Regular polymer containing quinoline-based condensed ring unit and preparation method and application thereof
阅读说明：本技术 一类含基于喹啉的稠环单元的规整型聚合物及其制备方法与应用 (Regular polymer containing quinoline-based condensed ring unit and preparation method and application thereof ) 是由 应磊 彭沣 钟知鸣 黄飞 曹镛 于 2018-07-31 设计创作，主要内容包括：本发明公开了一类含基于喹啉的稠环单元的规整型聚合物及其制备方法与应用。本发明以基于喹啉的稠环单元为核心,构建了具有规整结构的A-D和A-D-A单元,并将其引入到聚合物中,制备的聚合物具有宽光谱范围的吸收和高的载流子迁移率。此类含基于喹啉的稠环单元的规整型聚合物可作为活性层,应用在有机/聚合物光电探测器和有机/聚合物太阳电池等有机/聚合物电子器件中。(The invention discloses a regular polymer containing quinoline-based condensed ring units, and a preparation method and application thereof. The quinoline-based condensed ring unit is used as a core, A-D and A-D-A units with regular structures are constructed and introduced into the polymer, and the prepared polymer has wide spectral range absorption and high carrier mobility. The regular polymer containing the quinoline-based condensed ring unit can be used as an active layer and applied to organic/polymer electronic devices such as organic/polymer photodetectors, organic/polymer solar cells and the like.)
1. A regular polymer containing quinoline-based fused ring units is characterized in that the chemical structural formula satisfies one of the following general formulas:
wherein x and y are mole fractions of units, x is more than 0 and less than or equal to 1, y is more than or equal to 0 and less than 1, and x + y is equal to 1; n is the number of repeating units, and n is 2-1000;
pi is an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heterocyclic group having 0 to 60 carbon atoms and containing at least one hetero atom;
ar and Ar' are each an aromatic hydrocarbon group having 6 to 100 carbon atoms or an aromatic heterocyclic group having 3 to 100 carbon atoms.
2. A class of structured polymers containing quinoline-based fused ring units according to claim 1 wherein the quinoline-based fused ring units Fixed connection mode with the Ar unit: in the general formula, each Ar is connected with two quinoline-based condensed ring units
3. A class of structured polymers containing quinoline-based fused ring units according to claim 1 wherein the quinoline-based fused ring units
wherein R is 1Is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
4. A class of structured polymers containing quinoline-based fused ring units according to claim 1 wherein the electron donating units Ar and Ar' are each one or more of the following structures or halogenated, deuterated, alkyl-substituted derivatives of the following structures:
wherein R is 2Is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
5. A method for preparing a structured polymer containing quinoline-based fused ring units according to any one of claims 1 to 4, comprising the steps of:
(1) ar unit containing alkyltin functional group and double bromo-or iodo-quinoline-based fused ring unit
(2) by substitution of one-sided bromo-or iodo-and the other-substituted alkyltin
or by reacting Ar' units containing tin dialkyl functions with dibromo or iodo groups
6. The method according to claim 5, wherein the structure in (1) is regular single-side bromo-or iodo-substituted and the other side is alkyltin-substituted
7. The process according to claim 5, wherein the preparation of a structured polymer comprising quinoline-based fused ring units of the type described in (2) comprises the steps of:
(2.1) under the protection of inert gas, one side of the compound is brominated or iodinated, and the other side is substituted by alkyl tin
and (2.2) after the reaction is finished, purifying the obtained reaction liquid to obtain the target product.
8. The method of claim 7, wherein the quinoline-based fused ring unit-containing structured polymer comprises:
the organic solvent in the step (2.1) comprises at least one of toluene, tetrahydrofuran, xylene, chlorobenzene and dichlorobenzene;
the catalyst in step (2.1) is at least one of palladium including but not limited to tetrakis (triphenylphosphine), tris (dibenzylideneacetone) dipalladium/tris (o-methylphenylphosphine).
9. The method of claim 7, wherein the quinoline-based fused ring unit-containing structured polymer comprises:
the Ar' unit monomer containing the dialkyl tin functional group in the step (2.1) and the double bromo or iodo
the method also comprises the following steps between the step (2.1) and the step (2.2): adding alkyl tin thiophene, and keeping the temperature to continue reacting for 6-12 hours; adding bromothiophene, and continuing the heat preservation reaction for 6-12 hours; the dosage of the alkyl tin thiophene is 10-40% of the total molar amount of the reaction monomers, and the dosage of the bromothiophene is 1-20 times of the molar amount of the alkyl tin thiophene.
10. The method of claim 7, wherein the quinoline-based fused ring unit-containing structured polymer comprises:
and (3) the purification in the step (2.3) is to cool the obtained reaction liquid to room temperature, dropwise add the reaction liquid into stirred methanol for precipitation, filter and dry the reaction liquid to obtain a crude product, extract the crude product by using methanol and acetone in sequence, dissolve the crude product by using toluene, separate the crude product by column chromatography, precipitate the crude product in a methanol solution again after concentration, filter and dry the crude product to obtain the target product.
11. The use of a regular polymer comprising quinoline-based fused ring units according to any one of claims 1 to 4 in the preparation of an organic/polymer electronic device comprising at least one of an organic/polymer photodetector, an organic/polymer solar cell, an organic/polymer thin film transistor, an organic/polymer light emitting transistor, an organic/polymer phototransistor, an organic/polymer organic light emitting electrochemical cell, it is characterized in that the regular polymer containing quinoline-based condensed ring units is dissolved in an organic solvent, or mixing the active layer with at least one electron acceptor material or electron donor material, dissolving the mixture in an organic solvent, and forming a film through spin coating, ink-jet printing or printing to obtain the active layer of the organic/polymer electronic device.
12. Use according to claim 11, characterized in that: the organic solvent comprises more than one of dimethylbenzene, tetrahydrofuran, chlorobenzene and dichlorobenzene.
Technical Field
The invention belongs to the field of organic photoelectricity, and particularly relates to a preparation method of a regular polymer containing quinoline-based condensed ring units and application of the regular polymer in organic/polymer electronic devices, in particular to organic/polymer photodetectors and organic/polymer solar cells.
Background
The electric detector is a component for converting optical signals into electric signals based on photoelectric effect, and has important application in the fields of optical communication, image sensing, biomedical sensing, environmental monitoring, meteorology, military and the like. The photodetectors commonly used today are based essentially on inorganic semiconductor materials, such as Si-based, Ge-based, and InGaAs, etc.
Compared with inorganic materials, the organic/polymer material has the advantages of low cost, easy adjustment of absorption wavelength, film formation through a solution method and the like, so that the organic/polymer photodiode has the advantages of simple manufacturing process, low production cost, light weight, easy large-area preparation, realization of flexible devices and wide application prospect. Gong et al utilize a narrow-band conjugated polymer PDDTT and a fullerene derivative PC 61BM blending to prepare a full-color photodetector with a spectral response range of 300-1150 nm, wherein the detection rate of the detector under zero bias voltage exceeds 10 13cm Hz 1/2W -1The overall performance is superior to silicon-based devices.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a regular polymer containing quinoline-based fused ring units. The quinoline-based condensed ring unit has strong electric absorption property, can effectively adjust the absorption spectrum of the polymer under the action of strong D-A of the electron donating unit, has higher electron mobility,
the external quantum efficiency of the polymer can be improved. The regular structure enables polymer molecules to be more ordered, accumulation of the polymer molecules is facilitated, mobility can be further improved, absorption spectrum red shift is enabled, and in addition, the regular structure is beneficial to improvement of molecular weight and batch stability of the polymer.
Another object of the present invention is to provide a process for the preparation of structured polymers of the above-mentioned type containing quinoline-based fused ring units.
The invention further aims to provide application of the regular polymers containing the quinoline-based condensed ring unit in the field of organic photoelectricity.
In order to achieve the purpose, the invention adopts the following technical scheme.
A regular polymer containing quinoline-based fused ring units has a chemical structural formula satisfying one of the following general formulas:
wherein x and y are mole fractions of units, x is more than 0 and less than or equal to 1, y is more than or equal to 0 and less than 1, and x + y is equal to 1; n is the number of repeating units, and n is an integer in the range of 2-1000;
pi is an aromatic hydrocarbon group having 6 to 60 carbon atoms or a heterocyclic group having 0 to 60 carbon atoms and containing at least one hetero atom;
ar and Ar' are each an aromatic hydrocarbon group having 6 to 100 carbon atoms or an aromatic heterocyclic group having 3 to 100 carbon atoms.
Further, the regular polymers containing quinoline-based condensed ring units are characterized in that the quinoline-based condensed ring units
Further, the regular polymers containing quinoline-based fused ring units are characterized in that the quinoline-based fused ring units
wherein R is 1Is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
Further, in the above structured polymers containing quinoline-based fused ring units, the electron donor units Ar and Ar' are preferably one or more of the following structures or halogenated, deuterated, and alkyl substituted derivatives of the following structures, respectively:
wherein R is 2Is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms.
The preparation method of the regular polymer containing the quinoline-based condensed ring unit comprises the following steps:
(1) ar unit containing alkyltin functional group and double bromo-or iodo-quinoline-based fused ring unit Stille coupling is carried out to obtain the dibromo or iodo compound with regular structure
(2) by substitution of one-sided bromo-or iodo-and the other-substituted alkyltin
Or by reacting Ar' units containing tin dialkyl functions with dibromo or iodo groups
Further, the above-mentioned structural regular single-side bromo-or iodo-substituted with alkyltin on the other side
Further, the preparation method of the regular polymer containing the quinoline-based fused ring unit comprises the following steps:
(2.1) under the protection of inert gas, one side of the compound is brominated or iodinated, and the other side is substituted by alkyl tin
(2.2) adding alkyl tin thiophene, and keeping the temperature to continue reacting for 6-12 hours; adding bromothiophene, and continuing the heat preservation reaction for 6-12 hours;
and (2.3) after the reaction is finished, purifying the obtained reaction liquid to obtain the target product.
The organic solvent in the step (2.1) comprises but is not limited to at least one of toluene, tetrahydrofuran, xylene, chlorobenzene and dichlorobenzene;
the catalyst in step (2.1) is at least one of palladium including but not limited to tetrakis (triphenylphosphine), tris (dibenzylideneacetone) dipalladium/tris (o-methylphenylphosphine).
The Ar' unit monomer containing the dialkyl tin functional group in the step (2.1) and the double bromo or iodo
the dosage of the alkyl tin thiophene in the step (2.2) is 10-40% of the total mole amount of the reaction monomers, the dosage of the bromothiophene is 1-20 times of the mole amount of the alkyl tin thiophene, and the step (2.2) is an unnecessary step and can be omitted when necessary.
And (3) the purification in the step (2.3) is to cool the obtained reaction liquid to room temperature, dropwise add the reaction liquid into stirred methanol for precipitation, filter and dry the reaction liquid to obtain a crude product, extract the crude product by using methanol and acetone in sequence, dissolve the crude product by using toluene, separate the crude product by column chromatography, precipitate the crude product in a methanol solution again after concentration, filter and dry the crude product to obtain the target product.
The regular polymers containing quinoline-based condensed ring units are applied to the preparation of organic/polymer electronic devices, including organic/polymer photodetectors, organic/polymer solar cells, organic/polymer thin film transistors, organic/polymer light-emitting transistors, organic/polymer phototransistors and organic/polymer organic light-emitting electrochemical cells.
Further, the regular polymer containing the quinoline-based condensed ring unit is dissolved in an organic solvent or mixed with at least one other substance and dissolved in the organic solvent, and then the active layer of the organic/polymer electronic device is obtained by spin coating, ink-jet printing or film printing. The organic solvent includes but is not limited to xylene, tetrahydrofuran, chlorobenzene and dichlorobenzene.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) the quinoline-based condensed ring unit has stronger electric absorption property, can adjust the absorption spectrum of the polymer in a wide spectrum range, and meanwhile, the pyridine heterocyclic unit has higher electron mobility, thereby being beneficial to improving the external quantum efficiency of the polymer.
(2) The regular structure is beneficial to the accumulation of polymer molecules, further improves the mobility and enables the absorption spectrum to be red-shifted, and in addition, the regular structure is beneficial to the improvement of the molecular weight and the batch stability of the polymer.
Drawings
FIG. 1 shows an absorption spectrum of polymer P5, where P5 has absorption in a broad wavelength range of 400-1600 nm.
Fig. 2 is a current density-voltage curve of a polymer photodetector device based on polymer P1, and it can be seen that the current density of the device under light conditions is significantly improved compared to the current density under dark conditions.
Detailed Description
The practice of the present invention will be further described with reference to the accompanying drawings and detailed description, but the practice and protection of the invention are not limited thereto, and it is noted that the procedures or parameters which are not described in particular detail below are understood or realized by those skilled in the art with reference to the prior art.