CN114605619B - Organic photovoltaic device active layer material containing star-structure flexible chain segments, and preparation and application thereof - Google Patents

Organic photovoltaic device active layer material containing star-structure flexible chain segments, and preparation and application thereof Download PDF

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CN114605619B
CN114605619B CN202210053939.9A CN202210053939A CN114605619B CN 114605619 B CN114605619 B CN 114605619B CN 202210053939 A CN202210053939 A CN 202210053939A CN 114605619 B CN114605619 B CN 114605619B
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active layer
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CN114605619A (en
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应磊
甘梓琪
曹镛
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of organic photoelectric materials, and discloses an organic photovoltaic device active layer material containing a star-structure flexible chain segment, and preparation and application thereof. The structure of the active layer material is shown as the following formula I, and is composed of naphthalene [1,2-c:5,6-c ]']Bis ([ 1,2, 5)]Five-membered ring) unit derivative, star-shaped structure flexible chain segment unit and electron donating unit. The preparation method is simple, the purification is easy, and the preparation method can be used for large-scale production; and the active layer material of the series polymer photovoltaic device containing the star-shaped structure flexible chain segments can regulate and control the structure and the performance of the polymer by selecting different star-shaped structure flexible units, so as to meet the requirements of different scenes. The polymer active layer material containing the star-shaped structure flexible chain segment is beneficial to enhancing the deformation performance of the material, so that the high-performance stretchable organic photovoltaic device is obtained. The polymer active layer material containing the star-shaped structure flexible chain segment is used in the field of organic photovoltaic devices.

Description

Organic photovoltaic device active layer material containing star-structure flexible chain segments, and preparation and application thereof
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an organic photovoltaic device active layer material containing a star-structure flexible chain segment, and preparation and application thereof.
Background
In recent years, as the global energy demand increases, the problem of energy shortage becomes more pronounced, and photovoltaic devices start to enter into the field of view of people. Compared with inorganic solar cells, the organic solar cells have the characteristic of flexibility and stretchability, and have great potential and advantages in manufacturing next-generation wearable and stretchable electronic products. This has attracted considerable attention, making it the most promising class of materials in various photovoltaic devices in the course of development in the last decade. In practical application, the organic photovoltaic device is exposed to hot oxygen and tensile stress, so that the ageing of the device can be accelerated, and the photovoltaic performance of the device is reduced.
The active layer fracture caused by strain is one of the most important factors for efficiency degradation. As a key component of flexible and stretchable devices, a polymer active layer with excellent stretchability and optoelectronic properties has great advantages in terms of improved strain tolerance and deformability of the device, but its further development still presents a great challenge. Because the conjugated polymer popular at the present stage has a rigid pi-pi conjugated part and stronger crystallinity of polymer chains, the conjugated polymer film has limited tensile property and is easy to lose effectiveness compared with the traditional polymers such as rubber, plastics and the like, and the strain stability of flexible and stretchable photoelectric devices is limited. Therefore, to achieve stronger strain stability, it is important to prepare a ternary random copolymer containing flexible units by introducing flexible segment units into a conjugated polymer system.
Disclosure of Invention
In order to endow the organic photovoltaic device with intrinsic tensile properties, a novel active layer material is developed, and the primary aim of the invention is to provide an organic photovoltaic device active layer material containing a star-structure flexible chain segment. The active layer material is composed of naphthalene [1,2-c:5,6-c' ] double ([ 1,2,5] five-membered ring) unit derivatives, star-structure flexible chain segment units and electron donating units, and the star-structure flexible chain segments are introduced to enhance the deformation performance of the material, so that the high-performance stretchable organic photovoltaic device is obtained.
The invention also aims to provide a preparation method of the organic photovoltaic device active layer material containing the star-structure flexible chain segment.
The invention also aims to provide application of the organic photovoltaic device active layer material containing the star-shaped flexible chain segment in preparation of an organic photovoltaic device.
The aim of the invention is achieved by the following technical scheme:
an active layer material of an organic photovoltaic device containing a star-shaped structure flexible chain segment has the structure shown in formula I:
in formula I, m represents the number of star arms, m includes but is not limited to 2-10; the polymerization degree n is in the range of 5 to 300;
in the formula I, Y is relatively independently selected from O, S, se or N-R 1 One of the following;
in the formula I and Y, R 1 And R is 2 Relatively independent at each occurrence is a hydrogen atom, a straight chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a straight chain alkenyl group having 2 to 20 carbon atoms, a branched or cyclic alkenyl group having 3 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkenylthio group having 2 to 20 carbon atoms, a straight chain alkynyl group having 2 to 20 carbon atoms, a branched or cyclic alkynyl group having 3 to 20 carbon atoms, a straight chain alkylcarbonyl group having 2 to 20 carbon atoms, a branched or cyclic alkylcarbonyl group having 3 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an aralkyl group having 4 to 20 carbon atoms, a heteroarylalkyl group having 4 to 20 carbon atoms, an aryloxy group having 4 to 20 carbon atoms, a heteroaryloxy group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, or an alkoxy group having 4 to 20 carbon atoms, wherein R is one of the alkoxy groups 1 And R is 2 May be the same or different;
Z is, identically or differently, at each occurrence, CH or N;
the D unit is an electron donor unit and is one of the following structural formulas:
wherein R is 4 And R is 5 Relatively independently substitutedOr one of the following unsubstituted groups: an alkyl group having 1 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an aralkyl group having 4 to 20 carbon atoms, a heteroarylalkyl group having 4 to 20 carbon atoms, an aryloxy group having 4 to 20 carbon atoms, a heteroaryloxy group having 4 to 20 carbon atoms, an arylalkoxy group having 4 to 20 carbon atoms, and a heteroarylalkoxy group having 4 to 20 carbon atoms. Wherein the substitution means a group formed by substitution of one or more hydrogen atoms with at least one of branched alkyl, oxygen atom, alkenyl, alkynyl, aryl, etc.;
in the formula I, the flexible unit has the structure Ar 1 (Cn-Ar) m * Wherein- (Cn-Ar) -is part of a chain of star-shaped structures, and m is as defined for m in formula I, and represents the number of chains of star-shaped units, including but not limited to 2-10.
In the structure of the flexible unit, C n The flexible chain is one of a straight chain alkyl group having 2 to 20 carbon atoms, a branched alkyl group having 2 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms, an alkylthio group having 2 to 20 carbon atoms, a straight chain alkenyl group having 3 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, a cyclic alkenyl group having 3 to 20 carbon atoms, an alkenyloxy group having 3 to 20 carbon atoms, an alkenylthio group having 3 to 20 carbon atoms, a straight chain alkynyl group having 3 to 20 carbon atoms, a branched alkynyl group having 3 to 20 carbon atoms, a cyclic alkynyl group having 3 to 20 carbon atoms, a straight chain alkylcarbonyl group having 3 to 20 carbon atoms, a branched alkylcarbonyl group having 3 to 20 carbon atoms, a cyclic alkylcarbonyl group having 3 to 20 carbon atoms, an imino group having 3 to 20 carbon atoms with one carbon-nitrogen double bond.
In the structure of the flexible unit, ar is one or more of the following coupling structures:
wherein R is 3 And R is 6 Relatively independentIs one of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, wherein the substitution means a group formed by substitution of one or more hydrogen atoms with at least one of an oxygen atom, an alkenyl group, an alkynyl group, an aryl group, and the like;
in the structure of the flexible unit, ar 1 Is one or more of the following coupling structures:
the preparation method of the active layer material of the organic photovoltaic device containing the star-shaped flexible chain segment comprises the following steps:
in inert gas or nitrogen atmosphere and organic solvent, mixing monomer containing star-shaped flexible unit, monomer containing electron donating unit and monomer containing naphthalene [1,2-c:5,6-c' ] double ([ 1,2,5] five-membered ring) unit derivative, and then carrying out polymerization reaction under the catalysis of catalyst, and purifying to obtain the polymer active layer material containing flexible chain segment.
Wherein, the monomer containing naphthalene [1,2-c:5,6-c' ] double ([ 1,2,5] five-membered ring) unit derivative is preferably one of the following structural formulas:
Wherein R is 1 、R 2 Is defined as before.
The monomer containing the star-shaped flexible unit is preferably monomer with each star-shaped unit chain terminated by trimethyltin, such asPreferably Ar 1 (Cn-Ar-(SnMe 3 )) m The method comprises the steps of carrying out a first treatment on the surface of the The monomers containing electron-donating units are preferably monomers which are terminated by trimethyltin, e.g.>
The organic solvent can be one of chlorobenzene, dichlorobenzene, toluene and xylene; the catalyst comprises a palladium catalyst which can be one of tetraphenylphosphine palladium, palladium acetate and tris (dibenzylideneacetone) dipalladium; the sum of the amounts of the substances containing the reactive functional groups of the star-structure flexible unit monomer and the electron-donating unit monomer is equal to the amount of the substances containing the reactive functional groups of the naphthalene [1,2-c:5,6-c' ] double ([ 1,2,5] five-membered ring) unit monomer.
The reaction temperature of the polymerization reaction is 130-140 ℃, the reaction time is 40-48 h, and the stirring speed is 600-1000 rpm.
The mixing mode is physical mixing; the purification mode comprises more than one of precipitation, filtration, column chromatography and extraction.
The active layer material of the polymer photovoltaic device containing the star-shaped flexible chain segment is prepared through Stille coupling reaction, and the reaction equation is as follows:
the synthesis characteristic of the invention is: naphthalene [1,2-c:5,6-c' ] double ([ 1,2,5] five-membered ring) unit, star-structure flexible chain segment unit, electron donating unit and derivatives thereof are subjected to ternary random copolymerization reaction through Stille coupling reaction under the catalysis of palladium catalyst, so that star-structure flexible unit is introduced into a polymer system.
The active layer material of the organic photovoltaic device containing the star-shaped flexible chain segment is applied to the organic photovoltaic device.
Compared with the prior art, the invention has the beneficial effects that:
(1) The polymerized monomer material containing the star-shaped structure flexible chain segment has the advantages of simple preparation method, easy purification and mass production;
(2) According to the invention, the structural performance of the polymer can be regulated and controlled by selecting different star-shaped flexible units, so that the requirements of different scenes can be met;
(3) The polymer active layer material containing the star-shaped structure flexible chain segment is beneficial to enhancing the deformation performance of the material, so that the high-efficiency stretchable organic photovoltaic device is obtained.
(4) The invention adopts a method of introducing a flexible chain segment unit into a conjugated polymer system to prepare the ternary random copolymer containing the flexible unit, thereby realizing stronger strain stability.
Drawings
FIG. 1 is an ultraviolet-visible light absorption curve of a polymer active layer material P1 containing a star-structured soft segment;
FIG. 2 is a cyclic voltammetry characteristic of a polymer active layer material P1 containing a star-structured soft segment;
FIG. 3 is a graph of voltage-current density for polymer solar cells with polymer active layer materials P2 and P3, respectively, and N2200 as active layers, containing star-structured soft segments;
FIG. 4 is a graph of the wavelength-external quantum efficiency of polymer solar cells with polymer active layer materials P2 and P3 containing star-structured soft segments, respectively, and N2200 as the active layer;
fig. 5 is a graph of voltage-dark current density for polymer active layer materials P4, P5, and P6 containing star-structured soft segments, respectively, with N2200 being the active layer of the polymer photodetector.
Fig. 6 is a stress-strain curve of the polymer active layer materials P1, P2, P3 and P4 containing the star-structured soft segment and N2200 as active layer materials, respectively, and the polymers P1-1 and N2200 not containing the star-structured soft segment as active layer materials.
Detailed Description
The present invention will be described in further detail with reference to specific examples and drawings, but embodiments of the present invention are not limited thereto. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The reagents used in the examples are commercially available as usual unless otherwise specified.
1. Preparation of material monomer (M1)
(1) Synthesis of 1,3, 5-tris (3- (benzyloxy) prop-1-en-1-yl) benzene (M1-1): in a 500mL two-necked round bottom flask, 1,3, 5-tribromobenzene (31.18 g,100 mmol) was weighed, 150mL of acetonitrile and 32mL of triethylamine were added, the mixture was purged 3 times with air, and palladium acetate (1.12 g,5 mmol) and triphenylphosphine (2.24 g,10 mmol) were weighed. Under the protection of nitrogen, allyl benzyl ether (51.84 g,350 mmol) was added dropwise to the reaction mixture after stirring for 30 minutes, and the mixture was reacted at 90℃for 20 hours. And (3) post-reaction treatment: the reaction was quenched by adding 20mL of hydrochloric acid solution, followed by extraction with dichloromethane, washing with deionized water, repeating the extraction 3 times, drying over anhydrous magnesium sulfate, filtering, and removing the solvent using a rotary evaporator under reduced pressure. Further purification was carried out using a silica gel column chromatography, petroleum ether/ethyl acetate (8:1) as eluent, to give a brown oily liquid (M1-1) by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.34 (m, 3H), 7.31 (d, 6H), 7.28 (m, 6H), 6.65 (d, 3H), 6.55 (s, 3H), 6.25 (t, 3H), 4.88 (s, 6H), 4.04 (s, 6H). The chemical reaction equation of the preparation process is as follows.
(2) Synthesis of 1,3, 5-Benzene-glycerol (M1-2): a250 mL two-necked round bottom flask was purged with nitrogen, lithium aluminum hydride (3.80 g,100 mmol) was rapidly weighed and placed in a cooling circulation apparatus at 0deg.C. 30mL of anhydrous tetrahydrofuran was added dropwise thereto, and the reaction was stirred for 30 minutes. 1,3, 5-tris (3- (benzyloxy) prop-1-en-1-yl) benzene (M1-1) (1.63 g,30 mmol) was weighed and dissolved in 10mL of anhydrous tetrahydrofuran, and was added dropwise into a reaction flask 3 times at 20 minutes intervals, and after all the drops were completed, the reaction was continued for 1 hour, and then was allowed to proceed to room temperature for 2 hours. And (3) post-reaction treatment: the reaction was quenched with 20mL of ice water, then extracted with dichloromethane, washed with deionized water, repeatedly extracted 3 times, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed using a reduced pressure rotary evaporator. With a small amount ofTetrahydrofuran was dissolved in the initial product, and further purification by recrystallization from n-hexane was carried out using a silica gel column chromatography, methylene chloride/methanol (30:1) was used as a eluent, and a colorless oily liquid (M1-2) was obtained by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 6.82 (s, 3H), 4.42 (t, 3H), 3.47-3.38 (m, 6H), 2.61-2.49 (m, 6H), 1.73 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(3) Synthesis of 1,3, 5-tris (3-iodopropyl) benzene (M1-3): triphenylphosphine (23.61 g,90 mmol) and iodine (22.83 g,90 mmol) were weighed into a 500mL two-necked round bottom flask, 200mL of methylene chloride was added, the mixture was stirred at 25℃under nitrogen atmosphere, and after 30 minutes of reaction, imidazole (7.48 g,110 mmol) was added to the mixture, and the reaction was continued for 30 minutes after the addition was completed. 1,3, 5-Benzenoglyciol (M1-2) (6.30 g,25 mmol) was then added to the reaction flask, and the reaction was carried out at 60℃for 10 hours. And (3) post-reaction treatment: the reaction was quenched by adding 90mL of saturated sodium metabisulfite solution, then extracted with dichloromethane, washed with deionized water, repeatedly extracted 3 times, dried over anhydrous magnesium sulfate, filtered and the solvent was removed using a reduced pressure rotary evaporator. Further purification was carried out using a silica gel column chromatography, petroleum ether/ethyl acetate (8:1) as eluent, to give a yellow oily liquid (M1-3) by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 6.89 (s, 3H), 3.43 (t, 6H), 2.63 (t, 6H), 2.20 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(4) Synthesis of 1,3, 5-tris (3- (thiophen-2-yl) propyl) benzene (M1-4): round bottom to 100mL20mL of anhydrous tetrahydrofuran was added to the flask, followed by stirring with magnesium turnings (2.2 g,90 mmol). 2-bromothiophene (70 mmol,11.4 g) was dissolved in 20mL anhydrous tetrahydrofuran, the temperature was kept at 60℃and the mixture of magnesium turnings and tetrahydrofuran was added dropwise under nitrogen atmosphere, and after 2 hours of reaction, the Grignard reagent solution was separated from the remaining Mg using a syringe for use. Into a 100mL two-necked round bottom flask, compound M1-3 (1.16 g,20 mmol) and the above reaction solution were charged, 20mL of anhydrous tetrahydrofuran was placed in a cooling circulation apparatus at-10℃under nitrogen protection, and after cooling for 30 minutes, 0.1M dilithium tetrachlorocuprate (7.5 mL,0.75 mmol) was added dropwise to the reaction flask, and the reaction was carried out at this temperature for 5 hours. And (3) post-reaction treatment: the reaction was quenched by adding 20mL of saturated ammonium chloride solution, then poured into a beaker containing 200mL of deionized water, extracted with diethyl ether, dried over anhydrous magnesium sulfate, filtered and the solvent removed using a reduced pressure rotary evaporator. Further purification was carried out using a silica gel column chromatography, with pure petroleum ether as eluent, to give colorless oily liquid (M1-4) by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 h NMR (400 MHz, DMSO), delta (ppm): 7.39 (d, 3H), 7.09-6.85 (m, 9H), 2.83-2.57 (m, 12H), 1.86 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(5) Synthesis of 1,3, 5-tris (3- (5- (trimethylstannyl) thiophen-2-yl) propyl) benzene (M1): in a 250mL two-necked round bottom flask, compound M1-4 (2.50 g,5.55 mmol) was weighed, 40mL of anhydrous tetrahydrofuran was added, the mixture was put into a cooling circulation device at-78℃under the protection of nitrogen, after cooling for 30 minutes, 2.5M n-butyllithium solution (10.68 mL,26.70 mmol) was added dropwise to the reaction flask, the mixture was reacted at this temperature for 2 hours, and then 1.0M trimethyltin chloride solution (35.10 mL,35.10 mmol) was added dropwise to the reaction system, and after the addition, the reaction was resumed at room temperature for 3 hours. And (3) post-reaction treatment: adding a small amount of deionized water to quench the reaction, and pouring the reaction product into a container filled with 200mL of deionized waterIn a beaker, extraction was performed with methylene chloride, drying was performed using anhydrous magnesium sulfate, the solvent was removed using a reduced pressure rotary evaporator after filtration to obtain an initial product, and the obtained product was repeatedly recrystallized three times with ethanol, and then dried in a vacuum oven to finally obtain a white flaky solid (M1). 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.09-7.06 (m, 6H), 6.85 (d, 3H), 2.87-2.74 (m, 6H), 2.63-2.58 (m, 6H), 1.86-1.82 (m, 6H), 0.27 (s, 27H). The chemical reaction equation of the preparation process is as follows.
2. Preparation of material monomer (M2)
(1) Synthesis of 2- (4-bromobutyl) thiophene (M2-1): thiophene (8.42 g,100 mmol) was weighed into a 100mL two-necked round bottom flask, 40mL of anhydrous tetrahydrofuran was added, the mixture was put into a cooling circulation device at-78℃under the protection of nitrogen, after cooling for 30 minutes, 2.5M n-butyllithium solution (36.00 mL,90 mmol) was added dropwise to the reaction flask, the reaction was carried out at this temperature for 2 hours, 1, 4-dibromobutane (21.60 g,100 mmol) was added to the reaction system, and after the addition, the reaction was resumed at room temperature for 6 hours. And (3) post-reaction treatment: the reaction was quenched by adding a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, extracted with petroleum ether, dried over anhydrous magnesium sulfate, filtered, and the solvent removed using a reduced pressure rotary evaporator to give the initial product. Further purification was carried out using a silica gel column chromatography, with pure petroleum ether as eluent, to give colorless oily liquid (M2-1) by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.31 (d, 1H), 6.98 (m, 1H), 6.85 (d, 1H), 3.52 (t, 2H), 2.85 (t, 2H), 1.81 (m, 2H), 1.50 (m, 2H). The chemical reaction equation of the preparation process is as follows.
(2) Synthesis of tris (4- (4- (thiophen-2-yl) butoxy) phenyl) methane (M2-2): in a 250mL two-necked round bottom flask, 4' -methylenetriphenol (5.00 g,10.27 mmol) and 2- (4-bromobutyl) thiophene (M2-1) (7.83 g,35.94 mmol) and potassium carbonate (5.53 g,40.00 mmol) were weighed, 100mL of dimethylformamide was added, and after three times of air extraction, the mixture was heated to 100℃under nitrogen atmosphere and reacted for 6 hours. And (3) post-reaction treatment: the reaction was quenched by adding a small amount of deionized water, poured into a beaker containing 200mL of saturated aqueous sodium chloride solution, extracted with methylene chloride, washed with deionized water, repeatedly extracted 3 times, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed using a rotary evaporator under reduced pressure. Further purification was carried out using a silica gel column chromatography, petroleum ether/dichloromethane (4:1) as eluent, and a white solid material (M2-2) was obtained by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.38 (d, 3H), 7.13 (s, 6H), 7.01-6.85 (m, 12H), 5.41 (s, 1H), 4.11 (t, 6H), 2.81 (t, 6H), 1.73-1.50 (m, 12H). The chemical reaction equation of the preparation process is as follows.
(2) Synthesis of tris (4- (4- (5- (trimethylstannyl) thiophen-2-yl) butoxy) phenyl) methane (M2): in a 100mL two-necked round bottom flask, compound M2-2 (2.50 g,3.54 mmol) was weighed, 40mL of anhydrous tetrahydrofuran was added, the mixture was put into a cooling circulation device at-78℃under the protection of nitrogen, after cooling for 30 minutes, 2.5M n-butyllithium solution (5.10 mL,12.75 mmol) was added dropwise to the reaction flask, the reaction was carried out at this temperature for 2 hours, and then 1M trimethyltin chloride solution (15.20 mL,15.20 mmol) was added dropwise to the reaction system, and after the addition, the reaction was resumed at room temperature and overnight. And (3) post-reaction treatment: the reaction was quenched by adding a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, and quenched with methylene chlorideExtraction, drying with anhydrous magnesium sulfate, filtering, removing solvent with a reduced pressure rotary evaporator to obtain an initial product, repeatedly recrystallizing with ethanol for three times, and drying the obtained product in a vacuum oven to obtain a white solid substance (M2). 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, and the chemical reaction equation of the preparation process is as follows. 1 H NMR(400MHz,CDCl 3 ),δ(ppm):7.11(s,6H),7.06-6.85(m,12H),5.41(s,1H),4.15(t,6H),2.82(t,6H),1.73-1.50(m,12H)，0.27(s,27H)。
3. Preparation of material monomer (M3)
(1) Synthesis of N, N' - (benzene-1, 3, 5-triacyl) tris (6-bromohexane-1-imine) (M3-1): in a 250mL two-neck round bottom flask, 6-hydroxyhexanal (16.50 g,142.18 mmol) was weighed, 60mL of toluene was added and stirred, 1,3, 5-triaminobenzene (5.04 g,40.62 mmol) was added in three portions under nitrogen atmosphere, stirred at 30℃for half an hour to complete dissolution, and the temperature was raised to 100℃for stirring reaction for 6 hours. And (3) post-reaction treatment: the reaction solution was cooled to room temperature, quenched with 30mL of deionized water, poured into a beaker containing 200mL of deionized water, extracted with methylene chloride, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed using a reduced pressure rotary evaporator. Further purification was carried out using a silica gel column chromatography, petroleum ether/dichloromethane (4:1) as eluent, to give (M3-1) as a yellow oily liquid by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 8.52 (t, 3H), 6.65 (s, 3H), 4.73 (s, 3H), 3.65 (t, 6H), 2.21 (m, 6H), 1.58-1.53 (m, 12H), 1.31 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(2) Synthesis of N, N' - (benzene-1, 3, 5-triacyl) tris (5- (thiophen-2-yloxy) pentane-1-imine) (M3-2): to a 250mL round bottom flask, compound M3-1 (7.51 g,20 mmol), 2-bromothiophene (10.52 g,65 mmol) and tetrabutylammonium bromide (0.64 g,2 mmol) were weighed, 60mL of toluene was added to extract air 3 times, the temperature was raised to 100℃under nitrogen atmosphere, and the reaction was stirred for 6 hours. The temperature of the reaction solution was lowered to 60℃and an aqueous NaOH solution (mass fraction: 40%,20 mL) was added dropwise to the reaction system, followed by stirring at 80℃for 6 hours. And (3) post-reaction treatment: the reaction solution was cooled to room temperature, quenched with 30mL of deionized water, poured into a beaker containing 200mL of deionized water, extracted with methylene chloride, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed using a reduced pressure rotary evaporator. Further purification was carried out using a silica gel column chromatography, petroleum ether/dichloromethane (4:1) as eluent, to give (M3-2) as a yellow oily liquid by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 8.52 (t, 3H), 6.73-6.69 (m, 6H), 6.56 (m, 3H), 6.21 (d, 3H), 4.25 (t, 6H), 2.24 (m, 6H), 1.86 (m, 6H), 1.54 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(3) Synthesis of N, N ', N' - (benzene-1, 3, 5-triacyl) tris (5- ((5- (trimethylstannyl) thiophen-2-yl) oxy) pentan-1-imine) (M3): in a 100mL two-necked round bottom flask, compound M3-2 (2.48 g,4.00 mmol) was weighed, 30mL of anhydrous tetrahydrofuran was added, the mixture was placed in a cooling circulation device at-78℃under nitrogen atmosphere, after cooling for 30 minutes, 2.5M n-butyllithium solution (5.40 mL,13.50 mmol) was added dropwise to the reaction flask, the reaction was carried out at this temperature for 2 hours, and then 1.0M trimethyltin chloride solution (15.60 mL,15.60 mmol) was added dropwise to the reaction system, and after the addition, the reaction was resumed at room temperature for 3 hours. And (3) post-reaction treatment: adding a small amount of deionized water to quench the reaction, and then pouring the mixture intoIn a beaker containing 200mL of deionized water, extraction was performed with methylene chloride, drying was performed using anhydrous magnesium sulfate, the solvent was removed using a reduced pressure rotary evaporator after filtration to obtain an initial product, repeated recrystallization was performed three times with ethanol, and the obtained product was put into a vacuum oven to be dried, finally obtaining a yellow solid (M3). 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 8.50 (t, 3H), 6.73-6.69 (m, 6H), 6.24 (d, 3H), 4.25 (t, 6H), 2.24 (m, 6H), 1.86 (m, 6H), 1.54 (m, 6H), 0.27 (s, 27H). The chemical reaction equation of the preparation process is as follows.
4. Preparation of material monomer (M4)
(1) Synthesis of 1, 5-heneicosanyl naphthalene (M4-1): in a 250mL two-necked round bottom flask, naphthalene (6.4 g,50 mmol) and undecanoyl chloride (20.5 g,100 mmol) were weighed and dissolved in 70mL dichloromethane, the gas was evacuated and exchanged 2 times, aluminum trichloride (14.6 g,110 mmol) was added to the reaction solution 3 times in 30 minutes, and the temperature was raised to 65℃for 6 hours. And (3) post-reaction treatment: 50mL of ice water is slowly added into the reaction solution to quench the reaction, then dichloromethane is used for extraction, deionized water is used for cleaning, extraction is repeated for 3 times, anhydrous magnesium sulfate is used for drying, and a decompression rotary evaporator is used for removing the solvent after filtration for use. The obtained colorless oily substance was dissolved in concentrated hydrochloric acid, zinc powder (6.5 g,100 mmol) was added thereto, and the mixture was stirred at 65℃and reacted for 4 hours. And (3) post-reaction treatment: the reaction was quenched by the addition of 100mL of saturated sodium bicarbonate solution and the unreacted zinc powder was removed by filtration. The filtrate was repeatedly extracted with methylene chloride three times, then dried over anhydrous magnesium sulfate, and after filtration, the solvent was removed by using a rotary evaporator under reduced pressure to obtain the initial product. Further purification was carried out using a silica gel column chromatography, petroleum ether/dichloromethane (5:1) as eluent, and a colorless oily liquid (M4-1) was obtained by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.95 (d, 2H), 7.61 (t, 2H), 6.96 (d, 2H), 3.21 (t, 4H), 1.63 (m, 4H), 1.28-1.24 (m, 32H), 0.86 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(2) Synthesis of 2, 6-dibromo-4, 8-heneicosanyl naphthalene (M4-2): in a 250mL two-necked round bottom flask, compound M4-1 (6.50 g,14.89 mmol) and N-bromosuccinimide (5.83 g,32.74 mmol) were weighed, 60mL chloroform was added, the temperature was raised to 65℃under nitrogen protection, and the reaction was stirred for 8 hours. And (3) post-reaction treatment: the reaction was quenched by adding a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and the solvent removed using a reduced pressure rotary evaporator to give the initial product. Further purification was carried out using a silica gel column chromatography, petroleum ether/dichloromethane (6:1) as eluent, and a white solid powder (M4-2) was obtained by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 8.15 (d, 2H), 6.85 (d, 2H), 3.21 (t, 4H), 1.63 (m, 4H), 1.28-1.24 (m, 32H), 0.86 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(3) Synthesis of 2, 6-dibromo-1, 5-dinitro-4, 8-heneicosanyl naphthalene (M4-3): in a 250mL two-necked round bottom flask, compound M4-2 (3.76 g,10.00 mmol) was weighed, 50mL of glacial acetic acid was added, and the mixture was dissolved under stirring under nitrogen protection, concentrated nitric acid (10.22 mL,23.00 mmol) was added dropwise, the temperature was raised to 65℃and the reaction was stirred for 8 hours. And (3) post-reaction treatment: the reaction was quenched by addition of 50mL of saturated sodium bicarbonate solution, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and then depressurizedThe solvent was removed by rotary evaporator to give the initial product. Further purification was carried out using a silica gel column chromatography, petroleum ether/dichloromethane (6:1) as eluent, and a brown solid powder (M4-3) was obtained by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.67 (s, 2H), 3.11 (t, 4H), 1.63 (m, 4H), 1.28-1.24 (m, 32H), 0.87 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(4) Synthesis of N, N' - (1, 5-dinitro-4, 8-heneicosanyl naphthalene-2, 6-diacyl) bis (1, 1-diphenylazomethine) (M4-4): in a 100mL two-necked round bottom flask, sodium tert-butoxide (1.92 g,20.00 mmol) was weighed, dissolved in 30mL toluene, and purged 3 times to rapidly add tris dibenzylideneacetone dipalladium (0.17 g,0.18 mmol) and 2 '-bis (diphenylphosphine) -1,1' -binaphthyl (0.23 g,0.36 mmol). After stirring at room temperature for 10 minutes, the reaction solution became a dark red solution. 2, 6-dibromo-1, 5-dinitro-4, 8-heneicosanyl naphthalene (M4-3) (2.50 g,3.67 mmol) was then added to the reaction mixture in 3 portions, the reaction temperature was raised to 85℃and the reaction solution was stirred for an additional 30 minutes. To the reaction solution was added dropwise dibenzimine (1.85 mL,11.05 mmol), and the reaction was continued for 2 hours as a brown solid substance. And (3) post-reaction treatment: stopping heating, and filtering after the reaction solution is cooled to room temperature to obtain black solid substance as initial product (M4-4). 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.95 (d, 4H), 7.64-7.58 (m, 10H), 7.41-7.38 (m, 8H), 3.13 (t, 4H), 1.61 (m, 4H), 1.28-1.24 (m, 32H), 0.85 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(5)4,Synthesis of 8-heneicosyl-1, 2,5, 6-tetrahydronaphthalene-1, 2,5, 6-tetramine (M4-5): n, N' - (1, 5-dinitro-4, 8-heneicosanyl naphthalene-2, 6-diacyl) bis (1, 1-diphenylazomethine) (M4-4) (2.10 g,2.37 mmol) and stannous chloride (1.35 g,7.11 mmol) were weighed into a 100mL two port round bottom flask and dissolved in 35mL hydrochloric acid. The temperature was raised to 70℃and reacted for 5 hours. Then, the heating was stopped, cooled to room temperature, and then transferred to a cold trap at 0℃and stirred for 30 minutes, and a reddish brown solid substance appeared. And (3) post-reaction treatment: the reddish brown solid was obtained by filtration, and the solid was washed with absolute ethanol until the filtrate became colorless, and the obtained solid was a starting product (M4-5). 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 6.85 (s, 2H), 4.83 (d, 8H), 3.13 (t, 4H), 1.59 (m, 4H), 1.28-1.26 (m, 32H), 0.85 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(6) 4, 9-eicosanyl naphthalene [1,2-c:5,6-c ]' ]Bis ([ 1,2, 5)]Synthesis of thiadiazole) (M4-6): in a 250mL two-necked round bottom flask, 4, 8-heneicosyl-1, 2,5, 6-tetrahydronaphthalene-1, 2,5, 6-tetramine (M4-5) (5.00 g,10.00 mmol) was weighed and dissolved in 100mL anhydrous pyridine, after three times of air extraction, thionyl chloride (3.27 mL,45.00 mmol) was added dropwise under nitrogen atmosphere, and the mixture was heated to 80℃for 3 hours. And (3) post-reaction treatment: the reaction was quenched by adding 20mL of saturated aqueous sodium bicarbonate, poured into a beaker containing 200mL of saturated aqueous sodium chloride, extracted with dichloromethane, washed with deionized water, repeatedly extracted 3 times, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed using a reduced pressure rotary evaporator. Recrystallisation from a hot dioxane solution gave an orange solid (M4-6). 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 8.22 (d, 2H), 3.07 (t, 4H), 1.64 (m, 4H), 1.29-1.15 (m, 32H), 0.88 (m, 6H). Chemical reaction equations of the preparation process such asAnd (3) downwards.
(7) 5, 10-dibromo-4, 9-heneicosanyl naphthalene [1,2-c:5,6-c ]']Bis ([ 1,2, 5)]Thiadiazole) (M4) synthesis: in a 100mL two-necked round bottom flask, compound M4-6 (2.50 g,4.53 mmol) and N-bromosuccinimide (1.73 g,9.96 mmol) were weighed, 30mL chloroform was added, the temperature was raised to 65℃under nitrogen protection, glacial acetic acid (2 mL) was added dropwise, and the reaction was stirred for 5 hours. And (3) post-reaction treatment: the reaction was quenched by adding a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and the solvent removed using a reduced pressure rotary evaporator to give the initial product. Further purification was carried out using a silica gel column chromatography, petroleum ether/dichloromethane (6:1) as eluent, and an orange solid material (M4) was obtained by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 3.07 (t, 4H), 1.64 (m, 4H), 1.29-1.15 (m, 32H), 0.88 (m, 6H). The chemical reaction equation of the preparation process is as follows.
5. Preparation of material monomer (M5)
(1) 4, 9-eicosanyl naphthalene [1,2-c:5,6-c ]']Bis ([ 1,2, 5)]Synthesis of selenadiazole) (M5-1): in a 250mL two-necked round bottom flask, 4, 8-heneicosyl-1, 2,5, 6-tetrahydronaphthalene-1, 2,5, 6-tetramine (5.00 g,10.00 mmol) was weighed and dissolved in 100mL anhydrous pyridine, after three times of air extraction, the reaction solution was cooled to 0℃under the protection of nitrogen atmosphere, selenium oxychloride (7.46 g,45.00 mmol) was added dropwise, and the mixture was heated to 80℃and reacted for 3 hours. And (3) post-reaction treatment: the reaction was quenched by adding 20mL of saturated aqueous sodium bicarbonate, poured into a beaker containing 200mL of saturated aqueous sodium chloride, extracted with dichloromethane, deionized waterAfter washing and repeated extraction for 3 times, the mixture was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed by using a rotary evaporator under reduced pressure. Recrystallisation from a hot dioxane solution gives a brown solid (M5-1). 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 5.98 (d, 2H), 2.41 (t, 4H), 1.64 (m, 4H), 1.29-1.15 (m, 32H), 0.88 (m, 6H). The chemical reaction equation of the preparation process is as follows.
(2) 5, 10-dibromo-4, 9-heneicosanyl naphthalene [1,2-c:5,6-c ]']Bis ([ 1,2, 5)]Synthesis of selenadiazole) (M5): in a 100mL two-necked round bottom flask, compound M5-1 (3.00 g,4.62 mmol) and N-bromosuccinimide (1.81 g,10.18 mmol) were weighed, 40mL chloroform was added, the temperature was raised to 65℃under nitrogen protection, glacial acetic acid (2.10 mL) was added dropwise, and the reaction was stirred for 5 hours. And (3) post-reaction treatment: the reaction was quenched by adding a small amount of deionized water, then poured into a beaker containing 200mL of deionized water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered, and the solvent removed using a reduced pressure rotary evaporator to give the initial product. Further purification was carried out using a silica gel column chromatography, petroleum ether/dichloromethane (5:1) as eluent, and a brown solid substance (M5) was obtained by column chromatography. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 2.43 (t, 4H), 1.62 (m, 4H), 1.29-1.15 (m, 32H), 0.88 (m, 6H). The chemical reaction equation of the preparation process is as follows.
Example 1 Synthesis of Polymer active layer Material P1 containing Star-structured soft segment
Weighing M4 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6 ]c']Bis ([ 1,2, 5)]Thiadiazole) (70.82 mg,0.10 mmol), 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene (77.02 mg,0.085 mmol) and M1 monomer 1,3, 5-tris (3- (5- (trimethyltin) thiophen-2-yl) propyl) benzene (9.42 mg,0.01 mmol) and Pd (PPh 3 ) 4 (6.9 mg) in a 15mL pressure-resistant tube, 1.20mL of ultra-dry chlorobenzene was added under nitrogen atmosphere. The reaction system was heated to 140℃and maintained at that temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction solution was dropped into anhydrous methanol, and a crude product was obtained by filtration. And (3) treating the crude product by using a Soxhlet extraction device, sequentially extracting by using absolute methanol, acetone, normal hexane and chloroform, concentrating the solution of the chloroform component, then settling the solution into the absolute methanol again, filtering, and drying to obtain the purple black solid (P1). 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.74 (s, 3H), 7.36 (s, 3H), 7.31 (s, 9H), 7.24 (s, 3H), 6.78 (d, 9H), 3.32 (s, 6H), 3.07 (s, 6H), 2.97 (s, 9H), 2.77 (s, 3H), 2.63 (s, 3H), 2.44 (s, 9H), 2.27 (s, 18H), 2.01 (s, 3H), 1.90 (s, 3H), 1.61 (s, 12H), 1.55 (s, 6H), 1.38 (s, 6H), 1.35-1.13 (m, 123H), 0.91 (d, 48H). High temperature GPC: mn=37.6 kDa; mw=56.5 kDa. The chemical reaction equation of the preparation process is as follows:
Synthesis of polymer active layer material P1-1 corresponding to P1, which does not contain star-structured soft segments: weighing M4 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c ]']Bis ([ 1,2, 5)]Thiadiazole) (70.82 mg,0.10 mmol) and 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene (90.61 mg,0.10 mmol) and Pd (PPh) 3 ) 4 (6.9 mg) in a 15mL pressure-resistant tube, 1.20mL of ultra-dry chlorobenzene was added under nitrogen atmosphere. The reaction system was heated to 140℃and maintained at that temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction solution was dropped into anhydrous methanol, and filtration was performedThe crude product is obtained. And (3) treating the crude product by using a Soxhlet extraction device, sequentially extracting by using absolute methanol, acetone, normal hexane and chloroform, concentrating the solution of the chloroform component, then settling the solution into the absolute methanol again, filtering, and drying to obtain a purple brown solid (P1-1). 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.76 (s, 2H), 7.42 (s, 2H), 7.31 (d, 6H), 6.80 (s, 4H), 3.60 (s, 3H), 3.07 (s, 4H), 2.77 (s, 3H), 1.77 (s, 2H), 1.58 (d, 11H), 1.38 (s, 4H), 1.32-1.23 (m, 81H), 0.93 (s, 12H), 0.89 (s, 19H). High temperature GPC: mn=31.5 kDa; mw=49.3 kDa.
The ultraviolet-visible light absorption curve of the polymer active layer material P1 containing the star-structured soft segment is shown in FIG. 1, the main absorption peak of the polymer is about 593nm, and the absorption edge is about 684 nm. The absorption peak produces a degree of red shift and the intramolecular charge transfer effect is enhanced compared to the system polymer without the soft segment introduced.
The cyclic voltammetry characteristic curve of the polymer active layer material P1 containing the star-structured flexible chain segment is shown in figure 2, the initial oxidation potential of the polymer is 1.09V, and the initial reduction potential is-0.77V. By formula E HOMO ＝-e[E ox -E( Fc/Fc+ )+4.80](eV)；E LUMO ＝-e[E red -E( Fc/Fc+ )+4.80](eV) the LUMO and HOMO energy levels of the polymer were calculated to be-3.63 eV/-5.48eV.
Example 2 Synthesis of Polymer active layer Material P2 containing Star-structured Flexible segments
Weighing M4 monomer 5, 10-dibromo-4, 9-heneicosanyl naphthalene [1,2-c:5,6c ]']Bis ([ 1,2, 5)]Thiadiazole) (70.82 mg,0.10 mmol), 5 '-bis (trimethylstannyl) -2,2' -bithiophene (41.98 mg,0.085 mmol) and M2 monomer tris (4- (4- (5- (trimethylstannyl) thiophen-2-yl) butoxy) phenyl) methane (11.99 mg,0.01 mmol) and Pd (PPh) 3 ) 4 (6.90 mg) in a 15mL pressure-resistant tube, 1.2mL of ultra-dry chlorobenzene was added under nitrogen atmosphere. The reaction system was heated to 140℃and maintained at that temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature The reaction was dropped into anhydrous methanol, and the crude product was obtained by filtration. And (3) treating the crude product by using a Soxhlet extraction device, sequentially extracting by using absolute methanol, acetone, normal hexane and chloroform, concentrating the solution of the chloroform component, then settling the solution into the absolute methanol again, filtering, and drying to obtain a blue-black solid (P2). 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.50 (s, 3H), 7.39 (dd, 12H), 7.11 (s, 12H), 6.94 (s, 6H), 6.77 (dd, 24H), 6.72 (d, 15H), 6.72 (d, 45H), 5.41 (s, 1H), 4.11 (s, 3H), 3.07 (s, 6H), 2.81 (s, 3H), 2.44 (s, 9H), 1.80 (s, 3H), 1.61 (s, 6H), 1.50 (s, 3H), 1.26 (s, 93H), 0.89 (s, 15H). High temperature GPC: mn=43.0 kDa; mw=68.7 kDa.
The chemical reaction equation of the preparation process is as follows:
example 3 Synthesis of Polymer active layer Material P3 containing Star-structured soft segment
Weighing M5 monomer 5, 10-dibromo-4, 9-heneicosanyl naphthalene [1,2-c:5,6c ]']Bis ([ 1,2, 5)]Selenadiazole) (80.40 mg,0.10 mmol), 5 '-bis (trimethylstannyl) -2,2' -bithiophene (41.98 mg,0.085 mmol) and M2 monomer tris (4- (4- (5- (trimethylstannyl) thiophen-2-yl) butoxy) phenyl) methane (11.99 mg,0.01 mmol) and Pd (PPh) 3 ) 4 (6.90 mg) in a 15mL pressure-resistant tube, 1.2mL of ultra-dry chlorobenzene was added under nitrogen atmosphere. The reaction system was heated to 140℃and maintained at that temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction solution was dropped into anhydrous methanol, and a crude product was obtained by filtration. And (3) treating the crude product by using a Soxhlet extraction device, sequentially extracting by using absolute methanol, acetone, normal hexane and chloroform, concentrating the solution of the chloroform component, then settling the solution into the absolute methanol again, filtering, and drying to obtain the purple black solid (P3). 1 HNMR、 13 CNMR, MS and elemental analysis results indicateThe obtained compound is taken as a target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.50 (s, 3H), 7.39 (dd, 12H), 7.11 (s, 12H), 6.94 (s, 6H), 6.77 (dd, 24H), 6.72 (d, 15H), 6.72 (d, 45H), 5.41 (s, 1H), 4.11 (s, 3H), 3.07 (s, 6H), 2.81 (s, 3H), 2.44 (s, 9H), 1.80 (s, 3H), 1.61 (s, 6H), 1.50 (s, 3H), 1.26 (s, 93H), 0.89 (s, 15H). High temperature GPC: mn=38.7 kDa; mw=62.8 kDa.
The chemical reaction equation of the preparation process is as follows:
example 4 Synthesis of Polymer active layer Material P4 containing Star-structured soft segment
Weighing M4 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c ]' ]Bis ([ 1,2, 5)]Thiadiazole) (70.82 mg,0.10 mmol), 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene (63.43 mg,0.07 mmol) and M3 monomer N, N ', N' - (benzene-1, 3, 5-triacyl) tris (5- ((5- (trimethyltin) thiophen-2-yl) oxy) pentan-1-imine) (22.26 mg,0.02 mmol) and Pd (PPh) 3 ) 4 (6.9 mg) in a 15mL pressure-resistant tube, 1.20mL of ultra-dry chlorobenzene was added under nitrogen atmosphere. The reaction system was heated to 140℃and maintained at that temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction solution was dropped into anhydrous methanol, and a crude product was obtained by filtration. The crude product is treated by a Soxhlet extraction device, absolute methanol, acetone, normal hexane and chloroform are sequentially used for extraction, and finally, the solution of the chloroform component is concentrated, and then, the solution is settled into the absolute methanol again, filtered and dried, so that black solid (P4) is finally obtained. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ),δ(ppm):7.78(s,6H),7.65(s,3H),7.56(d,9H),7.33(d,6H),6.87(s,6H),6.80(s,12H),6.70(s,12H),6.25(s,6H),4.11(s,6H),3.38(s,9H),3.07(s,12H),2.94(s,9H),2.44(s,18H),2.25(d,21H),2.15(d,3H),1.82(t,42H),1.75-1.68(m,3H),1.64-1.48(m,54H),1.52-1.48(m,6H),1.38(s,12H),1.31-1.23 (m, 210H), 1.01 (s, 9H), 0.93 (s, 36H). High temperature GPC: mn=35.5 kDa; mw=51.7 kDa.
The chemical reaction equation of the preparation process is as follows:
example 5 Synthesis of Polymer active layer Material P5 containing Star-structured soft segment
Weighing M5 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c ]']Bis ([ 1,2, 5)]Selenadiazole) (80.40 mg,0.10 mmol), 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene (77.02 mg,0.085 mmol) and M1 monomer 1,3, 5-tris (3- (5- (trimethyltin) thiophen-2-yl) propyl) benzene (9.42 mg,0.01 mmol) and Pd (PPh 3 ) 4 (6.9 mg) in a 15mL pressure-resistant tube, 1.20mL of ultra-dry chlorobenzene was added under nitrogen atmosphere. The reaction system was heated to 140℃and maintained at that temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction solution was dropped into anhydrous methanol, and a crude product was obtained by filtration. The crude product is treated by a Soxhlet extraction device, absolute methanol, acetone, normal hexane and chloroform are sequentially used for extraction, and finally, the solution of the chloroform component is concentrated, and then, the solution is settled into the absolute methanol again, filtered and dried, so that black solid (P5) is finally obtained. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.78 (s, 3H), 7.31 (d, 15H), 6.75 (d, 15H), 3.70 (s, 6H), 3.06 (s, 6H), 2.74 (d, 9H), 2.62 (s, 3H), 2.43 (s, 9H), 2.26 (s, 18H), 1.97 (d, 9H), 1.39 (s, 6H), 1.30 (s, 6H), 1.28-1.23 (m, 114H), 0.91 (d, 42H). High temperature GPC: mn=37.2 kDa; mw=48.8 kDa.
The chemical reaction equation of the preparation process is as follows:
/>
EXAMPLE 6 Synthesis of Polymer active layer Material P6 containing Star-structured soft segment
Weighing M5 monomer 5, 10-dibromo-4, 9-heneicosyl naphthalene [1,2-c:5,6-c ]']Bis ([ 1,2, 5)]Selenadiazole) (81.40 mg,0.10 mmol), 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene (77.02 mg,0.085 mmol) and M3 monomer N, N ', N' - (benzene-1, 3, 5-triacyl) tris (5- ((5- (trimethyltin) thiophen-2-yl) oxy) pentan-1-imine) (11.13 mg,0.01 mmol) and Pd (PPh) 3 ) 4 (6.9 mg) in a 15mL pressure-resistant tube, 1.20mL of ultra-dry chlorobenzene was added under nitrogen atmosphere. The reaction system was heated to 140℃and maintained at that temperature for 48 hours. And (3) post-reaction treatment: after the reaction temperature was cooled to room temperature, the reaction solution was dropped into anhydrous methanol, and a crude product was obtained by filtration. The crude product is treated by a Soxhlet extraction device, absolute methanol, acetone, normal hexane and chloroform are sequentially used for extraction, and finally, the solution of the chloroform component is concentrated, and then, the solution is settled into the absolute methanol again, filtered and dried, and finally, black solid (P6) is obtained. 1 HNMR、 13 CNMR, MS and elemental analysis results show that the obtained compound is the target product, 1 H NMR(400MHz,CDCl 3 ) Delta (ppm): 7.78 (s, 9H), 7.55 (s, 3H), 7.49 (d, 18H), 7.41 (dd, 36H), 6.87 (s, 6H), 6.80 (s, 12H), 6.70 (s, 18H), 6.23 (s, 6H), 4.11 (s, 6H), 3.38 (s, 9H), 3.07 (s, 12H), 2.94 (s, 9H), 2.44 (s, 18H), 2.21 (d, 45H), 1.79 (d, 15H), 1.63-1.53 (m, 42H), 1.53-1.52 (m, 6H), 1.38 (s, 12H), 1.31-1.23 (m, 204H), 0.93 (s, 36H), 0.89 (s, 57H). High temperature GPC: mn=35.8 kDa; mw=51.6 kDa.
The chemical reaction equation of the preparation process is as follows:
example 7 preparation of organic photovoltaic device
The polymer active layer material P1 containing the star-shaped flexible segment in the above-mentioned example 1, the polymer active layer material P2 containing the star-shaped flexible segment in the above-mentioned example 2, the polymer active layer material P3 containing the star-shaped flexible segment in the above-mentioned example 3, and the above-mentioned materials are respectively usedThe polymer active layer material P4 containing the star-shaped soft segment in example 4, the polymer active layer material P5 containing the star-shaped soft segment in example 5 and the polymer active layer material P6 containing the star-shaped soft segment in example 6 were used as donor materials, and N2200 was used as acceptor material to prepare organic photovoltaic devices having the structure ITO/PEDOT: PSS/active layer/PFN-Br (methanol 0.5mg mL) -1 ) Ag. N2200 has the structure of formula III:
The method specifically comprises the following steps of:
(1) Cleaning a conductive glass ITO substrate: sequentially placing the ITO glass substrate in acetone, isopropanol, cleaning solution, deionized water and isopropanol for ultrasonic cleaning, removing stains (such as photoresist and the like) possibly remained on the surface of the ITO glass substrate, improving interface contact, and placing the cleaned ITO glass substrate in a vacuum oven for drying;
(2) Placing ITO in an oxygen plasma etcher, and bombarding for twenty minutes by using oxygen plasma to thoroughly remove organic matters possibly remained on the surface of the ITO glass substrate;
(3) Spin-coating a hole transport interface PEDOT: PSS of about 30nm thickness on ITO, and then thermally annealing at 100deg.C for 20 minutes;
(4) In a glove box under nitrogen atmosphere, the polymer active layer materials P1, P2, P3, P4, P5 and P6 containing the soft segment and N2200 were respectively prepared in the following manner: 1, dissolving in methyl tetrahydrofuran to prepare a solution with the concentration of 5mg/mL, spin-coating an active layer with the thickness of 120nm on a PEDOT (packet data processing) PSS layer, and heating and annealing for 20 minutes at the temperature of 120 ℃ on a heating table to remove residual solvents and improve the appearance of an active layer film;
(5) Spin-coating an electron transport material with a thickness of 20nm on the active layer material in a glove box under nitrogen atmosphere using 0.5mg/mL poly [ (9, 9-bis (3' - (N, N-dimethylamino) propyl) fluorenyl-2, 7-diyl) -ALT- [ (9, 9-di-N-octylfluorenyl 2, 7-diyl) -bromo (PFN-Br);
(6) And finally, placing the prepared device in an evaporation bin, and evaporating an electrode with the thickness of 100nm mAg in a vacuum environment.
(7) The photoelectric conversion efficiency, the current-voltage characteristic curve and the dark current-voltage characteristic curve of the polymer solar cell device were tested in an AM 1.5G simulated solar light.
The prepared organic solar cell devices were subjected to photoelectric performance tests, respectively, and the test results are shown in table 1.
Table 1 device parameters of organic solar cells
As can be seen from the data in table 1, the organic solar cell device having P1 as an active layer donor material and N2200 as an active layer acceptor material has excellent photoelectric properties. The short-circuit current density of the device is 18.53 milliamperes/square centimeter, the open-circuit voltage is 0.87 volt, the filling factor is 68.52 percent, and the final device efficiency is 10.06 percent; an organic solar cell device having P2 as an active layer donor material and N2200 as an active layer acceptor material has excellent photovoltaic properties. The short-circuit current density of the device is 18.04 milliamperes/square centimeter, the open-circuit voltage is 0.93 volt, the filling factor is 65.43 percent, and the final device efficiency is 10.92 percent; an organic solar cell device having P3 as an active layer donor material and N2200 as an active layer acceptor material has excellent photovoltaic properties. The device had a short circuit current density of 19.56 milliamp/square cm, an open circuit voltage of 0.91 volts, a fill factor of 71.40% and a final device efficiency of 12.64%. Wherein fig. 3 and 4 are voltage-current density curves and wavelength-external quantum efficiency curves of an organic solar cell with P2 and P3 as donors and N2200 as acceptors, respectively, corresponding to currents of 17.23 milliamp/square centimeter and 18.55 milliamp/square centimeter, respectively. Fig. 5 shows dark state voltage-current density curves obtained by testing an organic photovoltaic device prepared by taking polymer active layer materials P4, P5 and P6 containing star-shaped structure flexible chain segments as donors and N2200 as acceptors respectively, wherein the device shows obvious diode characteristics, namely, unidirectional conductivity of current, and forward dark current is obviously higher than reverse dark current, which plays an important role in improving the detection rate of a detector and improving the detection capability of the detector on weak light.
Fig. 6 is a stress-strain curve of polymer active layer materials P1, P2, P3 and P4 containing star-structured soft segments and N2200 as active layers and polymers P1-1 and N2200 not containing star-structured soft segments, respectively, as active layer materials. As can be seen from fig. 6, the polymer P1-1 without the star-structured soft segment: the elongation at break of the N2200 active layer was only 1.6%, whereas the polymer active layer material P1 comprising the star-structured soft segment: n2200, P2: n2200, P3: n2200, P4: the elongation at break of the N2200 active layer was 10.7%, 13.0%, 21.9% and 23.1%, respectively, which were higher than those of the polymer active layer without the star-structured soft segment. Thus, the tensile properties of the device can be improved without degrading the device efficiency after introducing the soft segment into the conjugated polymer backbone.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (8)

1. An active layer material of an organic photovoltaic device containing a star-shaped structure flexible chain segment is characterized by being shown in the following formula I:
Wherein n ranges from 5 to 300.
2. A method for preparing an active layer material of an organic photovoltaic device comprising a star-structured soft segment according to claim 1, characterized by comprising the steps of:
in inert gas or nitrogen atmosphere and organic solvent, mixing monomer containing star-shaped structure flexible unit, monomer containing electron donating unit and monomer containing naphthalene [1,2-c:5,6-c' ] double ([ 1,2,5] five-membered ring) unit derivative, and then carrying out polymerization reaction under the catalysis of catalyst, purifying to obtain the active layer material of the organic photovoltaic device containing star-shaped structure flexible chain segment.
3. The method for preparing an active layer material of an organic photovoltaic device containing a star-structured soft segment according to claim 2, wherein the method comprises the following steps:
the monomer containing the star-shaped structure flexible unit is a monomer with each star-shaped unit chain blocked by trimethyltin; the monomer containing the electron donating unit is a monomer capped by trimethyltin.
4. The method for preparing an active layer material of an organic photovoltaic device containing a star-structured soft segment according to claim 2, wherein the method comprises the following steps:
the organic solvent is one of chlorobenzene, dichlorobenzene, toluene and xylene;
The catalyst comprises a palladium catalyst.
5. The method for preparing an active layer material of an organic photovoltaic device containing a star-structured soft segment according to claim 2, wherein the method comprises the following steps:
the sum of the amounts of the substances of the reactive functional groups of the monomer containing the star-structure flexible unit and the monomer containing the electron donating unit is equal to the amount of the substances of the reactive functional groups of the monomer containing the naphthalene [1,2-c:5,6-c' ] double ([ 1,2,5] five-membered ring) unit.
6. The method for preparing an active layer material of an organic photovoltaic device containing a star-structured soft segment according to claim 2, wherein the method comprises the following steps:
the reaction temperature of the polymerization reaction is 130-140 ℃, and the reaction time is 40-48 h.
7. The method for preparing an active layer material of an organic photovoltaic device containing a star-structured soft segment according to claim 2, wherein the method comprises the following steps:
the mixing mode is physical mixing;
the purification mode comprises more than one of precipitation, filtration, column chromatography and extraction.
8. The use of an active layer material of an organic photovoltaic device comprising star-structured soft segments according to claim 1 in an organic photovoltaic device.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130014115A (en) * 2011-07-29 2013-02-07 중앙대학교 산학협력단 Dendrimer compound having tin core and organic electronic diodes comprising of the same
JP2014047139A (en) * 2012-08-29 2014-03-17 Hiroshima Univ Naphthobisthiadiazole derivative and method of producing the same
KR101799562B1 (en) * 2016-09-26 2017-11-20 한국과학기술연구원 Conjugated polymer for organic solar cells and Organic solar cells comprising the same
WO2018076247A1 (en) * 2016-10-27 2018-05-03 South University Of Science And Technology Of China A weak electron-donating building block, copolymers thereof and their preparation methods as well as their applications
CN111153858A (en) * 2020-01-16 2020-05-15 华南理工大学 Star-shaped electroluminescent material based on phenanthroimidazole unit and preparation method and application thereof
CN111788704A (en) * 2018-09-19 2020-10-16 科学与工业研究委员会 Thermoelectric material and method for producing same
CN112521934A (en) * 2019-12-31 2021-03-19 华南理工大学 Hyperbranched electroluminescent polymer, and polymerized monomer, preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775273B (en) * 2012-07-05 2014-09-10 北京大学 Bifurcate alkyl chain and preparation and application thereof in organic conjugated molecules
US10787538B2 (en) * 2018-01-29 2020-09-29 Phillips 66 Company Polymers for organic photovoltaics

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130014115A (en) * 2011-07-29 2013-02-07 중앙대학교 산학협력단 Dendrimer compound having tin core and organic electronic diodes comprising of the same
JP2014047139A (en) * 2012-08-29 2014-03-17 Hiroshima Univ Naphthobisthiadiazole derivative and method of producing the same
KR101799562B1 (en) * 2016-09-26 2017-11-20 한국과학기술연구원 Conjugated polymer for organic solar cells and Organic solar cells comprising the same
WO2018076247A1 (en) * 2016-10-27 2018-05-03 South University Of Science And Technology Of China A weak electron-donating building block, copolymers thereof and their preparation methods as well as their applications
CN111788704A (en) * 2018-09-19 2020-10-16 科学与工业研究委员会 Thermoelectric material and method for producing same
CN112521934A (en) * 2019-12-31 2021-03-19 华南理工大学 Hyperbranched electroluminescent polymer, and polymerized monomer, preparation method and application thereof
CN111153858A (en) * 2020-01-16 2020-05-15 华南理工大学 Star-shaped electroluminescent material based on phenanthroimidazole unit and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Baitian He et al.."Star-like n-type conjugated polymers based on naphthalenediimide for all-polymer solar cells".《Dyes and Pigments》.2018,第159卷85-91. *
Peng Liu et al.."Optimizing Light-Harvesting Polymers via Side Chain Engineering".《Adv. Funct. Mater.》.2015,第25卷6458–6469. *

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