CN110655637A - Regular polymer containing pyridine heterocyclic unit, preparation method and application thereof - Google Patents

Regular polymer containing pyridine heterocyclic unit, preparation method and application thereof Download PDF

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CN110655637A
CN110655637A CN201810693569.9A CN201810693569A CN110655637A CN 110655637 A CN110655637 A CN 110655637A CN 201810693569 A CN201810693569 A CN 201810693569A CN 110655637 A CN110655637 A CN 110655637A
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应磊
彭沣
钟知鸣
黄飞
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses a regular polymer containing pyridine heterocyclic units, and a preparation method and application thereof. The invention takes pyridine heterocyclic units as cores, constructs A-D-A units with regular structures, and introduces the A-D-A units into the multipolymer, and the prepared polymer has wide spectral range absorption and high carrier mobility. The regular polymer containing pyridine heterocyclic units can be used as an active layer and applied to organic/polymer electronic devices such as organic/polymer photoelectric detectors, organic/polymer solar cells and the like.

Description

Regular polymer containing pyridine heterocyclic unit, preparation method and application thereof
Technical Field
The invention belongs to the field of organic photoelectricity, and particularly relates to a regular polymer containing pyridine heterocyclic units, a preparation method and application thereof, in particular to application in an organic/polymer photoelectric detector and an organic/polymer solar cell.
Background
The photoelectric detector is a component for converting optical signals into electric signals based on the 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, 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 PC61BM 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 1013cm Hz1/2W-1The overall performance of the device is superior to that of silicon-based devices [ Science,2009,325(5948): 1665-1667-]。
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a regular polymer containing pyridine heterocyclic units. The pyridine heterocycle has stronger electricity absorption property, can effectively adjust the absorption spectrum of the polymer under the action of the strong D-A of the electron donor unit, and has higher electron mobility so as to improve the external quantum efficiency of the polymer. 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.
The invention also aims to provide a preparation method of the regular polymer containing pyridine heterocyclic units.
The invention further aims to provide application of the regular polymer containing the pyridine heterocyclic unit in the field of organic photoelectricity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a regular polymer containing pyridine heterocyclic units has a chemical structural formula which satisfies the following general formula:
Figure BDA0001713103330000021
wherein x and y are mole fractions of units, x is more than 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; n is the number of repeating units, and n is 2-1000;
R1h, D, F, Cl, cyano group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 60 carbon atoms, or aromatic heterocyclic group having 3 to 60 carbon atoms;
ar 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;
D1and D2Each of which is an aromatic hydrocarbon group having 6 to 100 carbon atoms or an aromatic heterocyclic group having 3 to 100 carbon atoms.
Furthermore, the regular polymer containing pyridine heterocyclic units,
Figure BDA0001713103330000022
A-D1in the A unit, the pyridine heterocyclic unit is bonded to D through a carbon atom ortho to the nitrogen1The units are connected.
Further, said heterocyclic unit containing pyridine
Figure BDA0001713103330000023
Preferred are the following structures or halogenated, deuterated, alkyl-substituted derivatives of the following structures:
Figure BDA0001713103330000031
Figure BDA0001713103330000041
wherein R is1H, D, F, Cl, cyano group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 60 carbon atoms, or aromatic heterocyclic group having 3 to 60 carbon atoms; r2An 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; r3 is H, D, F, Cl, cyano, nitro, acyl, alkoxy, carbonyl, sulfone, alkyl with 1-30 carbon atoms, cycloalkyl with 3-30 carbon atoms, aromatic hydrocarbon with 6-60 carbon atoms or aromatic heterocyclic with 3-60 carbon atoms.
Further, the electron supply unit D1And D2Respectively, the compound is preferably one or more of the following structures or halogenated, deuterated and alkyl substituted derivatives of the following structures:
Figure BDA0001713103330000071
wherein R is4An 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; r5H, D, F, Cl, cyano group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 60 carbon atoms, or aromatic heterocyclic group having 3 to 60 carbon atoms.
The method for preparing the regular polymer containing pyridine heterocyclic units comprises the following steps:
(1) d containing dialkyltin functional groups1Units with dibromo or iodo pyridine heterocyclic unitsStille coupling to obtain bromo-or iodo-substituted compounds of regular structure
Figure BDA0001713103330000073
A-D1-a unit;
(2) d containing dialkyltin functional groups2With units being di-bromo or iodo
Figure BDA0001713103330000074
A-D1And performing Stille polymerization reaction on the A unit to obtain the regular polymer containing the pyridine heterocyclic unit, wherein alkyl tin substituted thiophene and halogenated thiophene can be added at the end of the reaction for end capping.
Further, said structurally regular dibrominated or iodinated
Figure BDA0001713103330000081
A-D1Process for the preparation of the A units, step (1) D containing alkyltin functional groups1The molar ratio of the bis-brominated or iodo-substituted pyridine heterocyclic unit to the bis-brominated or iodo-substituted pyridine heterocyclic unit is 1: 2-1: 4, the reaction solvent includes but is not limited to toluene, xylene, chlorobenzene, tetrahydrofuran and the like, the reaction catalyst includes but is not limited to tetrakis (triphenylphosphine) palladium, palladium acetate/tri-tert-butylphosphine, tris (dibenzylideneacetone) dipalladium/tris (o-methylphenyl) phosphorus and the like, and the mass ratio of tris (dibenzylideneacetone) dipalladium/tris (o-methylphenyl) phosphorus is 1: 1-1: 3.
Further, the preparation method of the regular polymer containing pyridine heterocyclic units, step (2), comprises the following steps:
(1) under the protection of inert gas, adding D containing dialkyl tin functional group2With mono-monomers and di-bromo-or iodo-groupsA-D1Dissolving the monomer of the unit A in a solvent, adding a catalyst, and heating to 60-180 ℃ to perform Stille polymerization reaction for 0.5-36 hours;
(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;
(3) and after the reaction is finished, purifying the obtained reaction liquid to obtain the target product.
Further, the organic solvent in step (1) includes, but is not limited to, at least one of toluene, tetrahydrofuran, xylene, chlorobenzene, and dichlorobenzene;
further, the Stille polymerization catalyst in step (1) is at least one of tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium/tris (o-methylphenyl) phosphorus.
Further, D containing a dialkyltin functional group as described in the step (1)2With mono-monomers and di-bromo-or iodo-groups
Figure BDA0001713103330000083
A-D1The amount of monomer of the A unit is such that the total molar amount of monomer containing dialkyltin functional groups is equal to the total molar amount of monomer containing bisbromo and/or diiodo functional groups; the dosage of the catalyst is 2 per mill-3% of the total mole of the reaction monomers;
furthermore, the dosage of the alkyl tin thiophene in the step (2) is 10-40% of the total molar amount of the reaction monomers, the dosage of the bromothiophene is 1-20 times of the molar amount of the alkyl tin thiophene, and the step (2) is an unnecessary step and can be omitted when necessary.
Further, the purification in the step (3) is to cool the obtained reaction solution to room temperature, drip-add the reaction solution into methanol in stirring for precipitation, filter and dry the reaction solution to obtain a crude product, extract the crude product with methanol and acetone in sequence, dissolve the crude product with toluene, separate the crude product by column chromatography, precipitate the crude product in methanol solution again after concentration, filter and dry the crude product to obtain the target product.
The invention also provides application of the regular polymer containing pyridine heterocyclic units in 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 application of the regular polymer containing pyridine heterocyclic units in the preparation of organic/polymer photodetectors and organic/polymer solar cells comprises the following steps: dissolving the regular polymer containing pyridine heterocyclic units in an organic solvent, or mixing with at least one organic micromolecule or polymer and dissolving in the organic solvent, and then forming a film by spin coating, ink-jet printing or printing to obtain the active layer of the organic/polymer electronic device.
Further, the organic solvent includes, but is not limited to, xylene, tetrahydrofuran, chlorobenzene, dichlorobenzene.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) the pyridine heterocyclic unit has stronger electric absorption property, can adjust the absorption spectrum of the polymer in a wide spectrum range, and 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 is a diagram of a polymer photodetector device.
FIG. 2 is an absorption spectrum of polymer P1.
Fig. 3 is a graph of the external quantum efficiency at 0V bias for a polymer photodetector device based on polymer P5.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
Preparation of Compound 2
(1) Preparation of Compound 1
Dithienocyclopentadiene (1.78g, 10mmol), sodium tert-butoxide (2.88g, 30mmol) and bromohexadecane (6.67g, 22mmol) were added to 100mL of tetrahydrofuran under nitrogen atmosphere and ice-bath, and the reaction was stirred for 24 hours. The tetrahydrofuran was spin-dried under reduced pressure, extracted with dichloromethane, washed 3 times with saturated aqueous sodium chloride solution, and the dichloromethane was spin-dried. The crude product is purified by column chromatography by using petroleum ether as eluent to obtain a white solid product with the yield of 90 percent.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 2
Under the protection of nitrogen, compound 1(3.14g, 5mmol) was dissolved in 150mL of anhydrous tetrahydrofuran, cooled to-5 ℃, and n-butyllithium (8mL, 20mmol) was added dropwise, and stirred at-5 ℃ for 2 hours. A tetrahydrofuran solution of trimethyltin chloride (45mL, 45mmol) was injected, and the reaction was allowed to spontaneously warm to room temperature for 12 hours. After tetrahydrofuran was distilled off under reduced pressure, the product was extracted with dichloromethane, washed 3 times with deionized water, and dichloromethane was spin-dried. Recrystallization from isopropanol afforded the product as a white solid in 87% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for synthesizing the compounds 1-2 is shown as follows:
example 2
Preparation of Compound 4
(1) Preparation of Compound 3
Under the protection of nitrogen, 3 '-dibromo-2, 2' -bithiophene (3.24g, 10mmol), sodium 2-octyldodecylamine (3.57g, 12mmol), sodium tert-butoxide (2.40g, 25mmol), tris (dibenzylideneacetone) dipalladium (0.46g, 0.5mmol), 2 '-bis- (diphenylphosphino) -1, 1' -binaphthyl (0.62g, 1 mmol) were added) Added to 100mL of anhydrous toluene. Heating to 100 deg.C for reaction for 12 hr, washing with saturated sodium chloride water solution for 3 times, spin-drying the solvent in organic layer, and purifying the crude product by column chromatography with petroleum ether as eluent to obtain colorless oily product with a yield of 70%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 4
The reaction and purification of compound 4 were carried out in analogy to compound 2, giving the product as a pale yellow oil in 84% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for synthesizing the compounds 3-4 is shown as follows:
Figure BDA0001713103330000111
example 3
Preparation of Compound 8
(1) Preparation of Compound 5
Mixing 4H-cyclopenta [2,1-B:3, 4-B']Dithiophen-4-one (1.92g, 10mmol) was dissolved in a mixed solvent of 20mL of chloroform and 20mL of trifluoroacetic acid, followed by addition of sodium perborate (2.9g, 25mmol) and reaction at ordinary temperature for 4 hours. The product was extracted with 100mL of dichloromethane, washed three times with saturated aqueous sodium chloride solution and, after spin-drying of the solvent under reduced pressure, the crude product was purified with petroleum ether: 1-dichloromethane: column chromatography purification with eluent 1(v/v) gave the product as a white solid with a yield of 25%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 6
Under the protection of nitrogen, bromohexadecane and magnesium chips are used for preparing 1-hexadecyl magnesium bromide in anhydrous tetrahydrofuran. Compound 5(2.08g, 10mmol) was dissolved in 100mL of anhydrous tetrahydrofuran, cooled to-30 deg.C, and then 1-hexadecylmagnesium bromide in tetrahydrofuran (25mL, 25mmol) was slowly added dropwise to the reaction flask, allowed to naturally warm to room temperature and continued for 12 hours. 20mL of deionized water was added to quench the reaction and the reaction was quenched under reduced pressureAfter drying the solvent, the product is extracted with dichloromethane, washed three times with saturated aqueous sodium chloride solution and after spin-drying the solvent under reduced pressure, the crude product is purified with petroleum ether: ethyl acetate ═ 6: column chromatography purification of 1(v/v) as eluent gave the product as a pale yellow oil in 85% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(3) Preparation of Compound 7
Compound 6(6.61g, 10mmol) was dissolved in 100mL of acetic acid under a nitrogen atmosphere, heated to reflux, 2mL of concentrated hydrochloric acid was added, and the reaction was continued for 12 hours. After cooling, the reaction solution was poured into 500mL of ice water, the product was extracted with dichloromethane, and after drying the organic layer solvent under reduced pressure, the crude product was extracted with petroleum ether: dichloromethane ═ 4: column chromatography purification of 1(v/v) as eluent gave the product as a colourless oil in 90% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(4) Preparation of Compound 8
The reaction and purification of compound 8 were performed in analogy to compound 2, giving the product as a pale yellow oil in 88% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for synthesizing the compounds 5-8 is as follows:
Figure BDA0001713103330000121
example 4
Preparation of Compound 9
Under the protection of nitrogen, 2, 5-dibromo-3, 4-diaminopyridine (2.67g, 10mmol) and selenium dioxide (2.78g, 15mmol) were dissolved in 50mL of ethanol, and the mixture was heated to reflux for 12 hours. After cooling, recrystallization from chloroform gave the product as a bright yellow solid in 70% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for the synthesis of compound 9 is shown below:
Figure BDA0001713103330000122
example 5
Preparation of Compound 10
Under the protection of nitrogen, 2, 5-dibromo-3, 4-diaminopyridine (2.67g, 10mmol) was dissolved in 30mL of pyridine, cooled to 0 ℃, added with thionyl chloride (1.79g, 15mmol), and naturally warmed to room temperature and stirred for 12 hours. The product was extracted with dichloromethane and after drying the organic layer solvent under reduced pressure, the crude product was purified by distillation with petroleum ether: ethyl acetate 4: column chromatography purification of 1(v/v) as eluent gave the product as a white solid in 51% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for the synthesis of compound 10 is shown below:
Figure BDA0001713103330000131
example 6
Preparation of Compound 11
Under nitrogen, 2, 5-dibromo-3, 4-diaminopyridine (2.67g, 10mmol) and octadecane-9, 10-dione (4.24g, 15mmol) were dissolved in 50mL of acetic acid and stirred at room temperature for 12 hours. The product was extracted with dichloromethane and after drying the organic layer solvent under reduced pressure, the crude product was purified by distillation with petroleum ether: dichloromethane ═ 8: column chromatography purification of 1(v/v) as eluent gave the product as a white solid in 73% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for the synthesis of compound 11 is shown below:
Figure BDA0001713103330000132
example 7
Preparation of Compound 14
(1) Preparation of Compound 12
Compound 9(3.42g, 10mmol) was dissolved in 50mL fuming sulfuric acid under nitrogen protection, 1mL fuming nitric acid was added, and stirring was carried out at room temperature for 6 hours. The reaction solution was slowly poured into 500mL of ice water, filtered, and the residue was recrystallized with chloroform to a yellow solid product with a yield of 75%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 13
Compound 12(3.87g, 10mmol) and iron powder (1.12g, 20mmol) were added to 100mL of ethanol, and 5mL of concentrated hydrochloric acid was added thereto, followed by stirring and reacting for 6 hours. The product was extracted with dichloromethane and after 3 washes with deionized water, the organic layer solvent was spin dried to give the product as a brown solid with 90% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(3) Preparation of Compound 14
Compound 13(3.57g, 10mmol) was dissolved in 100mL dichloromethane with a small amount of polyvinyl alcohol, stirred at 0 ℃ for 1 hour with 5mL hydrochloric acid in ice bath, then stirred for 2 hours with the addition of sodium nitrite (1.38g, 20mmol), and finally stirred for 12 hours with the addition of cuprous chloride. The product was extracted with dichloromethane and after 3 washes with deionized water, the organic layer solvent was spin dried and the crude product was purified with petroleum ether: ethyl acetate 4: column chromatography purification of 1(v/v) as eluent gave the product as a bright yellow solid in 53% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for synthesizing the compounds 12-14 is shown as follows:
Figure BDA0001713103330000141
example 8
Preparation of Compound 15
Compound 9(7.52g, 22mmol), compound 2(9.53g, 10mmol), and tetrakis (triphenylphosphine) palladium (0.58g, 0.5mmol) were dissolved in 200mL of anhydrous toluene under a nitrogen atmosphere, and heated to 100 ℃ for reaction for 8 hours. After spin-drying of the toluene, the crude productUsing petroleum ether: ethyl acetate ═ 1: column chromatography purification of 1(v/v) as eluent gave the solid product in 57% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equation for the synthesis of compound 15 is shown below:
Figure BDA0001713103330000142
example 9
Preparation of Compound 16
The reaction and purification of compound 16 was carried out analogously to compound 15 to give the product as a solid in 62% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product. The reaction equation is as follows:
Figure BDA0001713103330000151
example 10
Preparation of Compound 17
The reaction and purification of compound 17 was carried out in analogy to compound 15 to give the solid product in 53% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product. The reaction equation is as follows:
Figure BDA0001713103330000152
example 11
Preparation of Compound 18
The reaction and purification of compound 18 was carried out analogously to compound 15 to give the product as a solid in 69% yield.1HNMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product. The reaction equation is as follows:
Figure BDA0001713103330000153
example 12
Preparation of Compound 19
The reaction and purification of compound 19 was carried out analogously to compound 15 to give the solid product in 59% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product. The reaction equation is as follows:
Figure BDA0001713103330000161
example 13
Preparation of Polymer P1
Compound 15(229.9mg, 0.2mmol) and compound 2(157.1mg,0.2mmol) were dissolved in 5mL of anhydrous chlorobenzene under nitrogen, and tetrakis (triphenylphosphine) palladium (8mg) was added. After 24 hours at 140 ℃ and the first capping with 2- (tributyltin) thiophene (20mg) and 6 hours, the second capping with 2-bromothiophene (30mg) was continued for 6 hours. And (3) finishing the reaction, precipitating the reaction solution in methanol after the reaction is cooled to room temperature, carrying out Soxhlet extraction on the polymer obtained by filtering by using methanol and acetone successively, carrying out column chromatography by using chloroform as an eluent, and drying to obtain the black fibrous polymer.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product.
FIG. 2 is an absorption spectrum of polymer P1, which shows that P1 has absorption over a broad wavelength range of 300 to 1350 nm.
The chemical reaction equation for the synthesis of polymer P1 is shown below:
Figure BDA0001713103330000162
example 14
Preparation of Polymer P2
The reaction and purification method of the polymer P2 were similar to those of the polymer P1, and a black fibrous polymer was obtained.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product. The reaction equation is as follows：
Figure BDA0001713103330000171
Example 15
Preparation of Polymer P3
The reaction and purification method of the polymer P3 were similar to those of the polymer P1, and a black fibrous polymer was obtained.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product. The reaction equation is as follows:
Figure BDA0001713103330000172
example 16
Preparation of Polymer P4
The reaction and purification method of the polymer P4 were similar to those of the polymer P1, and a black fibrous polymer was obtained.1The results of H NMR and elemental analysis showed that the obtained compound was the objective product. The reaction equation is as follows:
Figure BDA0001713103330000181
example 17
Preparation of Polymer P5
The reaction and purification method of the polymer P5 were similar to those of the polymer P1, and a black fibrous polymer was obtained.1The HNMR and the element analysis result show that the obtained compound is a target product. The reaction equation is as follows:
Figure BDA0001713103330000182
fig. 3 is a graph of external quantum efficiency of a polymer photodetector device based on polymer P5 under a bias voltage of 0V, as can be seen: the device is corresponding in the wide band range of 300-1350nm and has higher external quantum efficiency.
Example 18
Preparation of Polymer photodetector
Indium Tin Oxide (ITO) glass with the square resistance of 15 omega, which is prepared in advance, is taken, and ultrasonic cleaning and plasma treatment are sequentially carried out on the Indium Tin Oxide (ITO) glass for 10 minutes by using acetone, a detergent, deionized water and isopropanol. A film of polyethoxythiophene (PEDOT: PSS) doped with polystyrene sulfonic acid was spin-coated on ITO to a thickness of 40 nm. PEDOT PSS films were dried in a vacuum oven at 80 ℃ for 8 hours. The polymers P5 and PC were subsequently mixed in a mass ratio of 1:171A solution of BM in o-dichlorobenzene (1 wt.%) was spin coated on the surface of PEDOT: PSS film to a thickness of 100 nm. Then, a PFN-Br film with a thickness of about 5nm is spin-coated on the active layer. Finally, a metal Al layer with the thickness of 100nm is evaporated, and the structure of the device is ITO/PEDOT (indium tin oxide)/PSS/P5 (Polybutylece oxide)/PC (polycarbonate)71BM/PFN-Br/Al。
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (10)

1. A regular polymer containing pyridine heterocyclic units is characterized in that the chemical structural formula satisfies the following general formula:
Figure FDA0001713103320000011
wherein x and y are mole fractions of units, x is more than 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; n is the number of repeating units, and n is 2-1000;
R1h, D, F, Cl, cyano group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 60 carbon atoms, or aromatic heterocyclic group having 3 to 60 carbon atoms;
ar 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;
D1and D2Each of which is an aromatic hydrocarbon group having 6 to 100 carbon atoms or an aromatic heterocyclic group having 3 to 100 carbon atoms.
2. Pyridine containing according to claim 1A regular polymer of pyridine heterocyclic units, characterized in that,
Figure FDA0001713103320000012
A-D1in the A unit, the pyridine heterocyclic unit is bonded to D through a carbon atom ortho to the nitrogen1Unit connection, said heterocyclic unit containing pyridine
Figure FDA0001713103320000013
Is a halogenated, deuterated, alkyl-substituted derivative of the following structure or of the following structure:
Figure FDA0001713103320000021
wherein R is2An 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; r3H, D, F, Cl, cyano group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 60 carbon atoms, or aromatic heterocyclic group having 3 to 60 carbon atoms.
3. A structured polymer comprising pyridine heterocyclic units according to claim 1, wherein the electron donor unit D is1And D2Respectively is one or more of the following structures or halogenated, deuterated and alkyl substituted derivatives of the following structures:
Figure FDA0001713103320000041
Figure FDA0001713103320000051
wherein R is4An 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; r5H, D, F, Cl, cyano group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 60 carbon atoms, or aromatic heterocyclic group having 3 to 60 carbon atoms.
4. The method for preparing the regular polymer containing pyridine heterocyclic units as described in any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) d containing dialkyltin functional groups1Units with dibromo or iodo pyridine heterocyclic unitsStille coupling to obtain bromo-or iodo-substituted compounds of regular structure
Figure FDA0001713103320000061
A-D1-a unit;
(2) d containing dialkyltin functional groups2With units being di-bromo or iodo
Figure FDA0001713103320000062
A-D1And performing Stille polymerization reaction on the A unit to obtain the regular polymer containing the pyridine heterocyclic unit, and adding alkyl tin substituted thiophene and halogenated thiophene to end capping at the end of the reaction.
5. The preparation method of the regular polymer containing pyridine heterocyclic units according to claim 4, characterized in that step (1) is performed by using D containing dialkyl tin functional groups1The molar ratio of the catalyst to a dibromo or iodo pyridine heterocyclic unit is 1: 2-1: 4, the reaction solvent comprises toluene, xylene, chlorobenzene and tetrahydrofuran, and the reaction catalyst comprises palladium tetrakis (triphenylphosphine) and acetic acidOne of palladium/tri-tert-butylphosphine, tris (dibenzylideneacetone) dipalladium/tris (o-methylphenyl) phosphorus, and the reaction temperature is 20-140 ℃.
6. The method for preparing a regular polymer containing pyridine heterocyclic units according to claim 4, wherein the Stille polymerization reaction in step (2) comprises the following steps:
(1) under the protection of inert gas, adding D containing dialkyl tin functional group2With mono-monomers and di-bromo-or iodo-groups
Figure FDA0001713103320000063
Dissolving a unit monomer in an organic solvent, adding a catalyst, heating to 60-180 ℃ to perform Stille polymerization reaction for 0.5-36 hours;
(2) and (3) purifying the reaction liquid obtained in the step (1) to obtain a target product.
7. The method for preparing a regular polymer containing pyridine heterocyclic units according to claim 6, wherein: adding alkyl tin thiophene after (1) and before (2), 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 mole amount of all reaction monomers, and the dosage of the bromothiophene is 1-20 times of the mole amount of the alkyl tin thiophene.
8. The method for preparing a regular polymer containing pyridine heterocyclic units according to claim 6, wherein:
the organic solvent in the step (1) comprises more than one of toluene, tetrahydrofuran, xylene, chlorobenzene and dichlorobenzene;
the catalyst is one of tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium/tris (o-methylphenyl) phosphorus; d containing dialkyl tin functional group2With mono-monomers and di-bromo-or iodo-groups
Figure FDA0001713103320000071
A-D1The monomers of the A unit are used in an amount such that: the total molar amount of the monomer containing the double alkyl tin functional groups is equal to the total molar amount of the monomer containing the double bromine and/or the double iodine functional groups, wherein the monomer containing the double bromine and/or the double iodine functional groups refers to the monomer containing more than one of the double bromine or the double iodine functional groups; the dosage of the catalyst is 2 per mill-3% of the total mole of all reaction monomers; and (2) the purification refers to naturally cooling the obtained reaction liquid to room temperature, dripping the reaction liquid into stirred methanol for precipitation, filtering and drying to obtain a crude product, extracting the crude product by using methanol and acetone in sequence, dissolving the crude product by using toluene, carrying out column chromatography separation, concentrating, precipitating in a methanol solution again, filtering and drying to obtain the target product.
9. The use of a regular polymer comprising pyridine heterocyclic units according to any of claims 1 to 3 in the preparation of organic/polymeric electronic devices, wherein: organic/polymer electronic devices include applications in organic/polymer photodetectors, organic/polymer solar cells, organic/polymer thin film transistors, organic/polymer light emitting transistors, organic/polymer phototransistors, organic/polymer organic light emitting electrochemical cells.
10. The application of claim 9, wherein the active layer of the organic/polymeric electronic device is obtained by dissolving the regular polymer containing pyridine heterocyclic units in an organic solvent, or mixing the regular polymer with at least one organic small molecule or polymer, dissolving the mixture in the organic solvent, and forming a film by spin coating, ink-jet printing or printing.
CN201810693569.9A 2018-06-29 2018-06-29 Regular polymer containing pyridine heterocyclic unit, preparation method and application thereof Pending CN110655637A (en)

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