CN111944127B - D-A polymer based on perylene bisimide conjugated plane expansion and preparation method thereof - Google Patents
D-A polymer based on perylene bisimide conjugated plane expansion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel, stable and good-solubility D-A polymer based on perylene bisimide conjugated plane expansion and a preparation method thereof, and the polymer effectively improves the device performance of an organic semiconductor. The general structural formula of the D-A polymer based on perylene imide conjugated plane expansion is shown as the following formulas (I) and (II):
wherein R and R' are branched or straight chains of C5-C18, and n is a positive integer of 1-100.
Description
Technical Field
The invention relates to the technical field of material synthesis and organic semiconductors, in particular to a D-A polymer based on perylene bisimide conjugated plane expansion and a preparation method thereof.
Background
In recent years, research on conjugated polymers is underway, and a research field integrating multiple subjects such as chemistry, physics, materials science, information science and the like, including design and synthesis of conjugated polymers, structure-activity relationship of photoelectric functional materials of conjugated polymers and physical research of corresponding devices is gradually formed. Compared with the traditional inorganic semiconductor material, the conjugated polymer has more effective performance adjustability, and the solubility, optical performance, electrochemical performance, crystallization, assembly performance and the like of the polymer can be conveniently adjusted by changing the main chain and the side chain substituent of the polymer. In addition, the conjugated polymer material has excellent film forming processing performance, and can be made into large-area, light and flexible devices in modes of spin coating, screen printing, ink-jet printing and the like, thereby showing unique charm.
Perylene-3, 4:9, 10-tetracarboxylic diimide compounds, namely perylene bisimide (PDI), have high electron mobility and electron affinity, strong light absorption capability in a visible light region, easily adjustable energy level and low synthesis cost, and are widely applied to the technical field of organic semiconductors. The isoindigo molecule not only has the function of electron deficiency and becomes a core framework of a D-A type molecule, but also can adjust the molecular energy level (the highest occupied molecular orbital-HOMO and the lowest unoccupied molecular orbital-LUMO) of isoindigo through a series of modifications on the structure, so that the isoindigo molecule becomes an ideal electron-withdrawing framework group. However, in the conventional findings, the system has not been studied by fusing these two kinds of building units.
Therefore, a novel perylene bisimide fused isoindigo monomer is synthesized by a simple and green method, and the synthesis method has important significance for the development of D-A polymer.
Disclosure of Invention
The invention aims to provide a novel stable D-A polymer with good solubility and based on perylene imide conjugated plane expansion, which effectively improves the device performance of an organic semiconductor.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a D-A polymer based on perylene imide conjugated plane extension is disclosed, and the structural general formula of the polymer is shown as the following formula (I):
wherein R and R' are branched or straight chains of C5-C18, and n is a positive integer of 1-100; in the perylene imide conjugated plane expansion-based D-A polymer, R or R' is one of the following groups (n, m is a positive integer):
ar is one of the following groups:
ar' is one of the following groups:
the molecular structure of the polymer is shown as any one of the following:
the invention also provides another D-A polymer based on perylene bisimide conjugated plane expansion, and the structural general formula of the polymer is shown as the formula (II):
wherein R and R' are branched or straight chains of C5-C18, and n is a positive integer of 1-100; r or R' of the D-A polymer based on perylene imide conjugated plane expansion is one of the following groups:
the molecular structure of the polymer is as follows:
the invention also aims to provide a preparation method of the D-A polymer (I) based on perylene imide conjugated plane expansion, which comprises the following steps:
step S1: under the protection of inert gas, adding 1, 7-dibromo perylene imide and 6-boron ester isatin into tetrahydrofuran containing a catalyst, carrying out Suzuki coupling reaction at 80 ℃, carrying out photocatalytic ring-closing reaction, and purifying to obtain a compound a 1;
step S2: under the protection of inert gas, adding a compound a1 and 6-bromoindole diketone into a reaction vessel, reacting in acetic acid, and purifying to obtain a compound b 1;
step S3: under the protection of inert gas, adding the compound b1 and Ar-containing tin reagent into a reaction vessel, performing Still polymerization reaction in a solvent containing a catalyst at 110-120 ℃ for 12-36 hours, and purifying to obtain the polymer (I).
Furthermore, the molar ratio of the 1, 7-dibromo perylene bisimide and the 6-boron ester isatin in the step S1 is 1: 2-1: 2.5; the illumination is blue light of 450 nm; the catalyst is prepared from the following components in a molar ratio of 1: 3-1: 4 of a mixture of bis (triphenylphosphine) palladium dichloride and tris (o-methylphenyl) phosphine or tris (dibenzylideneacetone) dipalladium and tri-tert-butylphosphine tetrafluoroborate, wherein the molar ratio of the catalyst is 10-12% of that of the reactant A;
further, the compound a1 and the 6-bromoindole diketone in the step S2 have a molar ratio of 1: 1-1: 3; the reaction temperature is 110-120 ℃, and the reaction time is 12-24 hours;
further, the molar ratio of the compound b1 to the Ar-containing tin reagent in the step S3 is 1: 1-1: 1.2; the Ar-containing tin reagent is trimethyl tin thiophene, trimethyl tin bithiophene and trimethyl tin difluoride bithiophene; the catalyst is a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine in a molar ratio of 1: 3-1: 4; the solvent is at least one of tetrahydrofuran, dioxane, N-dimethyl diamide and toluene; the reaction temperature is 110-120 ℃, and the reaction time is 12-36 hours.
A process for the preparation of a polymer of formula (II) based on the extension of the conjugated plane of perylene bisimide as described above, comprising the following steps:
step S4: under the protection of inert gas, adding a perylene bisimide dibromide product and a 2, 7-trimethyltin symmetric indacenodithiophene derivative into a reaction vessel, carrying out Still polymerization reaction for 12-36 hours at 110-120 ℃ in a solvent containing a catalyst, carrying out ring closing reaction, and purifying to obtain a (II) polymer;
further, in step S4, the solvent is at least one of tetrahydrofuran, dioxane, N-dimethyl diamide, and toluene; the molar ratio of the perylene bisimide dibromide product to the 2, 7-trimethyltin symmetric indacenodithiophene derivative is 1: 1-1: 1.2; the catalyst is a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine in a molar ratio of 1: 3-1: 4; the molar ratio of the catalyst is 10-12% of the reactant A; the reaction temperature is 110-120 ℃, and the reaction time is 12-36 hours.
Specifically, the step S1 is: weighing 1, 7-dibromo perylene bisimide and 6-boron ester isatin, adding into a reaction sealed bottle, degassing, and exchanging high-purity nitrogen for three times continuously; adding a catalyst in an air blowing state, wherein the using amount of the catalyst is 10-12% of that of the reactant A, adding a toluene solvent, stirring to ensure that the molar concentration of the reactant A is 0.3-0.6mol.L, heating to 80 ℃ for reaction for 12 hours, recovering the room temperature after the reaction is finished, extracting, and purifying by a chromatographic column; weighing the obtained crude product, adding the crude product into a cylindrical reaction bottle, adding an iodine simple substance as a catalyst, then adding a toluene solvent to enable the molar concentration of a reactant to be 0.001-0.003mol.L, heating at 80-90 ℃, continuously irradiating for 12-24 hours by using LED blue light in the atmosphere of air, recovering the room temperature after the reaction is finished, carrying out reduced pressure distillation on the reaction solution, and then carrying out chromatographic column separation and purification to obtain a product a 1;
specifically, the step S2 is: adding a product a1, 6-bromoindole dione prepared by S1 into a two-mouth reaction bottle according to a molar ratio of 1: 2-1: 3, degassing to exchange high-purity nitrogen, repeating the operation for three times, injecting hydrochloric acid and a solvent acetic acid into an injector in a nitrogen environment to ensure that the molar concentration of a reactant is 0.1-0.3mol.L, heating to 110-120 ℃, heating and stirring, reacting for 12-24 hours, recovering to room temperature after the reaction is finished, extracting, rotationally evaporating the solvent, and finally separating and purifying by a chromatographic column to obtain a product b 1;
specifically, the step S3 is: weighing a polymerized monomer b1 and trimethyltin thiophene, trimethyltin bithiophene and trimethyltin difluoride bithiophene in a polymerization reaction bottle according to a molar ratio of 1:1 respectively, degassing to exchange high-purity nitrogen, repeating the operation for three times, sequentially adding a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine with a molar ratio of 1: 3-1: 4 as a catalyst under an air blowing state, wherein the molar ratio of the catalyst is 10-12% of a reactant A, adding an anhydrous toluene solvent to ensure that the molar concentration of the reactant is 0.01-0.02mol.L, pumping and exchanging air for 15-20 times to ensure a completely anhydrous and oxygen-free reaction environment, heating and stirring at 110-120 ℃, and reacting for 12-36 hours; after the reaction, recovering to room temperature, adding a toluene solvent, heating and stirring until the toluene solvent is dissolved, recovering to room temperature, dropwise adding the toluene solvent into a methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain pure polymers 1, 2 and 3;
specifically, the step S4 is: weighing a perylene bisimide dibromide product and a 2, 7-trimethyltin symmetric indacenodithiophene derivative in a polymerization reaction bottle according to a molar ratio of 1:1, degassing to exchange high-purity nitrogen, repeating the operation for three times, sequentially adding a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine with a molar ratio of 1: 3-1: 4 as a catalyst under an air blowing state, wherein the molar ratio of the catalyst is 10-12% of a reactant A, adding an anhydrous toluene solvent to ensure that the molar concentration of the reactant is 0.01-0.02mol.L, pumping and exchanging air for 15-20 times to ensure a completely anhydrous and oxygen-free reaction environment, heating and stirring at 110-120 ℃, and reacting for 12-36 hours; after the reaction, recovering to room temperature, adding a toluene solvent, heating and stirring until the toluene solvent is dissolved, recovering to room temperature, dropwise adding the toluene solvent into a methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain a pure polymer 4 unclosed ring precursor; adding the polymer into a round-bottom flask, adding a toluene solvent to enable the concentration of a reactant to be 0.001-0.003mol/L, slowly dropwise adding a mixed solution of anhydrous ferric trichloride and nitromethane, wherein the molar ratio of a catalyst is 1: 5-1: 10 of the reactant, heating and stirring at 60-80 ℃, reacting for 12-24 hours, recovering to room temperature after reaction, extracting, performing Soxhlet extraction, settling, and drying to obtain a polymer 4;
compared with the prior art, the invention has the following advantages:
(1) the novel perylene bisimide fused isoindigo monomer is synthesized by a simple and green method, the structure contains imide and amido bonds, and the perylene bisimide fused isoindigo monomer has lower and higher electron affinity and is a good electron acceptor unit.
(2) The polymerized monomer is polymerized with thiophene monomers rich in electron groups to obtain a series of D-A polymers. The polymer has good solubility, high yield and high thermal stability, and is beneficial to the preparation of large-area devices.
(3) Compared with the conventional polymer, the polymer has a larger conjugated structure, is more favorable for electron transmission, has a maximum absorption wavelength in the visible light field and a narrow optical band gap, and has potential application prospects in the fields of Organic Field Effect Transistors (OFETs) and organic solar cells (OPVs).
Drawings
FIG. 1 is a chemical reaction equation for the preparation of perylene imide conjugated flat expanded D-A polymers;
FIG. 2 is a 1HNMR spectrum of compound b1 in example 1;
FIG. 3 is a cyclic voltammogram of Polymer 1;
FIG. 4 is an ultraviolet absorption spectrum of Polymer 1;
FIG. 5 is a cyclic voltammogram of Polymer 2;
FIG. 6 is an ultraviolet absorption spectrum of Polymer 2;
FIG. 7 is a cyclic voltammogram of Polymer 3;
FIG. 8 is an ultraviolet absorption spectrum of Polymer 3;
fig. 9 shows an ultraviolet absorption spectrum of polymer 4.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The invention adopts AVANCE III 400M type liquid nuclear magnetic resonance spectrometer manufactured by Bruker company of Switzerland to detect the product to obtain 1HNMR and spectrogram, and the solvent is deuterated chloroform (CDCl)3) Tetramethylsilane (TMS) was used as an internal standard. In the experiment, an ultraviolet absorption spectrum of a product is measured by adopting a UV-3600 type ultraviolet-visible spectrophotometer of Shimadzu company, a quartz cuvette with the size of 1 multiplied by 1cm is used as a sample cell, and a CHI620E electrochemical analyzer of Shanghai Chenghua apparatus Limited is adopted. A high-temperature light parallel reaction instrument WP-TEC-1020HSL of the Huataikesi (WATTCAS) company Limited is adopted for carrying out the photocatalytic ring closing reaction.
The chemical reaction equation in the preparation process of the perylene bisimide conjugated plane extended D-A polymer in the following embodiment of the invention is shown in FIG. 1.
Example 1
(1) 0.76g of 2-decyltetradecan-1-amine-substituted 1, 7-dibromoperylene imide (DT-PDI) and 0.84g of 1-bromo-2-decyltetradecan-substituted 6-boroester isatin were added to a vial and degassed and ventilated for three consecutive times; then adding 20ML tetrahydrofuran solvent and 1.5ML (2mol.L) tripotassium phosphate aqueous solution, stirring, adding 17.2mg of tris (dibenzylideneacetone) dipalladium catalyst and 21.8mg of tri-tert-butylphosphine tetrafluoroborate in an air blowing state, pumping and ventilating for three times, then heating to 80 ℃ for reaction for 12 hours, recovering the room temperature after the reaction is finished, extracting, and then purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 3: 5; weighing 50mg of the obtained crude product, adding the crude product into a cylindrical reaction bottle, adding one iodine simple substance as a catalyst, adding 20ML of toluene solvent, heating at 90 ℃, continuously irradiating LED blue light for 12 hours in the atmosphere of air, recovering the room temperature after the reaction is finished, distilling the reaction solution under reduced pressure, separating and purifying by using a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 1:1, and obtaining a product a 1;
(2) 350mg of a1 and 309mg of 6-bromo-1- (2-decyltetradecyl) indol-2-one are put into a two-neck round-bottom reaction flask, the operation is repeated three times by purging the gas, 16.5mg of p-toluenesulfonic acid monohydrate and 17.2mg of phosphorus pentoxide are added under nitrogen by bubbling, 10ML of anhydrous toluene solvent is injected, and the reaction is stirred with heating at 115 ℃ for 48 hours; returning to room temperature, extracting, distilling the solution under reduced pressure, separating and purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane and petroleum ether is 2:3, and obtaining a product b 1;
(3) adding 54mg of b1 and 7.17mg of 2, 5-trimethyltin thiophene into a polymerization flask, pumping and ventilating the mixture, repeating the operation for three times, adding 1.5ML of anhydrous oxygen-free toluene solvent into the blowing gas, then adding 1.81mg of tris (dibenzylideneacetone) dipalladium catalyst and 2.41mg of tris (o-methylphenyl) phosphine ligand, pumping and ventilating the mixture for 15-20 times, and heating and stirring the mixture at 110 ℃ for 36 hours; after the reaction is finished, recovering the room temperature, adding 2ML toluene solvent, heating to 120 ℃ for dissolution, then recovering the room temperature, dropwise adding the solution into the methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain pure polymer 1;
example 2
(1) 0.76g of 2-decyltetradecan-1-amine-substituted 1, 7-dibromoperylene imide (DT-PDI) and 0.84g of 1-bromo-2-decyltetradecan-substituted 6-boroester isatin were added to a vial and degassed and ventilated for three consecutive times; then adding 20ML tetrahydrofuran solvent and 1.5ML (2mol.L) tripotassium phosphate aqueous solution, stirring, adding 17.2mg of tris (dibenzylideneacetone) dipalladium catalyst and 21.8mg of tri-tert-butylphosphine tetrafluoroborate in an air blowing state, pumping and ventilating for three times, then heating to 80 ℃ for reaction for 12 hours, recovering the room temperature after the reaction is finished, extracting, and then purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 3: 5; weighing 50mg of the obtained crude product, adding the crude product into a cylindrical reaction bottle, adding one iodine simple substance as a catalyst, adding 20ML of toluene solvent, heating at 90 ℃, continuously irradiating LED blue light for 12 hours in the atmosphere of air, recovering the room temperature after the reaction is finished, distilling the reaction solution under reduced pressure, separating and purifying by using a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 1:1, and obtaining a product a 1;
(2) 350mg of a1 and 309mg of 6-bromo-1- (2-decyltetradecyl) indol-2-one are put into a two-neck round-bottom reaction flask, the operation is repeated three times by purging the gas, 16.5mg of p-toluenesulfonic acid monohydrate and 17.2mg of phosphorus pentoxide are added under nitrogen by bubbling, 10ML of anhydrous toluene solvent is injected, and the reaction is stirred with heating at 115 ℃ for 48 hours; returning to room temperature, extracting, distilling the solution under reduced pressure, separating and purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane and petroleum ether is 2:3, and obtaining a product b 1;
(3) 63.16mg of b1 and 10.07mg of 5,5 '-bis (trimethylstannyl) -2,2' -bithiophene were added to a polymerization flask, the gas was evacuated and the operation was repeated three times, 1.5ML of an anhydrous oxygen-free toluene solvent was added to the gas, followed by 1.55mg of tris (dibenzylideneacetone) dipalladium catalyst and 2.06mg of tris (o-methylphenyl) phosphine ligand, the gas was evacuated and heated and stirred at 110 ℃ for 36 hours; after the reaction is finished, recovering the room temperature, adding 2ML toluene solvent, heating to 120 ℃ for dissolution, then recovering the room temperature, dropwise adding the solution into the methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain pure polymer 2;
example 3
(1) 0.76g of 2-decyltetradecan-1-amine-substituted 1, 7-dibromoperylene imide (DT-PDI) and 0.84g of 1-bromo-2-decyltetradecan-substituted 6-boroester isatin were added to a vial and degassed and ventilated for three consecutive times; then adding 20ML tetrahydrofuran solvent and 1.5ML (2mol.L) tripotassium phosphate aqueous solution, stirring, adding 17.2mg of tris (dibenzylideneacetone) dipalladium catalyst and 21.8mg of tri-tert-butylphosphine tetrafluoroborate in an air blowing state, pumping and ventilating for three times, then heating to 80 ℃ for reaction for 12 hours, recovering the room temperature after the reaction is finished, extracting, and then purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 3: 5; weighing 50mg of the obtained crude product, adding the crude product into a cylindrical reaction bottle, adding one iodine simple substance as a catalyst, adding 20ML of toluene solvent, heating at 90 ℃, continuously irradiating LED blue light for 12 hours in the atmosphere of air, recovering the room temperature after the reaction is finished, distilling the reaction solution under reduced pressure, separating and purifying by using a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 1:1, and obtaining a product a 1;
(2) 350mg of a1 and 309mg of 6-bromo-1- (2-decyltetradecyl) indol-2-one are put into a two-neck round-bottom reaction flask, the operation is repeated three times by purging the gas, 16.5mg of p-toluenesulfonic acid monohydrate and 17.2mg of phosphorus pentoxide are added under nitrogen by bubbling, 10ML of anhydrous toluene solvent is injected, and the reaction is stirred with heating at 115 ℃ for 48 hours; returning to room temperature, extracting, distilling the solution under reduced pressure, separating and purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane and petroleum ether is 2:3, and obtaining a product b 1;
(3) 43.24mg of b1 and 7.4mg of (3,3' -difluoro- [2,2' -dithiophene ] -5,5' -diyl) bis (trimethyltin) were charged into a polymerization flask, the gas was evacuated, the operation was repeated three times, 1.0ML of anhydrous oxygen-free toluene solvent was added to the gas blown, subsequently 2.47mg of tris (dibenzylideneacetone) dipalladium catalyst and 3.28mg of tris (o-methylphenyl) phosphine ligand were added, the gas was evacuated 15 to 20 times, and heated and stirred at 110 ℃ for 36 hours; after the reaction is finished, recovering the room temperature, adding 2ML toluene solvent, heating to 120 ℃ for dissolution, then recovering the room temperature, dropwise adding the solution into the methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain pure polymer 3;
example 4
(1) 80.66mg of undecaexamine-substituted dibromoperylene bisimide (isomers of 1, 7-substituted and 1, 6-substituted dibromides in a ratio of about 4:1) and 116.08mg of 2, 7-trimethyltin sym-indacenodithiophene derivative were added to a polymerization flask, the reaction was evacuated and purged, the operation was repeated three times, 2.0ML of anhydrous oxygen-free toluene solvent was added to the air, 2.59mg of tris (dibenzylideneacetone) dipalladium catalyst and 3.44mg of tris (o-methylphenyl) phosphine ligand were then added, the evacuation and purging were carried out 15 to 20 times, and the mixture was heated and stirred at 110 ℃ for 36 hours; after the reaction is finished, recovering the room temperature, adding 2ML toluene solvent, heating to 120 ℃ for dissolution, then recovering the room temperature, dropwise adding the solution into the methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain a precursor of the pure polymer 4;
(2) adding 60mg of a precursor of the polymer 4 into a single-opening round-bottom reaction bottle, adding 80ML of anhydrous toluene solvent, dropwise adding a mixed solution of 2ML of nitromethane and 50mg of anhydrous ferric trichloride, continuously blowing nitrogen into a reaction system, and heating and stirring at 65 ℃ for reacting for 48 hours; returning to room temperature, extracting, rotationally evaporating the solvent, dissolving and settling, putting the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting with methanol, acetone, n-hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain pure polymer 4;
Claims (5)
1. a D-A polymer based on perylene imide conjugated plane expansion is characterized in that the structural general formula of the polymer is shown as the formula (I):
formula (I);
wherein R and R' are branched or straight chains of C5-C18, and n is a positive integer of 1-100;
ar is one of the following groups:
ar' is one of the following groups:
2. the preparation method of the perylene imide conjugated plane expansion based D-A polymer according to claim 1, wherein the preparation method comprises the following steps:
step S1: under the protection of inert gas, adding 1, 7-dibromo perylene imide and 6-boron ester isatin into tetrahydrofuran containing a catalyst, carrying out Suzuki coupling reaction at 80 ℃, carrying out photocatalytic ring-closing reaction, and purifying to obtain a compound a 1;
step S2: under the protection of inert gas, adding a compound a1 and 6-bromoindole diketone into a reaction vessel, reacting in acetic acid, and purifying to obtain a compound b 1;
step S3: under the protection of inert gas, adding a compound b1 and an Ar-containing tin reagent into a reaction vessel, carrying out Stille polymerization reaction in a solvent containing a catalyst at 110-120 ℃ for 12-36 hours, and purifying to obtain the polymer shown in the formula (I).
3. The preparation method of the D-A polymer based on perylene imide conjugated plane expansion according to claim 2, wherein the molar ratio of 1, 7-dibromo perylene imide to 6-boron ester isatin in the step S1 is 1:2 to 1: 2.5; the illumination is blue light of 450 nm; the catalyst is a mixture of bis (triphenylphosphine) palladium dichloride and tri (o-methylphenyl) phosphine or tri (dibenzylideneacetone) dipalladium and tri-tert-butylphosphine tetrafluoroborate in a molar ratio of 1: 3-1: 4.
4. The preparation method of the perylene imide conjugated plane expansion based D-A polymer according to claim 2, wherein the molar ratio of the compound a1 to the 6-bromoindole dione in the step S2 is 1:1 to 1: 3; the reaction temperature is 110-120 ℃, and the reaction time is 12-24 hours.
5. The preparation method of the D-A polymer based on perylene imide conjugated plane expansion according to claim 2, wherein the molar ratio of the compound b1 and the Ar-containing tin reagent in the step S3 is 1: 1-1: 1.2; the Ar-containing tin reagent is trimethyl tin thiophene or trimethyl tin bithiophene; the catalyst is a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine in a molar ratio of 1: 3-1: 4; the solvent is at least one of tetrahydrofuran, dioxane, N-dimethyl diamide and toluene.
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| CN108840876A (en) * | 2018-07-11 | 2018-11-20 | 上海交通大学 | A kind of synthesis and its application of halogenated condensed ring acid imide electron transport material |
| CN109776769A (en) * | 2019-01-21 | 2019-05-21 | 福州大学 | It is a kind of based on thiophene, imidodicarbonic diamide and terpolymer of bioxindol unit and preparation method thereof |
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| CN108840876A (en) * | 2018-07-11 | 2018-11-20 | 上海交通大学 | A kind of synthesis and its application of halogenated condensed ring acid imide electron transport material |
| CN109776769A (en) * | 2019-01-21 | 2019-05-21 | 福州大学 | It is a kind of based on thiophene, imidodicarbonic diamide and terpolymer of bioxindol unit and preparation method thereof |
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