CN114874419B - Conjugated polymer based on alkyl substituted thiophene, preparation method and application thereof - Google Patents
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Abstract
The invention relates to a conjugated polymer based on alkyl substituted thiophene, which has the following structural general formula:the invention has the beneficial effects that the invention discloses a novel conjugated polymer based on alkyl substituted thiophene, which is a copolymer of alkyl thiophene units containing cyano groups and benzene propyl dithiophene units with branched chains connected with halogen groups, wherein the introduction method of alkyl is simple and convenient, and the solubility and the processability of the conjugated polymer can be well regulated; in the novel conjugated polymer donor material based on alkyl substituted thiophene, halogen has a strong electron-withdrawing induction effect, and the halogen is introduced into the conjugated polymer, so that the HOMO energy level of the conjugated polymer can be further reduced, the effect of obviously improving the open-circuit voltage of a device is achieved, and compared with the traditional donor material, the novel conjugated polymer donor material based on alkyl substituted thiophene has more obvious photovoltaic performance improvement and has good commercialization prospect.
Description
Technical Field
The invention belongs to the field of photoelectric materials, and particularly relates to a conjugated polymer based on alkyl substituted thiophene, a preparation method and application thereof.
Background
Along with the gradual consumption of fossil energy, the energy problem becomes one of the most outstanding problems faced by human beings, and the solar cell has the advantages of cleanness, greenness, no pollution, wide distribution, inexhaustible property and the like, has good development prospect, and is an effective method for coping with energy crisis. Solar water heater is the most dominant representative of photo-thermal conversion by utilizing solar energy mainly in two modes of photo-thermal conversion and photoelectric conversion, and the solar water heater is already in thousands of households at present. The photovoltaic cell is the best mode of photoelectric conversion, and the photovoltaic cell has been paid attention to since birth because solar energy is one of powerful alternative energy sources for solving the energy crisis.
Organic polymer solar cells have the characteristics of light weight, low cost, crimping, solution film forming, easy large-area preparation and the like, and have become the focus of research in recent decades. Polythiophene and its derivatives are organic photovoltaic donor materials with wide application, and conjugated polythiophene derivatives have simple preparation process, excellent environment stability, high doped conductivity and special photoelectric performance. The polythiophene without substituent groups has very strong rigidity of the main chain, any solvent can not dissolve or melt the polythiophene, and the processing performance is very poor, so that the practical application prospect is further limited; the polythiophene with substituent groups has good solubility and processability, and becomes one of main donor materials of the organic polymer solar cell.
In order to realize the synthesis of polythiophene with substituent groups, the modification of polythiophene by introducing substituent groups into thiophene units is the most direct method. The structure of the monomer thiophene is known that the monomer thiophene has moderate aromaticity, but the monomer itself is difficult to carry out ring opening reaction because the sulfur atom on the thiophene ring is difficult to react with other reagents. However, the atoms in the beta position of the thiophene monomers are very mobile and can be easily substituted. And the substitution reaction at the beta position has little possibility of influencing the coupling of the 2 position and the 5 position of thiophene. Therefore, it is mostly chosen to introduce different substituents at the β -position of the thiophene monomer. However, the method generally needs a chemical reagent with larger activity such as a butyl lithium reagent, a Grignard reagent and the like, has more severe reaction conditions, complex synthesis steps and higher production cost.
Therefore, how to synthesize a polymer structure of polythiophene units with substituent groups by a simple method and apply the polymer structure in a solar cell active layer to make the photoelectric effect of the polymer structure more obviously improved is a problem to be solved in the industry.
Disclosure of Invention
It is an object of the present invention to provide a conjugated polymer based on alkyl-substituted thiophenes having the following general structural formula:
wherein X is a halogen atom;
R 1 is a C1-C22 alkyl chain or alkyl chain derivative;
R 2 is a C1-C22 alkyl chain or alkyl chain derivative;
in the alkyl chain derivative, one or more carbon atoms are substituted by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups or nitro groups; or one or more hydrogen atoms are substituted with a halogen atom, an oxygen atom, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, an ester group, a cyano group, or a nitro group;
n is a positive integer.
Further, the R 1 Selected from the group consisting of C1-C22 linear alkyl chains.
Further, the R 2 A branched alkyl chain selected from C1-C22.
Further, the R 2 Has the following structural general formula:
wherein R is 3 And R is 4 Independently selected from the group consisting of C1-C22 alkyl chains.
Another object of the present invention is to provide a method for preparing the above-mentioned conjugated polymer based on alkyl-substituted thiophene, which comprises the following steps:
the raw material (I) and the raw material (II) are polymerized by Stille;
wherein the raw material (I) has the following structural general formula:
the raw material (II) has the following structural general formula:
wherein X is a halogen atom;
R 1 is a C1-C22 alkyl chain or alkyl chain derivative;
R 2 is a C1-C22 alkyl chain or alkyl chain derivative;
in the alkyl chain derivative, one or more carbon atoms are substituted by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups or nitro groups; or one or more hydrogen atoms are substituted with a halogen atom, an oxygen atom, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, an ester group, a cyano group, or a nitro group.
Further, the preparation method of the raw material (I) comprises the following steps:
s1, synthesizing a thiophene precursor 1 through Gewald reaction;
s2, brominating the thiophene precursor 1 to obtain a thiophene precursor 2;
s3, replacing the amino group of the thiophene precursor 2 with a bromine atom to obtain a raw material (I).
Further, the step of S1 is that alkyl ketone, malononitrile, sulfur and catalytic amount of morpholine are mixed, then heated for reaction, after the reaction is finished, water is used for washing and separating solid products, and the thiophene precursor 1 is obtained after recrystallization.
Further, the step of S2 is to react the thiophene precursor 1 with liquid bromine under the conditions of inert environment and ice water bath to obtain the thiophene precursor 2.
Further, the step S3 is that copper bromide is added into the thiophene precursor 2 under the inert environment, and then the tertbutyl nitrite is added dropwise into the thiophene precursor under the ice-water bath condition; after the reaction, a carbonate solution is added, extracted, concentrated and passed through a column to obtain a raw material (I).
It is another object of the present invention to provide the use of the above-described conjugated polymers based on alkyl-substituted thiophenes in organic solar cells.
The invention has the beneficial effects that:
1. the invention discloses a novel conjugated polymer based on alkyl substituted thiophene, which is a copolymer of an alkyl thiophene unit containing cyano and a benzene dithiophene unit with a branched chain connected with a halogen group, wherein the introduction method of alkyl is simple and convenient, and the solubility and the processability of the conjugated polymer can be well regulated.
2. In the novel conjugated polymer donor material based on alkyl substituted thiophene, halogen atoms have strong electron-withdrawing induction effect, and the halogen atoms are introduced into the conjugated polymer, so that the HOMO energy level of the conjugated polymer can be further reduced, the effect of obviously improving the open-circuit voltage of a device is achieved, and compared with the traditional donor material, the photovoltaic performance of the conjugated polymer donor material is obviously improved, and the conjugated polymer donor material has good commercialized prospect.
3. The novel conjugated polymer donor material based on alkyl substituted thiophene has the advantages of simple synthesis method, high yield and lower cost.
Drawings
FIG. 1 shows the synthetic route pattern of the raw material (I) in examples 1 to 3.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples are set forth. The starting materials, reactions and workup procedures used in the examples are those commonly practiced in the market and known to those skilled in the art unless otherwise indicated.
In an embodiment of the present invention, a method of manufacturing a semiconductor device,
the raw material (II) in the examples and the comparative examples is a series of products, and the specific alkyl chain structure on the thiophene branched chain of the raw material (II) in each example is different, or the halogen substitution condition on the thiophene branched chain is different, and the raw material (II) is purchased from Shenzhen Rui photoelectric materials technology Co.
Example 1
A method for preparing a conjugated polymer based on alkyl-substituted thiophene, comprising the steps of:
preparation of raw material (I):
s1, mixing acetone (1), malononitrile, elemental sulfur (1:1:1, n/n/n) and a catalytic amount of morpholine in sufficient ethanol, heating to 70 ℃, and stirring for reaction for 3 hours; after the reaction was completed, the system was cooled to room temperature, deionized water was then added, and the solid product was isolated by filtration, and after collecting the solid product, it was recrystallized from ethanol to obtain compound (3) (purity=98%; yield=90%).
S2, dissolving the compound (3) in enough ethanol under the nitrogen atmosphere, and then slowly dropwise adding bromine water which is 1.2 times of the amount of the compound (3) in an ice water bath by using a dropping funnel, and reacting for 2 hours at room temperature to obtain a solution containing the compound (4). The resulting solution was directly subjected to the next step without purification.
S3, adding copper bromide powder which is 1.2 times of the amount of the substances of the compound (3) into the solution containing the compound (4) under the ice water bath condition, and stirring for 30min; then, the tert-butyl nitrite which is 1.2 times the amount of the substance of the compound (3) was slowly added dropwise with a dropping funnel, and after stirring for 30 minutes, the reaction was allowed to warm to room temperature and stirred for 1 hour. After the reaction is finished, the mixed solution is slowly dripped into the saturated K 2 CO 3 In solution, then extracted with dichloromethane, extracted with Na 2 SO 4 The combined organic layers were dried and evaporated to dryness. The residue was purified on silica gel eluting with petroleum ether-dichloromethane (7:3) to give starting material (I).
Preparation of conjugated polymers based on alkyl-substituted thiophenes:
the method is carried out by Stille polymerization, and the chemical equation is as follows:
under the nitrogen atmosphere, the raw materials (I) and (II) are strictly put into a three-mouth bottle according to the mass ratio of 1:1, a sufficient amount of anhydrous toluene is added, and Stille polymerization is carried out for 72 hours at 120 ℃ under the action of catalytic amount of palladium acetate, so that the product is obtained.
Example 2
S1, mixing 2-hexanone (1), malononitrile, elemental sulfur (1:1:1, n/n/n) and a catalytic amount of morpholine in sufficient ethanol, heating to 70 ℃, and stirring for reaction for 3 hours; after the reaction was completed, the system was cooled to room temperature, deionized water was then added, and the solid product was isolated by filtration, and after collecting the solid product, it was recrystallized from ethanol to obtain compound (3) (purity=98%; yield=90%).
S2, dissolving the compound (3) in enough ethanol under the nitrogen atmosphere, and then slowly dropwise adding bromine water which is 1 time of the amount of the compound (3) in an ice water bath condition by using a dropping funnel, and reacting for 2 hours at room temperature to obtain a solution containing the compound (4). The resulting solution was directly subjected to the next step without purification.
S3, adding copper bromide powder which is 1 time of the amount of the substances of the compound (3) into the solution containing the compound (4) under the ice water bath condition, and stirring for 30min; then, the tert-butyl nitrite which is 1 time the amount of the substance of the compound (3) was slowly added dropwise with a dropping funnel, and after stirring for 30 minutes, the reaction was allowed to warm to room temperature and stirred for 1 hour. After the reaction is finished, the mixed solution is slowly dripped into the saturated K 2 CO 3 In solution, then extracted with dichloromethane, extracted with Na 2 SO 4 The combined organic layers were dried and evaporated to dryness. The residue was purified on silica gel eluting with petroleum ether-dichloromethane (7:3) to give starting material (I).
Preparation of conjugated polymers based on alkyl-substituted thiophenes:
the method is carried out by Stille polymerization, and the chemical equation is as follows:
under the nitrogen atmosphere, the raw materials (I) and (II) are strictly put into a three-mouth bottle according to the mass ratio of 1:1, a sufficient amount of anhydrous toluene is added, and Stille polymerization is carried out for 48 hours at 100 ℃ under the action of catalytic amount of palladium acetate, so that the product is obtained.
The structure of the raw material (I) in example 2 is similar to that of the raw material (I) in example 1; the structure of the raw material (II) is similar to that of the raw material (II) in example 1, and only the specific alkyl chain structure on the thiophene branched chain is different.
Example 3
S1, mixing 2-tridecanone (1), malononitrile, elemental sulfur (1:1:1, n/n/n) and a catalytic amount of morpholine in sufficient ethanol, heating to 70 ℃, and stirring for reaction for 3 hours; after the reaction was completed, the system was cooled to room temperature, deionized water was then added, and the solid product was isolated by filtration, and after collecting the solid product, it was recrystallized from ethanol to obtain compound (3) (purity=98%; yield=90%).
S2, dissolving the compound (3) in enough ethanol under the nitrogen atmosphere, and then slowly dropwise adding bromine water which is 1 time of the amount of the compound (3) in an ice water bath condition by using a dropping funnel, and reacting for 2 hours at room temperature to obtain a solution containing the compound (4). The resulting solution was directly subjected to the next step without purification.
S3, adding copper bromide powder which is 1.2 times of the amount of the substances of the compound (3) into the solution containing the compound (4) under the ice water bath condition, and stirring for 30min; then, the tert-butyl nitrite which is 1.2 times the amount of the substance of the compound (3) was slowly added dropwise with a dropping funnel, and after stirring for 30 minutes, the reaction was allowed to warm to room temperature and stirred for 1 hour. After the reaction is finished, the mixed solution is slowly dripped into the saturated K 2 CO 3 In solution, then extracted with dichloromethane, extracted with Na 2 SO 4 The combined organic layers were dried and evaporated to dryness. The residue was purified on silica gel eluting with petroleum ether-dichloromethane (7:3) to give starting material (I).
Preparation of conjugated polymers based on alkyl-substituted thiophenes:
the method is carried out by Stille polymerization, and the chemical equation is as follows:
under the nitrogen atmosphere, the raw materials (I) and (II) are strictly put into a three-mouth bottle according to the mass ratio of 1:1, a sufficient amount of anhydrous toluene is added, and Stille polymerization is carried out for 24 hours at 100 ℃ under the action of catalytic amount of palladium acetate, so that the product is obtained.
The structure of the raw material (I) in example 3 is similar to that of the raw material (I) in example 1; the structure of the raw material (II) is similar to that of the raw material (II) in example 1, and only the specific alkyl chain structure on the thiophene branched chain is different.
Comparative example 1
The conjugated polymer of comparative example 1 was prepared in the same manner as in example 1, except that the reaction substrates, namely, raw material (I) and raw material (II), were different:
the method is carried out by Stille polymerization, and the chemical equation is as follows:
under the nitrogen atmosphere, the raw materials (I) and (II) are strictly put into a three-mouth bottle according to the mass ratio of 1:1, a sufficient amount of anhydrous toluene is added, and Stille polymerization is carried out for 24 hours at 100 ℃ under the action of catalytic amount of palladium acetate, so as to obtain a comparative polymer.
The structure of the raw material (I) in comparative example 1 is similar to that of the raw material (I) in example 1, except that the methyl group on the thiophene ring is substituted with a hydrogen atom; the structure of the raw material (II) was the same as that of the raw material (II) in example 1.
Comparative example 2
The conjugated polymer of comparative example 2 was prepared in the same manner as in example 1, except that the reaction substrates, namely, raw material (I) and raw material (II), were different:
the method is carried out by Stille polymerization, and the chemical equation is as follows:
the structure of the raw material (I) in comparative example 2 is the same as that of the raw material (I) in example 1; the structure of the raw material (II) is similar to that of the raw material (II) in example 1, except that halogen on the thiophene branch is replaced with a hydrogen atom.
Test case
The organic solar cell devices of examples 1 to 3 and comparative examples 1 to 2 described above, in which the conjugated polymer based on alkyl-substituted thiophene was used as the active layer P-type material, were subjected to photovoltaic performance test. The conditions tested were the polymer donor examples 1-3, the polymers of comparative examples 1-2, small molecule acceptor Y6 (1:1.2, m/m, chloroform solvent, and 0.5wt% CN added). Y6 is available as stock from commercial resources, synopsis organic phototechnology (beijing). Prior to BHJ solar cell testing, the fundamental properties of the material, such as energy level and absorption spectrum, were measured by air photoelectron spectroscopy (PESA) and ultraviolet-visible absorption spectroscopy (UV-vis), respectively. As shown in fig. 1, the device structure is ITO (135 nm)/PEDOT: PSS (40 nm))/polymer: y6 (100 nm)/PDINN (5 nm)/Ag (100 nm), wherein PEDOT: PSS and PDINN are a hole transport layer and an electron transport layer, respectively.
Methods of making organic solar cell devices are conventional means well known to those skilled in the art.
The experimentally obtained current-voltage (J-V) curve was operated by a computer-controlled Keithley2400sourcemeter program at 100mWcm -2 The next (1 sun, AM1.5G spectrum, calibrated by standard silicon solar cells before testing, manufactured by San-EIelectric Co, ltd., japan) was tested and a square light-passing hole mold was used with an accurate area of 0.04cm 2 To define the device active area before the PCE is obtained. External Quantum Efficiency (EQE) measurements were made by the QE-C system (Entittech, taiwan, china). The EQE system was calibrated with silicon photodiodes prior to measurement.
The results obtained are shown in Table 1.
Table 1 photovoltaic performance parameters of the organic solar cell devices in examples 1-3, comparative examples 1-2
4. The above data indicate that: different alkyl chains are introduced into the material, so that the solubility and the processability of the conjugated polymer can be well regulated, and meanwhile, the HOMO energy level of the conjugated polymer can be reduced due to the introduction of halogen atoms, so that the effect of obviously improving the open-circuit voltage of the device is achieved, the photovoltaic performance of the device is effectively enhanced, the energy conversion efficiency is greatly improved, and the cost of the organic solar cell device is reduced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
1. A conjugated polymer based on alkyl-substituted thiophene, characterized in that the conjugated polymer based on alkyl-substituted thiophene has the following structural general formula:
；
wherein X is a halogen atom;
R 1 is a C1-C22 alkyl chain or alkyl chain derivative;
R 2 is a C1-C22 alkyl chain or alkyl chain derivative;
in the alkyl chain derivative, one or more carbon atoms are substituted by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups or nitro groups; or one or more hydrogen atoms are substituted with a halogen atom, an oxygen atom, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, an ester group, a cyano group, or a nitro group;
n is a positive integer.
2. The alkyl-substituted thiophene-based conjugated polymer according to claim 1, wherein the R 1 Selected from the group consisting of C1-C22 linear alkyl chains.
3. The alkyl-substituted thiophene-based conjugated polymer according to claim 1, wherein the R 2 A branched alkyl chain selected from C1-C22.
4. The conjugated polymer based on alkyl-substituted thiophene according to claim 3, wherein the R 2 Has the following structural general formula:
；
wherein R is 3 And R is 4 Independently selected from the group consisting of C1-C22 alkyl chains.
5. The method for preparing the conjugated polymer based on the alkyl-substituted thiophene according to any one of claims 1 to 4, wherein the method for preparing the conjugated polymer based on the alkyl-substituted thiophene comprises the following steps:
the raw material (I) and the raw material (II) are polymerized by Stille;
wherein the raw material (I) has the following structural general formula:
；
the raw material (II) has the following structural general formula:
；
wherein X is a halogen atom;
R 1 is a C1-C22 alkyl chain or alkyl chain derivative;
R 2 is a C1-C22 alkyl chain or alkyl chain derivative;
in the alkyl chain derivative, one or more carbon atoms are substituted by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups or nitro groups; or one or more hydrogen atoms are substituted with a halogen atom, an oxygen atom, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an amino group, a carbonyl group, a carboxyl group, an ester group, a cyano group, or a nitro group.
6. The process for the preparation of conjugated polymers based on alkyl-substituted thiophenes according to claim 5, wherein said starting material (I) is prepared as follows:
s1, synthesizing a thiophene precursor 1 through Gewald reaction;
s2, brominating the thiophene precursor 1 to obtain a thiophene precursor 2;
s3, replacing amino groups of the thiophene precursor 2 with bromine atoms to obtain a raw material (I);
mixing alkyl ketone, malononitrile, sulfur and catalytic amount of morpholine, then heating for reaction, washing with water and separating solid products after the reaction is finished, and recrystallizing to obtain the thiophene precursor 1;
the step S2 is that the thiophene precursor 1 reacts with liquid bromine under the conditions of inert environment and ice water bath to obtain a thiophene precursor 2;
the step S3 is that copper bromide is added into the thiophene precursor 2 under the inert environment, and then the tertbutyl nitrite is added dropwise into the thiophene precursor under the ice-water bath condition; after the reaction, a carbonate solution is added, extracted, concentrated and passed through a column to obtain a raw material (I).
7. Use of the conjugated polymers based on alkyl-substituted thiophenes according to any of claims 1 to 4 in organic solar cells.
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