阅读说明：本技术 环化靛蓝受体及聚合物及其制备方法与应用 (Cyclized indigo receptor and polymer as well as preparation method and application thereof ) 是由 刘云圻 杨杰 蒋雅倩 赵志远 易征然 郭云龙 王帅 于 2018-08-29 设计创作，主要内容包括：本发明公开了一种环化靛蓝受体及聚合物及其制备方法与应用。该聚合物的结构如式I所示,其中,R为C<Sub>1</Sub>～C<Sub>40</Sub>的直链或支链烷基。本发明还提供了式I所示聚合物的制备方法。本发明的原料为商业化产品；合成路线简单；合成方法具有普适性。以本发明的新型环化靛蓝聚合物为有机半导体层制备的有机场效应晶体管的空穴迁移率最高为1.83cm<Sup>2</Sup>V<Sup>-1</Sup>s<Sup>-1</Sup>,电子迁移率最高为1.21cm<Sup>2</Sup>V<Sup>-1</Sup>s<Sup>-1</Sup>,在双极性有机场效应晶体管器件中有良好的应用前景。<Image he="426" wi="700" file="DDA0001781772680000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses a cyclized indigo receptor and a polymer as well as a preparation method and application thereof. The structure of the polymer is shown as a formula I, wherein R is C 1 ～C 40 Linear or branched alkyl. The invention also provides a preparation method of the polymer shown in the formula I. The raw materials of the invention are commercial products; the synthetic route is simple; the synthesis method has universality. The hole mobility of an organic field effect transistor prepared by taking the novel cyclized indigo polymer as an organic semiconductor layer is up to 1.83cm 2 V ‑1 s ‑1 The electron mobility is 1.21cm at most 2 V ‑1 s ‑1 The preparation method has good application prospect in bipolar organic field effect transistor devices.)

1. A polymer of formula I:

in the formula I, R is a straight chain or branched chain alkyl group with the total number of carbon atoms of 1-40;

X₁and X₂Any one selected from the following A groups;

ar is selected from any one of the following B groups;

wherein the structural formula of the A group is shown as follows:

the structural formula of the B group is shown as follows:

n is 5 to 100.

2. The polymer of claim 1, wherein: in the formula I, R is a straight chain or branched chain alkyl group with the total number of carbon atoms of 1-20; in particular 2-octyl dodecyl;

n is 10 to 100; specifically 10-50 or 10-20; more specifically 13-14.

3. The polymer of claim 1 or 2, characterized in that: the polymer shown in the formula I is specifically polymer P2FBAI-V and P2 ClBAI-V;

wherein the structural formula of the polymer P2FBAI-V is as follows:

polymer P2ClBAI-V has the following structural formula:

4. a process for preparing a polymer of formula I as defined in any one of claims 1 to 3, comprising the steps of:

carrying out polymerization reaction on a compound shown as a formula VI-a or VI-b and a bistin compound under the action of a catalyst and a ligand to obtain a polymer shown as a formula I after the reaction is finished;

in said formulae VI-a or VI-b, R has the same meaning as R in formula I in claim 1.

5. The method of claim 4, wherein: the double tin compound is selected from any one of the following compounds:

the catalyst is at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium;

the ligand is selected from at least one of triphenylphosphine, tri (o-tolyl) phosphine and triphenylarsine.

6. The method according to claim 4 or 5, characterized in that: the feeding mole fraction of the compound shown as the formula VI-a or VI-b is 1.00 part;

the feeding molar part of the bistin compound is 0.95-1.05 parts; specifically 1.00 part;

the feeding mole fraction of the catalyst is 0.01-0.10; specifically 0.028 to 0.029 portion;

the feeding mole fraction of the ligand is 0.04-0.80; specifically 0.236 to 0.243 part;

in the step of polymerization reaction, the temperature is 90-140 ℃; in particular 110 ℃;

the reaction time is 1 minute to 24 hours; specifically 4 minutes to 24 hours;

the polymerization reaction is carried out in a solvent;

the solvent for the polymerization reaction is specifically selected from at least one of toluene, chlorobenzene, and xylene.

7. Use of a polymer of formula I as defined in any of claims 1 to 3 for the preparation of an organic effect transistor.

8. An organic field effect transistor, characterized by: in the organic field effect transistor, a material constituting a semiconductor layer is a polymer represented by the formula I as claimed in any one of claims 1 to 3.

9. A compound of formula VI-a or VI-b,

in said formula VI-a or VI-b, R has the same meaning as R in formula I as defined in claim 1.

Technical Field

The invention belongs to the field of materials, and relates to a cyclized indigo receptor and a polymer, and a preparation method and application thereof.

Background

Organic field-effect transistors (OFETs) are active devices that use pi-conjugated Organic semiconductor materials as transport layers and control the conductivity of the materials by vertical electric fields. OFETs are key unit devices of organic photoelectric devices and circuits, have the advantages of light weight, solution-soluble processing, good flexibility and the like, and have wide application prospects in foldable display screens, mobile phones, computers and other electronic products in the future.

The materials of the OFETs semiconductor layer can be organic micromolecule materials or high molecular polymer materials. The high molecular polymer material has the advantages of good flexibility, large-area preparation and processing by a solution method and the like, and draws wide attention of researchers. The synthesis of novel organic polymeric materials is an important driver for the development of the art. Organic semiconductor materials that play a key role in OFETs are classified into p-type, n-type and bipolar materials according to their carrier transport properties, and their carriers are holes, electrons, holes and electrons, respectively. Most of the current high-performance OFETs materials are p-type materials, and the development of high-performance n-type materials and bipolar materials is delayed. The invention develops a universal method, synthesizes a plurality of novel cyclized indigo (BAI) receptors and polymers, and researches the application of the receptors and polymers in organic field effect transistors. The LUMO energy level of the polymer is low, and the injection of electrons is facilitated, and test results show that the polymer shows excellent bipolar transmission characteristics. The cyclized indigo polymer expands the types of bipolar materials and has good application prospect.

Disclosure of Invention

The invention aims to provide a cyclized indigo Blue (BAI) receptor and a polymer as well as a preparation method and application thereof.

The structural general formula of the BAI polymer provided by the invention is shown as formula I:

in the formula I, R is a straight chain or branched chain alkyl group with the total number of carbon atoms of 1-40;

X₁and X₂Any one selected from the following A groups;

ar is selected from any one of the following B groups;

wherein the structural formula of the A group is shown as follows:

the structural formula of the B group is shown as follows:

all represent a substitution;

in the formula I, R is a straight chain or branched chain alkyl of 1-20; more specifically, 2-octyldodecyl group;

n is 5-100, specifically, n is 10-100, specifically 10-50 or 10-20; more specifically, n is 14 or 13.

The polymer shown in the formula I is specifically polymer P2FBAI-V and P2 ClBAI-V;

wherein the structural formula of the polymer P2FBAI-V is as follows:

the structural formula of the polymer P2ClBAI-V is as follows:

the invention provides a method for preparing a polymer shown as a formula I, which comprises the following steps:

carrying out polymerization reaction on a compound shown as a formula VI-a or VI-b and a bistin compound under the action of a catalyst and a ligand to obtain a polymer shown as a formula I;

r is as defined for R in formula I above.

In the above method, the di-tin compound is selected from any one of the following compounds:

the catalyst is at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium;

the ligand is selected from at least one of triphenylphosphine, tri (o-tolyl) phosphine and triphenylarsine.

The feeding mole fraction of the compound shown as the formula VI-a or VI-b is 1.00 part;

the feeding molar part of the bistin compound is 0.95-1.05 parts; specifically 1.00 part;

the feeding mole fraction of the catalyst is 0.01-0.10; specifically 0.028 to 0.029 portion;

the feeding mole fraction of the ligand is 0.04-0.80; specifically 0.236 to 0.243 part;

in the step of polymerization reaction, the temperature is 90-140 ℃; specifically 110 ℃ or 120 ℃;

the reaction time is 1 minute to 24 hours; specifically 4 minutes to 24 hours;

the feeding molar ratio of the compound shown in the formula VI-a or VI-b, the bistin compound, the catalyst and the ligand is specifically 1.0: 1.0: 0.03: 0.24;

the solvent for the polymerization reaction is specifically selected from at least one of toluene, chlorobenzene, and xylene.

The method may further comprise the following purification steps:

after the polymerization reaction is finished, cooling the obtained reaction system, sequentially adding concentrated hydrochloric acid and methanol, stirring and filtering at room temperature, sequentially extracting the obtained precipitate with methanol, acetone and n-hexane by using a Soxhlet extractor until the precipitate is colorless, removing micromolecules and a catalyst, and extracting with trichloromethane to obtain the product; wherein, the volume ratio of the methanol to the hydrochloric acid can be specifically 20: 1, the concentration of hydrochloric acid may be 12M.

Furthermore, the compounds of formula VI-a or VI-b as starting materials as described above are also within the scope of the present invention.

R is as defined for R in formula I.

The compounds of the formulae VI-a and VI-b described above can be prepared as follows:

1a) reacting 5-fluoro-2-nitrobenzaldehyde with acetone in an acetone/water solution of sodium hydroxide to obtain difluoroindigo (namely 2F-indigo) shown as a formula II-a;

1b) carrying out condensation reaction on the difluoroindigo shown in the formula II-a obtained in the step 1a) and 2-thiopheneacetyl chloride in an o-xylene solution to obtain difluorocycloindigo shown in the formula III-a (namely 2 FBAI);

1c) reacting the difluorocycloindigo shown in the formula III-a obtained in the step 1b) with N-bromosuccinimide (namely NBS) in a trichloromethane solution to obtain difluorocycloindigo-dibromo (namely 2FBAI-2Br) shown in the formula IV-a;

1d) performing coupling reaction on the difluorocyclotomic indigo-dibromide and 3- (2-octyldodecyl) -5-tributyltin thiophene shown in the formula IV-a obtained in the step 1c) under the catalysis of tris (dibenzylideneacetone) dipalladium and tris (o-tolyl) phosphine to obtain difluorocyclotomic indigo-dithiophene (namely 2FBAI-2T) shown in the formula V-a;

r is as defined for R in formula I.

1e) Reacting the difluorocyclogenated indigo-dithiophene shown in the formula V-a obtained in the step 1d) with N-bromosuccinimide (namely NBS) in a trichloromethane solution to obtain difluorocyclogenated indigo-dithiophene-dibromo (namely 2FBAI-2T-2Br) shown in the formula VI-a;

r is as defined for R in formula I.

2a) Reacting 5-chloro-2-nitrobenzaldehyde with acetone in acetone/water solution of sodium hydroxide to obtain dichloroindigo (i.e. 2Cl-indigo) shown as formula II-b;

2b) carrying out condensation reaction on the dichloroindigo shown in the formula II-b obtained in the step 2a) and 2-thiopheneacetyl chloride in an o-xylene solution to obtain dichlorocyclized indigo shown in the formula III-b (namely 2 ClBAI);

2c) reacting the dichlorocyclized indigo shown in the formula III-b obtained in the step 2b) with N-bromosuccinimide (namely NBS) in a trichloromethane solution to obtain dichlorocyclized indigo-dibromo (namely 2ClBAI-2Br) shown in the formula IV-b;

2d) carrying out coupling reaction on the dichlorocyclized indigo-dibromo compound shown in the formula IV-b and the 3- (2-octyldodecyl) -5-tributyltin thiophene obtained in the step 2c) under the catalysis of tris (dibenzylideneacetone) dipalladium and tris (o-tolyl) phosphine to obtain the dichlorocyclized indigo-dithiophene (namely 2ClBAI-2T) shown in the formula V-b;

r is as defined for R in formula I.

2e) Reacting the dichlorocyclized indigo-dithiophene shown in the formula V-b obtained in the step 2d) with N-bromosuccinimide (namely NBS) in a trichloromethane solution to obtain dichlorocyclized indigo-dithiophene-dibromo (namely 2ClBAI-2T-2Br) shown in the formula VI-b;

r is as defined for R in formula I.

In step 1a) or 2a) of the above process, the ratio of water to acetone is 1: 0.5 to 5, preferably 1: 2.3; in the reaction step, the temperature is-20-40 ℃, and the time is 2-60 hours;

in the step 1b) or 2b), the feeding molar ratio of the difluoroindigo or dichloroindigo to the 2-thiopheneacetyl chloride is 1: 2.0-8.0, preferably 1: 4; in the reaction step, the temperature is 100-150 ℃, and the time is 4-48 hours;

in the step 1c) or 2c), the molar ratio of the raw materials of the difluorocycloindigo or dichlorocycloindigo to the N-bromosuccinimide is 1: 2.0-2.6, preferably 1: 2.2; in the reaction step, the temperature is-10-35 ℃, and the time is 2-24 hours;

in the step 1d) or 2d), the molar ratio of the charge molar amount of the difluorocyclized indigo-dibromo or dichlorocyclized indigo-dibromo and the 3- (2-octyldodecyl) -5-tributylstannylthiophene is 1: 2.0-6.0, preferably 1: 2.4; in the reaction step, the temperature is 80-140 ℃, and the time is 1-48 hours;

in the step 1e) or 2e), the molar ratio of the charge of the difluorocycloindigo-dithiophene or dichlorocycloindigo-dithiophene to the N-bromosuccinimide is 1: 2.0-2.6, preferably 1: 2.2; in the reaction step, the temperature is-10-35 ℃, and the time is 2-24 hours;

in the step 1d) or 2d), the solvent is at least one selected from toluene, chlorobenzene or o-dichlorobenzene.

The synthetic route of the above method is shown in fig. 5A and 5B.

The application of the compound shown in the formula I in the preparation of the organic field effect transistor and the organic field effect transistor using the compound as an organic semiconductor layer also belong to the protection scope of the invention.

The invention has the advantages that:

1. the raw materials are commercial products, the synthetic route is simple, the monomers and the polymers are new molecules, and meanwhile, the method can be popularized to the synthesis of various straight chain or branched chain cyclized indigo polymers;

2. the cyclized indigo polymer has a lower LUMO energy level, is favorable for the injection and transmission of electrons, and can be used for preparing a high-performance bipolar field effect transistor device;

3. the organic field effect transistor prepared by using the cyclized indigo polymer as the semiconductor layer has higher mobility (mu) and on-off ratio (the highest hole mobility is 1.83 cm)²V^-1s^-1The electron mobility is 1.21cm at most²V^-1s^-1) And has good application prospect in bipolar OFETs.

Drawings

FIG. 1 is a diagram showing an ultraviolet-visible absorption spectrum of a cyclized indigo polymer provided by the present invention.

Fig. 2 is a cyclic voltammogram of a cyclized indigo polymer provided by the present invention.

Fig. 3 is a schematic structural diagram of a cyclized indigo polymer field-effect transistor provided by the present invention.

FIG. 4 is a graph showing an output characteristic and a transfer characteristic (P2 FBAI-V and P2ClBAI-V in this order) of a polymer field effect transistor using the cyclized indigo polymer of the present invention as a semiconductor layer.

FIG. 5 is a synthetic route provided by the present invention for the preparation of compounds of formulas VI-a and VI-b.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are all commercially available from the open.