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 PDF

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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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conjugated polymer
idt
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CN105418897A (en
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吴建
周祥梅
张清
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Shanghai Jiaotong University
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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

Indoles and the conjugated polymer of fen class compound and its production and use
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

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