CN105418897B - Indoles and the conjugated polymer of fen class compound and its production and use - Google Patents
Indoles and the conjugated polymer of fen class compound and its production and use Download PDFInfo
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- CN105418897B CN105418897B CN201510875894.3A CN201510875894A CN105418897B CN 105418897 B CN105418897 B CN 105418897B CN 201510875894 A CN201510875894 A CN 201510875894A CN 105418897 B CN105418897 B CN 105418897B
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Abstract
The invention provides a kind of indoles and thiophene conjugated polymer and its production and use, and the structure of the polymer is shown in formula I：(I), wherein, R is C8~C24 alkyl chains, and X is S or Se, 300 >=n ＞ 1.Compared with prior art, the present invention has following beneficial effect：It is provided by the invention using brand-new synthetic method, synthesis is simple, cost is cheap and energy conversion efficiency is high, reaches 7.32%；It can be applied in the synthesis of donor material and in solar energy inversion device, the development and application to solar battery technology are extremely important.
Description
Technical field
The present invention relates to a kind of indoles and the conjugated polymer of fen class compound and its production and use, it is related to solvable
The organic semiconductor material field of liquid processing.
Background technology
Modern society increasingly increases the demand of the energy, and oil, coal, natural gas etc. are all non-renewable energy resources, increasingly
Exhaustion, development development solar cell utilize the effective way that solar energy is the energy problem that solution human society faces.
The active layer donor material common problem of solar cell of the energy conversion efficiency more than 7% is that structure is non-
Normal complicated, suitable trouble, cost are especially high, it is difficult to industrialized production and application.There is an urgent need to it is simple in construction, synthesis is simple, production
The low donor material of cost.
The content of the invention
For in the prior art the defects of, it is an object of the invention to provide the conjugated polymers of a kind of indoles and fen class compound
Thing and its production and use.
The present invention is achieved by the following technical solutions：
In a first aspect, the invention provides a kind of indoles and the conjugated polymer of fen class compound, its structure such as Formulas I institute
Show：
Wherein, R is C8~C24 alkyl chains, and X is S or Se, 300 >=n ＞ 1.
Second aspect, the present invention also provide a kind of preparation side of indoles and the conjugated polymer of fen class compound as the aforementioned
Method, this method comprise the following steps：
R-I or R-Br and 6- bromo-isatins are reacted at 60~120 DEG C, obtain compound 1
The compound 1 is reacted at 20~50 DEG C with phosphorus pentachloride, obtains compound 2
The compound 2 is subjected to reduction reaction at 20~50 DEG C, obtains compound 3
The compound 3 and 2- aldehyde radical -5- bromothiophenes are reacted at 60~130 DEG C, obtain compound IDT
The compound IDT and double methyl tin thiophene or double methyl tin selenium phenol are subjected to Stille idols at 60~120 DEG C
Connection reaction, obtains compound of formula I.
Preferably, the mol ratio of the compound R-I or R-Br and 6- bromo-isatins is 1:1~4:1.
Preferably, the mol ratio of the phosphorus pentachloride and compound 1 is 2.2:1~4:1.
Preferably, the catalyst of the reduction reaction is zinc powder, and the mol ratio of the zinc powder and compound 2 is 4:
1~8:1.
Preferably, the compound 2 and the mol ratio of 2- aldehyde radical -5- bromothiophenes are 1:1.1~1:1.3.
Preferably, the Stille coupling reactions are using three (dibenzalacetone) two palladium as catalyst, three (adjacent first
Base) phenyl phosphorus is part, IDT is 1 with the mol ratio of double methyl tin thiophene or double methyl tin selenophens:1~1:1.3.
The third aspect, present invention also offers a kind of indoles as the aforementioned to prepare organic photovoltaic with thiophene conjugated polymer
Purposes in device.
Preferably, the conjugated polymer is applied to polymer too with fullerene derivate blending as active layer
The test of positive energy battery.
Compared with prior art, the present invention has following beneficial effect：
1st, provided by the invention using brand-new synthetic method, synthesis is simple, cost is cheap and energy conversion efficiency is high,
Reach 7.32%；
2nd, can be applied in the synthesis of donor material and in solar energy inversion device, the development to solar battery technology
It is extremely important with application.
Brief description of the drawings
The detailed description made by reading with reference to the following drawings to non-limiting example, further feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the polymer P IDT-T of embodiment 1 synthetic route chart；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of the compound 1 of embodiment 1；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of the compound 2 of embodiment 1；
Fig. 4 is the compound IDT of embodiment 1 nucleus magnetic hydrogen spectrum figure；
Fig. 5 is the polymer P IDT-T of embodiment 2 chloroformic solution and solid film uv absorption spectra；
Fig. 6 is the polymer P IDT-T of embodiment 2 cyclic voltammetry curve figure；
Fig. 7 is the polymer P IDT-T of embodiment 2 thermogravimetric analysis spectrogram；
Fig. 8 is that the I-V for the thin-film solar cells device that embodiment 3 polymer P IDT-T and PC61BM are semiconductor layer is bent
Line chart；
Fig. 9 is the polymer P IDT-Se of example 4 synthetic route chart.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1 prepares diindyl and spread out and thiophene conjugated polymer
This implementation provides the synthesis of a kind of indoles and thiophene conjugated polymer (PIDT-T), and its structural formula is as shown in table 1,
Synthetic route is shown in Fig. 1.
Table 1
Comprise the following steps that：
(a) synthesis of compound 1：As shown in figure 1, by 6- bromo-isatins (2.26g, 10mmol), potassium carbonate (2.07g,
15mmol), the iodo- 2- octyldodecyls (4.90g, 12mmol) of 1- and DMF (50mL) are added in two-mouth bottle, the standby pressure of nitrogen, 80 DEG C
24h is reacted, is cooled to room temperature, 100mL watery hydrochloric acid stirring 2h is added, adds a large amount of water, dichloromethane extracts 3 times, merges organic
Phase, washed with saturated sodium-chloride, anhydrous MgSO4Dry, be spin-dried for solvent, petroleum ether：Dichloromethane is 3:1 (volume ratio) is elution
Agent, post separation is chromatographed, brown oil liquid (3.15g, 62%) is obtained after being spin-dried for.Nuclear magnetic spectrogram is as shown in Figure 2.
(b) synthesis of compound 2：As shown in figure 1, compound 1 (12.65g, 25mmol), phosphorus pentachloride (PCl5),
(11.5g, 55mmol), toluene (150ml) are added in bottle with two necks, nitrogen displacement 15min, standby pressure, are reacted at room temperature 24 hours, are used carbon
Sour hydrogen sodium water solution is quenched, and toluene extracts 3 times, anhydrous Na2SO4Dry, filtering, be spin-dried for solvent, direct plunge into and react in next step.
Nuclear magnetic spectrogram as shown in Figure 3
(c) synthesis of compound 3：As shown in figure 1, add zinc powder (3.63g, 55mmol), acetic acid (200ml) and compound
2, react at room temperature 20 minutes, filtering, add sodium bicarbonate aqueous solution and extracted three times with dichloromethane, anhydrous sodium sulfate drying, stone
Oily ether：Ethyl acetate (1:15) leacheate, the isolated colourless viscous liquid of chromatographic column (10.60g, 85%) are used as.
(d) compound IDT synthesis：As shown in figure 1, by compound 3 (9.86g, 20mmol), 5- bromine 2- formylthiophenes
(3.82g, 22mmol), pyridine (5ml), methanol (50ml) are added in bottle with two necks, are passed through nitrogen discharge air 15min, and nitrogen is standby
Pressure, flow back 24h, is cooled to room temperature, is washed successively with a large amount of water, watery hydrochloric acid, dichloromethane, is spin-dried for solvent, petroleum ether：Dichloromethane
Alkane leaching is 1:10, which wash post separation, can obtain yellow oily liquid (11.44g, 86%).Nuclear magnetic spectrogram is as shown in Figure 4.
(e) double methyl tin monomer T synthesis
Double methyl tin monomer T structural formulas are：
Its preparation method is referring to document《Chen,C.H；Hsieh,C.H；Dubosc,M；Cheng,Y.J；HsuC.S；
Synthesis and Characterization ofBridged Bithiophene-Based Conjugated
Polymers for PhotovoltaicApplications:Acceptor Strength and Ternary
Blends.Macromolecules 2010,43,697–708.》。
(f) polymer P IDT-T synthesis
As shown in figure 1, under nitrogen protection, respectively by stannous methide conjugative monomer T (0.2mmol) and IDT (0.1335g,
0.2mmol), catalyst Pd2(dba)3(0.0037g, 0.0040mmol), part P (o-tol)3(0.0048g,
0.0160mmol), and solvent dry toluene (10ml), nitrogen displacement 15min, quick tube sealing.Temperature 60 needed for being to slowly warm up to
~110 DEG C, 1~8 hour reaction time；Room temperature is cooled to, appropriate absolute methanol is added and a few drop hydrochloric acid is precipitated, stirring 1
After~2h, filtering, the graininess crude product with metallic luster is obtained.Product is carried with methanol, petroleum ether and chloroform Soxhlet successively
Take, be spin-dried for chloroform, precipitate in methyl alcohol, filter, obtain the particulate copolymer PIDT-T of metallic luster.PIDT-T is 0.08g,
Yield is 69%, number-average molecular weight 135.0kDa, molecular weight distribution 1.3, n=229.
The ultra-violet absorption spectrum and electrochemical properties of embodiment 2, polymer P IDT-T
The present invention relates to the polymer P IDT-T of embodiment 1 in chloroformic solution and the UV-vis absorption spectrums of solid film,
Referring to Fig. 5, absorption maximum peak positions of the conjugated polymer PIDT-T in chloroformic solution is in 615nm, the maximum absorption band of film
Position is in 642nm, optical band gap 1.57eV.Fig. 6 gives polymer P IDT-T cyclic voltammetry curve.Cyclic voltammetry is surveyed
Try to carry out on the CHI610D telephone wire analyzers of computer control, using three traditional electrode test systems, platinum electrode is work
Make electrode, silver/silver ion electrode is reference electrode, and electrolyte is the acetonitrile solution (0.1M) of tetra-n-butyl ammonium hexafluorophosphate, is swept
It is 50mv/s to retouch speed, using ferrocene as reference.The oxidizing potential that ferrocene measures under the system is 0.09eV, because of vacuum bar
The energy level of ferrocene is 4.8eV under part, and the energy level of material can be calculated by the formula of following energy level：E (LUMO)=-
(Ered, onset-0.09+4.8) eV=- (Ered, onset+4.71) eV, E (HOMO)=- (Eox, onset-0.09+4.8)
EV=- (Eox, onset+4.71) eV,.Electro-chemical test shows that its initial reduction current potential in -1.06eV, thus calculates
Lumo energy is -3.65eV, and initial reduction oxidizing potential is -5.33eV in 0.62eV, the HOMO energy levels thus calculated.Fig. 7 is
Polymer P IDT-T thermogravimetric analysis spectrogram, show that conjugated polymer has good heat endurance in figure.
The polymer P IDT-T of embodiment 3 photovoltaic performance
The present invention relates to the polymer P IDT-T of embodiment 1 as hole mobile material in thin-film solar cells should
With.Acceptor material (A) is used as, is to acceptor ratio as donor material (D), fullerene (PC61BM) using polymer P IDT-T
1:1.5, addition different additive DIO optimization performances, using inverted structure device optimization test material photovoltaic performance.Polymer is too
Positive energy battery device test transformation efficiency data are shown in Table 2, and I-V curve is shown in Fig. 8.The PIDT-T transformation efficiencies of preliminary test are up to
7.32%, polymer has higher open-circuit voltage and fill factor, curve factor.
Table 2
Embodiment 4 prepares diindyl and spread out and selenophen conjugated polymer
This implementation provides the synthesis of a kind of indoles and selenophen conjugated polymer (PIDT-Se), and synthetic route is shown in Fig. 9.
(a) double methyl tin monomer Se synthesis
Double methyl tin monomer Se structural formulas are：
Its preparation method is referring to document《Kim,Y.H；Hong,J.Y；Oh,J.H；Yang,Y.D；Naphthalene
Diimide Incorporated Thiophene-Free Copolymers with Acene and Heteroacene
Units:Comparison of Geometric Features and Electron-Donating Strength ofCo-
units.Chem.Mater.2013,25,3251-3259.》。
(b) polymer P IDT-Se synthesis
As shown in figure 9, under nitrogen protection, respectively by stannous methide conjugative monomer Se (0.2mmol) and IDT
(0.1335g, 0.2mmol), catalyst Pd2(dba)3(0.0037g, 0.0040mmol), part P (o-tol)3(0.0048g,
0.0160mmol), and solvent dry toluene (10ml), nitrogen displacement 15min, quick tube sealing.Temperature 60 needed for being to slowly warm up to
~110 DEG C, 1~8 hour reaction time；Room temperature is cooled to, appropriate absolute methanol is added and a few drop hydrochloric acid is precipitated, stirring 1
After~2h, filtering, the graininess crude product with metallic luster is obtained.Product is carried with methanol, petroleum ether and chloroform Soxhlet successively
Take, be spin-dried for chloroform, precipitate in methyl alcohol, filter, obtain the particulate copolymer PIDT-Se of metallic luster.PIDT-Se is
0.09g, yield 71%, number-average molecular weight 141.0kDa, molecular weight distribution 1.4, n=231.
In summary, the synthesis side of brand-new monomer and its polymer with dissymmetrical structure alkylation of the present invention
Method, as well as application of the semiconducting organic layer in polymer solar battery test.Synthetic method provided by the invention
It is simple to operate, cost of material is low, obtained subject polymer has the characteristics of molecular weight big narrow distribution；Base provided by the invention
It can be processed in the polymer for the monomer being alkylated with dissymmetrical structure with good main body conjugated system, material with solution,
Film is can apply to narrower band gap, good heat endurance, film photovoltaic device test surfaces, polymeric material
Photovoltaic device active layer, in the body heterojunction photovoltaic device test of inverted structure, energy conversion efficiency can reach 7.32%,
Had a good application prospect in organic thin film solar.
It should be noted that when substituent R is other alkyl chains, although alkyl chain is different, experiment reaction condition and
Principle is identical, belongs to allogeneic reaction；And X be S or Se they belong to same major element, reaction principle of the invention is complete
Group VIA allied substances are used entirely, synthesis is feasible.The n values of polymer depend on raw material donor and acceptor amount ratio with
And reaction time etc., it can be seen from general knowledge known in this field, n takes 300 >=n to be more than 1 suitable for the present invention.When n is more than 300,
Polymer molecular weight is excessive, causes polymer to be difficult to solvent, is also unfavorable for making devices and improves efficiency.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (6)
1. the preparation method of a kind of indoles and fen class compound conjugated polymer, it is characterised in that comprise the following steps：
R-I or R-Br and 6- bromo-isatins are reacted at 60~120 DEG C,
The compound 1 is reacted at 20~50 DEG C with phosphorus pentachloride,
The compound 2 is subjected to reduction reaction at 20~50 DEG C, obtains compound 3
The compound 3 and 2- aldehyde radical -5- bromothiophenes are reacted at 60~130 DEG C, obtain compound IDT
The compound IDT and double methyl tin thiophene or double methyl tin selenophens are subjected to Stille couplings instead at 60~120 DEG C
Should, obtain compound of formula I；
Indoles and fen class compound conjugated polymer, it is characterised in that structure is shown in formula I：
Wherein, R is C8~C24 alkyl chains, and X is S or Se, 300 >=n ＞ 1.
2. the preparation method of conjugated polymer as claimed in claim 1, it is characterised in that the compound R-I or R-Br with
The mol ratio of 6- bromo-isatins is 1:1~4:1.
3. the preparation method of conjugated polymer according to claim 1, it is characterised in that the phosphorus pentachloride and compound
1 mol ratio is 2.2:1~4:1.
4. the preparation method of conjugated polymer according to claim 1, it is characterised in that the catalyst of the reduction reaction
For zinc powder, the mol ratio of the zinc powder and compound 2 is 4:1~8:1.
5. the preparation method of conjugated polymer according to claim 1, it is characterised in that the compound 3 and 2- aldehyde radicals-
The mol ratio of 5- bromothiophenes is 1:1.1~1:1.3.
6. the preparation method of conjugated polymer according to claim 1, it is characterised in that the Stille coupling reactions with
Three (dibenzalacetone) two palladium is catalyst, three (adjacent methyl) phenyl phosphorus are part, IDT and double methyl tin thiophene or double first
The mol ratio of base tin selenophen is 1:1~1:1.3.
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| CN108727567A (en) * | 2018-05-03 | 2018-11-02 | 上海交通大学 | Introduce preparation and the purposes of the bioxindol derivative conjugated polymer of heavy atom selenium |
| CN111234183B (en) * | 2020-01-19 | 2021-08-31 | 福州大学 | Single-component active layer photovoltaic material containing perylene diimide unit |
| CN113881019A (en) * | 2021-10-18 | 2022-01-04 | 福州大学 | 2-indolone-based polymer donor material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159925A (en) * | 2011-12-09 | 2013-06-19 | 海洋王照明科技股份有限公司 | Isoindigo based co-polymer solar cell material, and preparation method and application thereof |
| CN103467711A (en) * | 2013-08-27 | 2013-12-25 | 上海交通大学 | Bi-thiophene oxindolyl semiconductor polymer, and preparation and application thereof |
| CN103626975A (en) * | 2013-11-05 | 2014-03-12 | 合肥工业大学 | Semiconductor conjugated polymer and preparation method thereof |
| CN104086752A (en) * | 2014-05-16 | 2014-10-08 | 中国华能集团清洁能源技术研究院有限公司 | Benzodithiophene polymer, its preparation method, semiconductor composition containing it, and solar cell using it |
| CN105367561A (en) * | 2015-11-19 | 2016-03-02 | 上海交通大学 | Preparation and use of indole derivative and conjugated polymer thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159925A (en) * | 2011-12-09 | 2013-06-19 | 海洋王照明科技股份有限公司 | Isoindigo based co-polymer solar cell material, and preparation method and application thereof |
| CN103467711A (en) * | 2013-08-27 | 2013-12-25 | 上海交通大学 | Bi-thiophene oxindolyl semiconductor polymer, and preparation and application thereof |
| CN103626975A (en) * | 2013-11-05 | 2014-03-12 | 合肥工业大学 | Semiconductor conjugated polymer and preparation method thereof |
| CN104086752A (en) * | 2014-05-16 | 2014-10-08 | 中国华能集团清洁能源技术研究院有限公司 | Benzodithiophene polymer, its preparation method, semiconductor composition containing it, and solar cell using it |
| CN105367561A (en) * | 2015-11-19 | 2016-03-02 | 上海交通大学 | Preparation and use of indole derivative and conjugated polymer thereof |
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