visible light area, and can be applied to organic thin-film transistors and organic photovoltaic devices.
Description
Technical field
What the present invention relates to is a kind of organic semiconductor material of solution processable, specifically a kind of based on bioxindol and trans-1, semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene and preparation method thereof.
Background technology
Give in recent years ,/applied research of acceptor (D/A) conjugated polymers in OTFT (OTFT) and organic photovoltaic (OPV) progressively cause people's attention.With traditional inorganic materials, compare, it is lightweight that polymkeric substance is that basic semiconductor material has, cost is low, snappiness is good and easily by solution, process, the advantages such as spin-coating film, making polymkeric substance is that basic OPV and OTFT has broad application prospects in fields such as the energy, combinational circuit and flexible demonstrations.The D/A structure is to design at present one of the most frequently used means of high-performance conjugated polymers, and on the one hand, due to the mutual push-and-pull action between D unit and A unit, the D/A multipolymer replaced easily forms the interior pi-pi accumulation of molecule closely, is conducive to improve mobility.On the other hand, the D/A structure can make conjugated polymers obtain low band gap, can make even near infrared region of polymkeric substance absorption spectrum covering visible light, can effectively absorb the solar photon energy, is conducive to obtain high short-circuit current in OPV.Different iodine indigo plant is a kind of at dyestuffs industries pigment commonly used, in many natural resourcess, can easily obtain, simultaneously, the bioxindol molecule has strong electrophilic lactim group, can make polymkeric substance obtain low highest occupied molecular orbital energy level (HOMO), not only improve the stability of polymkeric substance, can also effectively improve open circuit voltage in OPV, therefore, the bioxindol molecule is the effective unit that builds the high-performance semiconductor conjugated polymers.(referring to document: Wang E, Ma Z, Zhang Z, Henriksson P, Inganas O, Zhang F, Andersson M. An easily accessible isoindigo-based polymer for high-performance polymer solar cells, J Am Chem Soc, 2011, 133, 14244. Lei T, Cao Y, Fan Y, Liu C, Yuan S, Pei J. High-performance air-stable organic field-effect transistors:isoindigo-based conjugated polymers, J Am Chem Soc, 2011, 133, 6099.).In the bioxindol polymkeric substance of former report, polymkeric substance is very weak in the absorption intensity of high energy region, (referring to document: Wang E, Ma Z, Zhang Z, Henriksson P, Inganas O, Zhang F, Andersson M. An isoindigo-based low band gap polymer for efficient polymer solar cells with high photo-voltage. Chem Commun, 2011, 47, 4908. Zhang G, Fu Y, Xie Z, Zhang Q. Synthesis and photovoltaic properties of new low bandgap isoindigo-based conjugated polymers. Macromolecules, 2011, 44, 1414.)
Affect like this polymkeric substance and effectively absorb the solar photon energy, this is that the method for solution is exactly the effective conjugate length that increases the D unit due to due to the strong electrophilic impact of bioxindol.Therefore, here introduce trans-ly 1,2-bis-(2-thienyl) ethene, as the D unit, can effectively increase pi-conjugated length, with the bioxindol monomer, form Optical Properties of Novel Conjugated by the polymerization of Stille cross-coupling, effectively increase the absorption intensity of polymkeric substance in the high energy region.
Summary of the invention
The object of the invention is exactly in order to provide a kind of based on bioxindol and trans-1, semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of based on bioxindol and trans-1, the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene, the structural formula of described conjugated polymers is:
Wherein, R is C
12-C
24Alkane chain, n>=1.
A kind of based on bioxindol and trans-1, the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene, described alkane chain can be selected C
12-C
24Straight chain or C
8-C
24Branched paraffin.
A kind of based on bioxindol and trans-1, the preparation method of the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene, the preparation method of described semiconductive conjugated polymer is: with trans-1, the two tin monomers of 2-bis-(2-thienyl) ethene, the two bromine monomers of bioxindol are raw material, adopt the Stille reaction to obtain described semiconductive conjugated polymer.
A kind of based on bioxindol and trans-1, the preparation method of the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene, the reaction of described acquisition conjugated polymers is to be catalyzer take three (dibenzalacetone) two palladiums, and three (o-methyl-phenyl-) phosphorus is that the polymerization under the system of part completes.
A kind of based on bioxindol and trans-1, the preparation method of the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene, described copolyreaction temperature is 80-130
oC.
A kind of based on bioxindol and trans-1, the preparation method of the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene, the described copolyreaction time is 8-72 hour.
Advantage of the present invention is:
The novel semi-conductor conjugated polymers that the present invention relates to synthesize is in conjunction with bioxindol and trans-1, the advantage of 2-bis-(2-thienyl) ethene, take the side chain the introduced alkyl chain as flexible dissolution, synthetic a kind of novel semiconductive conjugated polymer, the prepared conjugated polymers solution processable of the present invention is processed, in whole visible region, strong absorption is arranged, can be applicable to OTFT and organic photovoltaic devices.
The accompanying drawing explanation
Fig. 1 is based on bioxindol and trans-1, the synthesis path schematic diagram of the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene;
Fig. 2 is that monomer is trans-1, the synthesis path schematic diagram of the two tin monomers of 2-bis-(2-thienyl) ethene and the two bromine monomers of bioxindol;
Fig. 3 is the synthesis path schematic diagram of polymer P 1 in embodiment 1;
Fig. 4 is the abosrption spectrogram of the conjugated polymers P1 of solution processable.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated: this example is implemented take technical solution of the present invention under prerequisite, combine detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
As shown in Figure 1, the present invention is with trans-1, and two tin monomers of 2-bis-(2-thienyl) ethene and two bromine monomers copolymerization under the Stille reaction conditions of bioxindol, use methanol extraction, and then Soxhlet is extracted, and obtains subject polymer.
The conjugated polymers that solution processable of the present invention contains different iodine indigo plant has following structure:
Wherein, R is C
12-C
24Alkane chain, n>=1.
Above-mentioned alkane can be selected straight chain or side chain, preferably C
12-C
24Straight chain or C
8-C
24Branched paraffin.
The preparation method:
Preparation method to each monomer describes, as follows:
Prepare trans-1, the two tin monomers of 2-bis-(2-thienyl) ethene
Trans-1, the synthesis path schematic diagram of the two tin monomers of 2-bis-(2-thienyl) ethene as shown in Figure 2.Two tin monomers adopt literature method to make, and detailed preparation method is referring to bibliographical information (Adv Mater 2012,24,4618.)
Prepare the two bromine monomers of bioxindol
The synthesis path schematic diagram of the two bromine monomers of bioxindol is as shown in 2.Two bromine monomers be take 6-bromo-isatin and 6-bromo indole-2-ketone and are raw material, adopt the literature method preparation and obtain, and detailed preparation method is referring to bibliographical information (Macromolecules, 2011,44,1414.)
Embodiment 1, synthetic polymer P1
The synthesis path schematic diagram of polymer P 1 as shown in Figure 3, concrete steps are: in 100 mL glass reaction bottles, add the two tin monomers of 0.6 mmol and the two bromine monomers (R that two bromine monomers are corresponding is as shown in table 1) of 0.6 mmol, add again dry toluene (also can be anhydrous tetrahydro furan, chlorobenzene) 20 mL, stirred the while nitrogen replacement 30 minutes, add 2% catalyzer three (dibenzalacetone) two palladiums, three (o-methyl-phenyl-) phosphorus of take is part, in 110
oC reaction 48 hours, be cooled to room temperature by reaction, adds 200 mL methanol extractions, crosses filter solid, by methyl alcohol and normal hexane Soxhlet, extracted 24 hours respectively, then use the chlorobenzene dissolved solids, and last methanol extraction obtains blue polymer.
Embodiment 2-4, synthetic polymer P2-P3
Concrete steps are with embodiment 1: in 100 mL glass reaction bottles, add the two tin monomers of 0.6 mmol and the two bromine monomers (R that two bromine monomers are corresponding is as shown in table 1) of 0.6 mmol, adding dry toluene (also can be anhydrous tetrahydro furan, chlorobenzene) 20 mL, stirred the while nitrogen replacement 30 minutes, add 2% catalyzer three (dibenzalacetone) two palladiums, three (o-methyl-phenyl-) phosphorus of take is part, in 110
oC reaction 48 hours, be cooled to room temperature by reaction, adds 200 mL methanol extractions, crosses filter solid, by methyl alcohol and normal hexane Soxhlet, extracted 24 hours respectively, then use the chlorobenzene dissolved solids, and last methanol extraction obtains blue polymer P2-P3, and its structure is as shown in table 1.
Table 1
Fig. 4 has provided the abosrption spectrogram of polymer P 1, and absorption peak covers whole visible light, with 500-800 nm zone, great absorption peak is arranged in 300-500 nm zone.Maximum absorption band is at 602 nm, and the optical energy band gap is 1.63 eV.
In sum, the present invention relates to based on bioxindol and trans-1, the novel semi-conductor conjugated polymers of 2-bis-(2-thienyl) ethene, the constitutional features of this new polymers is the large pi-conjugated system of copline with rigidity, increase effective conjugate length, thereby improve the absorption in the high energy region, introduced simultaneously flexible dissolution alkyl chain, a synthetic class is novel, semiconductive conjugated polymer solution processable, and semiconductive conjugated polymer of the present invention can be applicable to OTFT and organic photovoltaic devices.
Claims (6)
1. one kind based on bioxindol and trans-1, the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene, and it is characterized in that: the structural formula of described conjugated polymers is:
Wherein, R is C
12-C
24Alkane chain, n>=1.
2. according to claim 1 a kind of based on bioxindol and trans-1, the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene, it is characterized in that: described alkane chain can be selected C
12-C
24Straight chain or C
8-C
24Branched paraffin.
3. one kind as require 1 described based on bioxindol and trans-1, the preparation method of the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene, the preparation method who it is characterized in that described semiconductive conjugated polymer is: with trans-1, the two tin monomers of 2-bis-(2-thienyl) ethene, the two bromine monomers of bioxindol are raw material, adopt the Stille reaction to obtain described semiconductive conjugated polymer.
4. according to claim 3 a kind of based on bioxindol and trans-1, the preparation method of the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene, it is characterized in that: the reaction of described acquisition conjugated polymers is to be catalyzer take three (dibenzalacetone) two palladiums, and three (o-methyl-phenyl-) phosphorus is that the polymerization under the system of part completes.
5. according to claim 3 a kind of based on bioxindol and trans-1, the preparation method of the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene is characterized in that described copolyreaction temperature is 80-130
oC.
6. according to claim 3 a kind of based on bioxindol and trans-1, the preparation method of the semiconductive conjugated polymer of 2-bis-(2-thienyl) ethene is characterized in that the described copolyreaction time is 8-72 hour.
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|---|---|---|---|---|
| CN105418895A (en) * | 2015-12-02 | 2016-03-23 | 上海交通大学 | Preparation method and application of isoindigo conjugated polymer taking thiofuran as spatial isolation group |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013028791A (en) * | 2011-06-24 | 2013-02-07 | Univ Of Tsukuba | Polymer dye |
| CN103159926A (en) * | 2011-12-09 | 2013-06-19 | 海洋王照明科技股份有限公司 | Isoindigo based co-polymer organic semiconductor material, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013028791A (en) * | 2011-06-24 | 2013-02-07 | Univ Of Tsukuba | Polymer dye |
| CN103159926A (en) * | 2011-12-09 | 2013-06-19 | 海洋王照明科技股份有限公司 | Isoindigo based co-polymer organic semiconductor material, and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418895A (en) * | 2015-12-02 | 2016-03-23 | 上海交通大学 | Preparation method and application of isoindigo conjugated polymer taking thiofuran as spatial isolation group |
| CN105418895B (en) * | 2015-12-02 | 2017-11-14 | 上海交通大学 | Thiophene is the preparation for the bioxindol conjugated polymer that space isolates group, purposes |
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