Copolymer comprising silafluorene and thiophene pyrroledione units and preparation method as well as application thereof

Abstract

The invention relates to the technical field of organic materials, and provides a copolymer comprising silafluorene and thiophene pyrroledione units. The copolymer is polymer which is expressed by a structural formula (I), wherein R1, R2 and R3 are selected from C1-C20 alkyl groups; and n is an integer of 1-100. The invention also provides a preparation method and application of the copolymer comprising the silafluorene and thiophene pyrroledione units. In the copolymer, the silafluorene and thiophene pyrroledione units are organically combined together to form an extremely strong donor-receptor structure, so that the stability of a copolymer material is favorably improved, energy band gap of the material is favorably reduced, the sunlight absorption range is expanded, and the photoelectric conversion efficiency is increased.

Description

technical field

[0001] The invention belongs to the technical field of organic materials, and in particular relates to a copolymer containing silicon fluorene and diketone thienylpyrrole units, its preparation method and application. Background technique

[0002] Today's world economy is mainly based on fossil energy, such as coal, oil and natural gas. However, these non-renewable fossil energy sources are constantly being exhausted. Since the beginning of the 21st century, global energy issues and the ensuing environmental pollution and climate warming have become increasingly prominent and gradually intensified. Solar energy is considered to be one of the most promising renewable energy sources because of its widespread and vast distribution, large amount of resources, no pollution, cleanliness, safety, and easy access.

[0003] In order to make full use of the energy irradiated by sunlight, people continue to develop new materials that can absorb sunlight. Among them, i...

Examples

preparation example Construction

[0029] see figure 1 , the preparation method of the above-mentioned copolymer containing silicon fluorene and thienylpyrrole diketone unit comprises the steps:

[0030] S10, providing compounds A and B represented by the following structural formula,

[0031] Where: R 1 , R 2 , R 3 from C 1 -C 20 the alkyl group;

[0032] S20, in an organic solvent, the compound B is brominated with a brominating agent to obtain a dibrominated product;

[0033] S30, in catalyst, alkali solution and organic solvent, carry out Suzuki reaction with compound A and dibromo product, obtain the copolymer containing silicon fluorene and thienopyrrole dione unit represented by following structural formula (I):

[0034] In the formula, n is an integer of 1-100.

[0035] In step S10, compounds A and B can be directly purchased from the market or prepared by existing synthetic methods. Among them, the structures of compounds A and B are basically the same as those described above for the copo...

Embodiment 1

[0053] The copolymer (I 1 ), R 1 , R 2 , R 3 Both are methyl, and its structural formula is as follows:

[0054]

[0055] In the above formula, n=20.

[0056] The copolymer of the present embodiment (I 1 ) preparation comprises the following specific steps:

[0057] 1. The preparation of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-9,9-dimethylsilfluorene, compound A A concrete example, its structural formula is as follows:

[0058]

[0059]The specific preparation process is as follows: at -100°C under nitrogen, add 40.00mL (1.00M) n-butyllithium solution to a solution containing 3.68g 2,7-dibromo-9,9-dimethylsilafluorene and 120mL In the tetrahydrofuran reactor, after stirring for 2 hours, slowly add 4.33mL 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane dropwise to restore to Stirring was continued for 48 hours at room temperature. After the reaction, the reaction solution was poured into water, extracted with ether, dried over anhydrous magnesium sul...

Embodiment 2

[0073] The copolymer (I 1 ), R 1 , R 2 , R 3 Both are C 8 h 17 , its structural formula is as follows:

[0074] In the above formula, n=58.

[0075] The copolymer of the present embodiment (I 2 ) preparation comprises the following specific steps:

[0076] 1. The preparation of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-9,9-dioctylsilfluorene, compound A A concrete example, its structural formula is as follows:

[0077]

[0078] The specific preparation process is as follows: Add 10.00mL (2.00M) n-butyllithium solution with a syringe to 5.65g 2,7-dibromo-9,9-dioctylsilafluorene at -78°C under nitrogen gas and 100.00mL tetrahydrofuran in a two-necked flask, after stirring for 2 hours, slowly add 4.90mL 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane , returned to room temperature, and continued to stir for 33 hours. After the reaction, the reaction solution was poured into water, extracted with ether, dried over anhydrous magnesium sulfate, rotary evap...

technical field

[0001] The invention belongs to the technical field of organic materials, and in particular relates to a copolymer containing silicon fluorene and diketone thienylpyrrole units, its preparation method and application. Background technique

[0002] Today's world economy is mainly based on fossil energy, such as coal, oil and natural gas. However, these non-renewable fossil energy sources are constantly being exhausted. Since the beginning of the 21st century, global energy issues and the ensuing environmental pollution and climate warming have become increasingly prominent and gradually intensified. Solar energy is considered to be one of the most promising renewable energy sources because of its widespread and vast distribution, large amount of resources, no pollution, cleanliness, safety, and easy access.

[0003] In order to make full use of the energy irradiated by sunlight, people continue to develop new materials that can absorb sunlight. Among them, i...

Examples

preparation example Construction

[0029] see figure 1 , the preparation method of the above-mentioned copolymer containing silicon fluorene and thienylpyrrole diketone unit comprises the steps:

[0030] S10, providing compounds A and B represented by the following structural formula,

[0031] Where: R 1 , R 2 , R 3 from C 1 -C 20 the alkyl group;

[0032] S20, in an organic solvent, the compound B is brominated with a brominating agent to obtain a dibrominated product;

[0033] S30, in catalyst, alkali solution and organic solvent, carry out Suzuki reaction with compound A and dibromo product, obtain the copolymer containing silicon fluorene and thienopyrrole dione unit represented by following structural formula (I):

[0034] In the formula, n is an integer of 1-100.

[0035] In step S10, compounds A and B can be directly purchased from the market or prepared by existing synthetic methods. Among them, the structures of compounds A and B are basically the same as those described above for the copo...

Embodiment 1

[0053] The copolymer (I 1 ), R 1 , R 2 , R 3 Both are methyl, and its structural formula is as follows:

[0054]

[0055] In the above formula, n=20.

[0056] The copolymer of the present embodiment (I 1 ) preparation comprises the following specific steps:

[0057] 1. The preparation of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-9,9-dimethylsilfluorene, compound A A concrete example, its structural formula is as follows:

[0058]

[0059]The specific preparation process is as follows: at -100°C under nitrogen, add 40.00mL (1.00M) n-butyllithium solution to a solution containing 3.68g 2,7-dibromo-9,9-dimethylsilafluorene and 120mL In the tetrahydrofuran reactor, after stirring for 2 hours, slowly add 4.33mL 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane dropwise to restore to Stirring was continued for 48 hours at room temperature. After the reaction, the reaction solution was poured into water, extracted with ether, dried over anhydrous magnesium sul...

Embodiment 2

[0073] The copolymer (I 1 ), R 1 , R 2 , R 3 Both are C 8 h 17 , its structural formula is as follows:

[0074] In the above formula, n=58.

[0075] The copolymer of the present embodiment (I 2 ) preparation comprises the following specific steps:

[0076] 1. The preparation of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-9,9-dioctylsilfluorene, compound A A concrete example, its structural formula is as follows:

[0077]

[0078] The specific preparation process is as follows: Add 10.00mL (2.00M) n-butyllithium solution with a syringe to 5.65g 2,7-dibromo-9,9-dioctylsilafluorene at -78°C under nitrogen gas and 100.00mL tetrahydrofuran in a two-necked flask, after stirring for 2 hours, slowly add 4.90mL 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane , returned to room temperature, and continued to stir for 33 hours. After the reaction, the reaction solution was poured into water, extracted with ether, dried over anhydrous magnesium sulfate, rotary evap...

Images