Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer

A bis-thienylpyrrole, 4-c technology is applied in the field of chemical preparation of high molecular polymer materials, which can solve the problems of poor stability of raw material organometallic reagents, inability to be prepared, poisoning human and animal health, etc. Environmental friendliness, avoidance of organometallic waste, and beneficial effects on industrial production

Inactive Publication Date: 2015-05-20
SICHUAN UNIV
View PDF4 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this type of traditional coupling reaction has obvious disadvantages: (1) From the starting raw material aromatic (hetero) ring to the coupling product, there are at least three organic synthesis steps, involving the synthesis of intermediate C-X compounds and the synthesis of C-M compounds. Synthesis and coupling reaction, many steps, long route, complex organic synthesis operation, harsh conditions, and low total yield; (2) one of the reaction intermediates is an organometallic reagent, which is difficult to prepare, except for raw materials (boric acid reagent, organic tin Reagents, etc.) are expensive, the steps are cumbersome, the conditions are harsh (such as anhydrous and oxygen-free environment, etc.), the operation difficulty increases, the total yield is also reduced, and the cost is increased; at the same time, the raw material organometallic reagents have poor stability, and some cannot withstand acceptance. Some of the following coupling reactions cannot even be prepared and exist stably, which greatly limits the breadth of raw materials and products, and limits the possibility of molecular modification and property adjustment of materials; (3) traditional coupling reactions It will produce an equivalent amount of metal organic reagent waste, such as tin reagent waste, poisoning human and animal health and causing environmental pollution

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer
  • Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer
  • Preparation method of bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Step (1): 2,5-bis(2-octyldodecyl)-3,6-bis(2-thienyl)pyrrolo[3,4-c]pyrrole-1,4-dione ( 1.72g, 2.0mmol), 4,7-dibromo-2,1,3-benzothiadiazole (588mg, 2.0mmol), the catalyst is palladium acetate (22mg, 0.1mmol), and the ligand is triphenylphosphine (105mg, 0.4mmol), the additive is pivalic acid (204mg, 2.0mmol), the base is potassium carbonate (829mg, 6.0mmol), the solvent is N,N-dimethylacetamide (10mL), the above reagents are added to the reaction In an anhydrous and oxygen-free condition, stir evenly and then heat to 120°C, and react for 24 hours;

[0036] Step (2): After the reaction is completed, cool the reaction bottle to room temperature, add a small amount of chloroform and stir evenly, pour into the mixed system of methanol and water, stir, and filter. The collected solids were placed in a Soxhlet extractor, extracted with methanol, acetone, and n-hexane in sequence, and the remaining solids were extracted with chloroform, the chloroform solution was collected, co...

Embodiment 2

[0038] Step (1): 2,5-bis(2-octyldodecyl)-3,6-bis(2-(4-fluorothiophene)yl)pyrrolo[3,4-c]pyrrole-1, 4-diketone (1.79g, 2.0mmol), 4,7-dibromo-5,6-dimethyl-2,1,3-benzothiadiazole (515mg, 1.6mmol), the catalyst is trans- Bis(μ-acetic acid)bis[o-(bis(o-tolylphosphino)benzyl]dipalladium(II) (18.8mg, 0.02mmol), the ligand is tri(o-methoxyphenyl)phosphine ( 28.2mg, 0.08mmol), the additive is adamantaneic acid (541mg, 3.0mmol), the base is cesium carbonate (2.28g, 7.0mmol), and the solvent is tetrahydrofuran (4mL). Stir evenly under oxygen conditions, heat to 90°C, and react for 48 hours;

[0039] Step (2): the operation step (2) of reference example 1 obtains target multipolymer 1.39g, productive rate is 82%, M n =14600Da, M w / M n =4.67. Proton nuclear magnetic resonance spectrum (deuterated chloroform is solvent, Bruker AMX-400 nuclear magnetic resonance instrument) 1 H NMR (400MHz, CDCl 3 ): 1 H NMR (400MHz, CDCl 3 ): δ=0.85 (br, 12H), 1.20-1.60 (m, 64H), 2.05-2.21 (m, 8H),...

Embodiment 3

[0041]Step (1): 2,5-bis(2-(2-ethoxy)ethoxy)methyl)-3,6-bis(2-(3,4-dimethylthienyl))pyrrolo [3,4-c]pyrrole-1,4-dione (1.12g, 2.0mmol), 2,7-dibromo-N-(2-octyldodecyl)carbazole (1.51g, 2.5mmol ), the catalyst is palladium chloride (7.1mg, 0.04mmol), the ligand is tricyclohexylphosphine tetrafluoroborate (14.7mg, 0.04mmol), no additives are added, the base is potassium phosphate (849mg, 4.0mmol), The solvent is N, N-dimethylacetamide / xylene = 1:1 (v / v, 20mL). Add the above reagents into the reactor, stir evenly under anhydrous and oxygen-free conditions, then heat to 135°C, and react 3 hours;

[0042] Step (2): the operation step (2) of reference example 1 obtains target multipolymer 1.73g, productive rate is 86%, M n =32000Da, M w / M n = 3.85. Proton nuclear magnetic resonance spectrum (deuterated chloroform is solvent, Bruker AMX-400 nuclear magnetic resonance instrument) 1 H NMR (400MHz, CDCl 3 ): δ=0.79 (br, 6H), 1.16-1.61 (m, 38H), 1.96-2.35 (m, 13H), 3.20-4.41 (m, 18H...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The invention relates to preparation method of a bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone and (hybrid) arene copolymer, which belongs to the technical field of chemical preparation of high-molecular polymer materials. According to the preparation method, under an appropriate condition, bis-thienyl pyrrolo-[3,4-c] pyrrole-1,4-diketone as a raw material A and a dibromo-(hybrid) aromatic compound as a raw material B are directly react to obtain a target copolymer. Compared with the traditional method, the preparation method provided by the invention has obvious advantages, prevents the preparation link of an organic metal reagent, decreases the preparation steps, increases the overall yield, reduces the cost, prevents a great amount of toxic and harmful organic metal reagent wastes from being generated and is more conductive to the industrialized production.

Description

technical field [0001] The invention relates to a preparation method of a bisthienylpyrrolo[3,4-c]pyrrole-1,4-dione and (hetero)arene copolymer, which belongs to the chemical preparation technology of high molecular polymer materials. Background technique [0002] Pyrrolo[3,4-c]pyrrole-1,4-dione polymers have a special planar molecular structure, which can form good intermolecular packing, and have unique optoelectronic properties, such as low energy gap, electron / hole High mobility, large molar absorptivity, especially strong absorption in the near-infrared spectral region, strong fluorescence emission, high quantum yield, and good light and thermal stability, so it is widely used in biochemistry, medicine, analytical chemistry and materials Science and other fields have been widely concerned and applied. In recent years, the use of this type of polymer to develop various photovoltaic functional materials has become a very active field at home and abroad. For example, in ...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Patents(China)
IPC IPC(8): C08G61/12
Inventor 吴迪郭强游劲松董嘉兴
Owner SICHUAN UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products