CN102643410A - Benzopyrrolidiketone-based semiconductor polymer and preparation and purpose thereof - Google Patents

Benzopyrrolidiketone-based semiconductor polymer and preparation and purpose thereof Download PDF

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CN102643410A
CN102643410A CN2012100970668A CN201210097066A CN102643410A CN 102643410 A CN102643410 A CN 102643410A CN 2012100970668 A CN2012100970668 A CN 2012100970668A CN 201210097066 A CN201210097066 A CN 201210097066A CN 102643410 A CN102643410 A CN 102643410A
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benzopyrrole
semi
diketo
conducting polymer
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邓平
张清
李树岗
曹康丽
胡超
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Shanghai Jiaotong University
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Abstract

The invention relates to a benzopyrrolidiketone-based semiconductor polymer and preparation and a purpose thereof. The structural formula of a benzopyrrolidiketone derivative is as follow: FORMULA, wherein R1 is a C8-C20 paraffin chain; R2 is a C8-C20 paraffin chain; and n is not less than 1. The invention further relates to a preparation method of the benzopyrrolidiketone-based semiconductor polymer and a purpose of the benzopyrrolidiketone-based semiconductor polymer as a semiconductor active layer in an organic thin-film photovoltaic device. The benzopyrrolidiketone-based semiconductor polymer provided by the invention includes a novel, rigid-plane, big-pi-conjugated and soluble benzopyrrolidiketone unit and the flexible and solution-promoting paraffin chains, and is a main-chain-conjugated and low-energy-gap polymer processed by a soluble solution, and the research on the thin-film photovoltaic device shows that the material has thin-film photovoltaic application potential.

Description

The semi-conducting polymer of benzopyrrole diketo and preparation thereof, purposes
Technical field
The present invention relates to a kind of organic semiconductor material of solution-processible, especially a kind of semi-conducting polymer of benzopyrrole diketo and preparation thereof, purposes.
Background technology
Energy problem more and more becomes the matter of utmost importance that countries in the world need face and solve.Sun power in the renewable energy source receives significant concern.The development of inorganic solar cell at present is rapid, and electricity conversion improves constantly.But receive expensive restriction, be difficult to carry out large-scale application.And organic polymer solar cell receives scientific research person's very big attention in recent years.The characteristics of organic polymer solar cell material are that the kind of organic materials is many, structure have can cut out, performance has adjustablely, can realize that solution processing handles, and prepares large-area flexible device, is expected to realize low-cost and large-scale industrial application.(referring to document: Gao, J., Yu, G., and Heeger, A.J., Polymer p-i-n Junction Photovoltaic Cells, Adv.Mater., 10,692-695. (1998); Dennler, G., Scharber, M.C.& Brabec, C.J.Polymer-fullerene bulk-heterojunction solar cells.Adv.Mater.21,1323-1338 (2009) .).
Based on hanging down the hole mobile material that the energy gap conjugated polymers is used for solar cell body heterojunction structure, become the big focus of organic thin film solar cell research in recent years, and the effciency of energy transfer of polymer solar battery improves rapidly in recent years (referring to document: Li; G., Zhu, R.; And Yang, Y., polymer solar cells; Nature photonics, 6,153-161 (2012)).The design of novel hole transport polymer material, synthetic and applied research are important directions, also have very big challenge, and synthetic, the exploitation of new polymeric materials have important contribution to the development of organic solar batteries.
Summary of the invention
Semi-conducting polymer and the preparation thereof, the purposes that the purpose of this invention is to provide a kind of benzopyrrole diketo of solubility.Semi-conducting polymer of the present invention has the benzopyrrole diketone unit and the flexible short alkyl chain that dissolves of the big pi-conjugated solubility of novel rigid plane; Be the low energy gap polymkeric substance of main chain conjugated solution processable, preliminary film photovoltaic device research shows that this type material has the film photovoltaic application potential.
The objective of the invention is to realize through following technical scheme:
First aspect the present invention relates to a kind of semi-conducting polymer of benzopyrrole diketo, and the structural formula of said semi-conducting polymer is suc as formula shown in (I):
Figure BDA0000150450470000021
Wherein, R 1Be C 8～C 20Alkane chain; R 2Be C 8～C 20Alkane chain, n>=1.
Second aspect the present invention relates to a kind of method for preparing the semi-conducting polymer of aforesaid benzopyrrole diketo, comprises the steps:
A, will be not by the intermediate A of the substituted benzopyrrole diketone of alkyl, reacting by heating is introduced flexible alkyl group side chain in organic solvent, obtains the substituted benzopyrrole diketone of alkyl monomer M;
B, with monomer M and tin methide conjugative monomer D copolymerization in anhydrous organic solvent of the substituted benzopyrrole diketo of alkyl, Suo Shi extracts and obtains described semi-conducting polymer.
The substituted benzopyrrole diketone of abovementioned alkyl monomer M has fine solubleness in usual vehicle; Said usual vehicle is chloroform, toluene or dichlorobenzene.
Preferably, among the step a, the structural formula of said intermediate A is suc as formula shown in (II):
Figure BDA0000150450470000022
The structural formula of said monomer M is suc as formula shown in (III):
Figure BDA0000150450470000023
Wherein, R 2Be C 8～C 20Alkane chain.
Preferably, among the step a, the said alkyl group side chain that reacting by heating is introduced solubility in organic solvent is specially: with intermediate A is medium with the polar organic solvent, and mineral alkali is a catalyzer, 50～100 ℃ of heating 4～48 hours; With weight ratio is that 1: 0.05～1: 20 methylene dichloride and sherwood oil is eluent, and wash-out obtains monomer M.
Preferably, said polar organic solvent is a N-Methyl pyrrolidone; Said mineral alkali is a tertiary butyl potassium alcoholate.
Preferably, among the step b, the structural formula of said tin methide conjugative monomer D is suc as formula shown in (IV):
Figure BDA0000150450470000024
Wherein, R 1Be C 8～C 20Alkane chain.
Preferably, among the step b, the reaction times of said copolymerization is 6～48 hours, and temperature of reaction is 80 ℃～120 ℃; Said anhydrous organic solvent is dry toluene, anhydrous chlorobenzene or THF.
Preferably, among the step b, it is methyl alcohol, normal hexane and chloroform that said Suo Shi extracts the solvent that adopts successively.
The third aspect, semi-conducting polymer and the PC71BM blend of benzopyrrole diketo that the present invention relates to a kind of aforementioned solubility is as the purposes of Semiconductor Organic layer in the organic film photovoltaic device test.
The present invention has following beneficial effect: the compound method that the present invention discloses is simply effective; Raw material is easy to synthetic preparation, and the synthetic cost is low, and the target compound purity that obtains is high; Big pi-conjugated system and side chain that the semi-conducting polymer main chain of benzopyrrole diketo of the present invention has rigid plane are the flexible short alkyl chain that dissolves, and the material solution processable is handled, and has low band gap, can be applied to photovoltaic device.
Description of drawings
Fig. 1 is embodiment 1 compound M1, M2 and M3 synthetic route chart.
Fig. 2 is embodiment 1 polymkeric substance DP-111, DP-122 and DP-133 synthetic route chart.
Fig. 3 is the gel permeation chromatography GPC of polymkeric substance DP-133.
Fig. 4 is the uv absorption spectrum of polymkeric substance DP-133 in chloroform.
Fig. 5 is the cyclic voltammetry curve of polymkeric substance DP-133, and wherein a is reduction potential-current curve, and b is oxidizing potential-current curve.
Fig. 6 is the thermogravimetric analysis curve of polymkeric substance DP-133.
Fig. 7 is for being the structural representation of the thin-film solar cells device of semiconductor layer with DP-133/PC71BM.
Fig. 8 for DP-133/PC71BM be semiconductor layer the thin-film solar cells device the I-V graphic representation wherein a be the voltage-to-current density relationship curve of different activities layer thickness; B has or not the voltage-to-current density relationship curve that adds modifier DIO.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.Following examples will help those skilled in the art further to understand the present invention, but not limit the present invention in any form.Should be pointed out that to those skilled in the art, under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement.These all belong to protection scope of the present invention.
The semi-conducting polymer of embodiment 1, preparation benzopyrrole diketo
Present embodiment provides the semi-conducting polymer of the benzopyrrole diketo of 3 kinds of solubilities, its structural formula (wherein, n >=1) as shown in table 1, and its synthetic route is referring to Fig. 1.
Table 1
1.1, preparation Compound D P-111, DP-122 and DP-133
The said preparation method who contains the polymkeric substance (DP-111, DP-122 and DP-133) of benzopyrrole diketo comprises the steps:
(a) midbody compound A's is synthetic
The structural formula of midbody compound A does
Figure BDA0000150450470000042
its detailed preparation method sees document " Greenhalgh; C.W., Carey, J.L.and Newton; D.F.; The synthesis of quinodimethanes in the benzodifuranone anf benzodipyrrolidone series, Dyes Pigm., 1; 103-120, (1980) ".
(b) compound M1, M2 and M3's is synthetic
The structural formula of compound M1, M2 and M3 does
its basic preparation method comprises the steps: under nitrogen protection; With intermediate A (1.16g; 2.3mmol), tertiary butyl potassium alcoholate (0.6g; 5.13mmol) join in the two-mouth bottle that contains N-Methyl pyrrolidone (30mL); Be warming up to 60 ℃, dripping bromine is for alkane, and 60 ℃ (can be the arbitrary value in 50～100 ℃) reacted 24h (can be the arbitrary value in 4～48 hours).With the reaction solution cool to room temperature, add toluene and water, separatory; Water is used extracted in toluene, merges organic phase, washing; Saturated nacl aqueous solution is washed, dried over mgso, and steaming desolventizes; Use sherwood oil: methylene dichloride=1: 1～4: 1 (can be 0.05: 1～in 20: 1 arbitrary value) is eluent, and silica gel is that sorbent material crosses that post separates, vacuum-drying obtains brown solid M.(productive rate: monomer M 1 is 0.42g, 25%; Monomer M 2 is 0.67g, 31%; Monomer M 3 is 1.16g, 48%.)
(c) Compound D 1 and D2's is synthetic
The structural formula of Compound D 1 and D2 does
Figure BDA0000150450470000051
its preparation method is referring to document " Zhang, G., Fu; Y., Xie, Z.; And Zhang, Q., Synthesis and Photovoltaic Properties of New Low Bandgap Isoindigo-based Conjugated Polymers; Macromolecules; 44,1414-1420, (2011) ".
(d) polymkeric substance DP-111, DP-122 and DP-133's is synthetic
Under nitrogen protection, with two tin monomeric compound D1 or D2 (all being 0.3mmol) and two bromine monomeric compound M1 or M2 or M3 (all being 0.3mmol) catalyst P d 2(dba) 3(6mg, 2mol%), part P (o-toly) 3(7mg, 8%), dry toluene (10mL) (also can be anhydrous chlorobenzene or THF) add in the reaction flask; In 110 ℃ (can be the arbitrary value in 80 ℃～120 ℃) reaction 48h (can be the arbitrary value in 6～48 hours),, add the 100mL methanol extraction with the reaction solution cool to room temperature; Filter out solid; Extract with methyl alcohol, normal hexane and chloroform Suo Shi successively, collect chloroformic solution, revolve and get blue polymer with methanol extraction again after doing.Productive rate: DP-111 is 401mg, 89%; DP-122 is 337mg, 81%; DP-133 is 342mg, 85%.
The gel permeation chromatography of embodiment 2, polymkeric substance DP-133, uv absorption spectrum and electrochemical properties
It is 20710 that Fig. 3 has provided the number-average molecular weight that the gel permeation chromatography GPC of polymkeric substance records, and distribution coefficient PDI is 2.54.Fig. 4 has provided the uv absorption spectrum of polymkeric substance DP-133 in chloroform, and its maximum absorption peak position is about 614nm, and optical band gap is 1.57eV.Fig. 5 has provided the cyclic voltammetry curve of Compound D P-133.The cyclic voltammetry test is carried out on computer-controlled CHI610D telephone wire analyser; Adopt three traditional electrode test systems; Platinum electrode is a working electrode, and silver/silver ion electrode is a reference electrode, and ionogen is the dichloromethane solution (0.1M) of tetra-n-butyl ammonium hexafluorophosphate; Sweep velocity is 50mv/s, is reference with the ferrocene.The oxidizing potential that ferrocene records under this system is 0.05eV; Because of the energy level of ferrocene under the vacuum condition is 4.8eV; The energy level of material can be calculated by the formula of following energy level: ELUMO=-(Ered, onset-0.05+4.8) eV=-(Ered, onset+4.75) eV.The initial reduction potential that electro-chemical test shows it is about-1.22eV, and the lumo energy that calculates thus is-3.53eV; Initial reduction-oxidation current potential is about 0.63eV, and the lumo energy that calculates thus is-5.38eV.Fig. 6 shows that polymkeric substance DP-133 has good thermostability.
Embodiment 3, polymkeric substance DP-133 conduct are as the purposes of hole mobile material in thin-film solar cells
It is that hole mobile material and P71BM are the structural representation of the organic thin film solar cell device of acceptor blended body heterojunction type that Fig. 7 has provided with polymkeric substance DP-133.Solar cell device test I-V curve is seen Fig. 8, and the transformation efficiency data are seen table 2: the transformation efficiency of preliminary test is 0.2%, and device shows to have higher open circuit voltage (0.90V).
Table 2 is the supplemental characteristic of the thin-film solar cells device of semiconductor layer with DP-133/PC71BM
Figure BDA0000150450470000061
In sum; The semi-conducting polymer of the benzopyrrole diketo that the present invention relates to, constitutional features are the big pi-conjugated main chain bodies and the flexible short alkyl group side chain chain that dissolves with rigid plane, have low band gap; Low HOMO energy level; The thin-film solar cells device detection shows, does hole mobile material with this material and can obtain higher open circuit voltage (0.9V), and the transformation efficiency of preliminary test is 0.2%; Further adjustment side-chain structure and device is optimized is expected to obtain better conversion efficient.

Claims (9)

1. the semi-conducting polymer of a benzopyrrole diketo is characterized in that, the structural formula of said semi-conducting polymer is suc as formula shown in (I):
Figure FDA0000150450460000011
Wherein, R 1Be C 8～C 20Alkane chain; R 2Be C 8～C 20Alkane chain, n>=1.
2. a method for preparing the semi-conducting polymer of benzopyrrole diketo as claimed in claim 1 is characterized in that, comprises the steps:
A, will be not by the intermediate A of the substituted benzopyrrole diketone of alkyl, reacting by heating is introduced flexible alkyl group side chain in organic solvent, obtains the substituted benzopyrrole diketone of alkyl monomer M;
B, with monomer M and tin methide conjugative monomer D copolymerization in anhydrous organic solvent of the substituted benzopyrrole diketo of alkyl, Suo Shi extracts and obtains described semi-conducting polymer.
3. the preparation method of the semi-conducting polymer of benzopyrrole diketo according to claim 2 is characterized in that, among the step a, the structural formula of said intermediate A is suc as formula shown in (II):
The structural formula of said monomer M is suc as formula shown in (III):
Figure FDA0000150450460000013
Wherein, R 2Be C 8～C 20Alkane chain.
4. the preparation method of the semi-conducting polymer of benzopyrrole diketo according to claim 2; It is characterized in that; Among the step a; The said alkyl group side chain that reacting by heating is introduced solubility in organic solvent is specially: with intermediate A is medium with the polar organic solvent, and mineral alkali is a catalyzer, 50～100 ℃ of heating 4～48 hours; With weight ratio is that 1: 0.05～1: 20 methylene dichloride and sherwood oil is eluent, and wash-out obtains monomer M.
5. the preparation method of the semi-conducting polymer of benzopyrrole diketo according to claim 4 is characterized in that, said polar organic solvent is a N-Methyl pyrrolidone; Said mineral alkali is a tertiary butyl potassium alcoholate.
6. the preparation method of the semi-conducting polymer of benzopyrrole diketo according to claim 2 is characterized in that, among the step b, the structural formula of said tin methide conjugative monomer D is suc as formula shown in (IV):
Figure FDA0000150450460000021
Wherein, R 1Be C 8～C 20Alkane chain.
7. the preparation method of the semi-conducting polymer of benzopyrrole diketo according to claim 2 is characterized in that, among the step b, the reaction times of said copolymerization is 6～48 hours, and temperature of reaction is 80 ℃～120 ℃; Said anhydrous organic solvent is dry toluene, anhydrous chlorobenzene or THF.
8. the preparation method of the semi-conducting polymer of benzopyrrole diketo according to claim 2 is characterized in that, among the step b, it is methyl alcohol, normal hexane and chloroform that said Suo Shi extracts the solvent that adopts successively.
9. the semi-conducting polymer of a benzopyrrole diketo as claimed in claim 1 and PC71BM blend are as the purposes of Semiconductor Organic layer in the organic photovoltaic devices test.
CN2012100970668A 2012-04-05 2012-04-05 Benzopyrrolidiketone-based semiconductor polymer and preparation and purpose thereof Pending CN102643410A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087711A (en) * 2020-01-08 2021-07-09 北京夏禾科技有限公司 Organic electroluminescent materials and devices

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012003918A1 (en) * 2010-07-09 2012-01-12 Merck Patent Gmbh Semiconducting polymers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012003918A1 (en) * 2010-07-09 2012-01-12 Merck Patent Gmbh Semiconducting polymers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087711A (en) * 2020-01-08 2021-07-09 北京夏禾科技有限公司 Organic electroluminescent materials and devices

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Application publication date: 20120822