Diamine monomer containing carbazole structure and having high planarity, synthetic method and application thereof

A technology of diamine monomer and synthesis method, applied in the field of material science, to achieve the effects of easy purification, strong interaction force and high yield

Active Publication Date: 2016-01-13
HUNAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The focus of the research on this system is the design and synthesis of a highly planar new diamine monomer containing a carbazole structure. Howev

Method used

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  • Diamine monomer containing carbazole structure and having high planarity, synthetic method and application thereof
  • Diamine monomer containing carbazole structure and having high planarity, synthetic method and application thereof
  • Diamine monomer containing carbazole structure and having high planarity, synthetic method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0070] Synthesis of N1,N1'-(9-methyl-9H-carbazole-3,6-diyl)bis(benzene-1,4-diamine):

[0071] Synthetic intermediate 3,6-dibromo-9-methyl-9H-carbazole:

[0072] Pour 3.25g (0.01mol) of 2,7-dibromocarbazole (3,6-dibromo-9H-carbazole), 150ml of DMF, and 1.5g of NaH suspension into a 250ml three-necked flask, and add 4ml of iodomethane successively, Methyl iodide was added for more than 10 minutes, protected by argon, and refluxed for 18 hours. The reaction solution was poured into ice water, a large amount of precipitation was precipitated, filtered with suction, washed with water, and a white solid was obtained. It was dried in vacuum at 80°C for 24 hours, and the yield was about 90%. The intermediate structure is as follows:

[0073]

[0074] Synthetic intermediate 9-methyl-9H-carbazole-3,6-diamine:

[0075] Add 3.39g (0.01mol) of 3,6-dibromo-9-methyl-9H-carbazole, appropriate amount of cuprous oxide, 50ml of NMP, 13ml of ammonia water (29%, 0.2mol) into a 200ml pressure ...

Embodiment 2

[0083] Synthesis of N3,N6-bis(4-aminophenyl)-9H-carbazole-3,6-dicarboxamide:

[0084]

[0085] Synthetic intermediate 9H-carbazole-3,6-dicarbonitrile:

[0086] Add 3.25g (0.01mol) 3,6-dibromo-9H-carbazole, 2.762g (0.05mol) cyanocopper, and 50ml of dry NMP into a 500ml three-necked flask, reflux at 140°C for 24h, then add water (180mL), HCl ( 60 mL) and FeCl3 (4.19 g, 25.8 mmol) were poured into the reaction solution and stirred for 1 h, cooled to room temperature, filtered to obtain a brown precipitate, and washed with water, the obtained solid was redissolved in dichloromethane and washed with water, and the solvent was removed under reduced pressure to obtain a crude product It was a brown solid, which was triturated with methanol to give the desired product 9H-carbazole-3,6-dicarbonitrile as an off-white solid 0.65 g, 31% yield. The intermediate structure is as follows:

[0087]

[0088] Synthetic intermediate 9H-carbazole-3,6-dicarboxylic acid:

[0089] Add 2.17g ...

Embodiment 3

[0100] Synthesis of 4,4'-((9H-carbazole-3,6-diyl)bis(oxy))dianiline:

[0101]

[0102] Synthesis of intermediate 3,6-bis(4-nitrophenoxy)-9H-carbazole:

[0103] Add 3.250g (0.01mol) 2,7-dichloro-9H-carbazole and 3.478g (0.025mol) 4-nitrophenol into a 500ml three-necked flask, use DMF as a solvent, add an appropriate amount of NaOH, heat the oil bath to 110°C and add An appropriate amount of CuI was refluxed for 22 hours, and the reaction solution was poured into water, and a large amount of precipitates precipitated out. Filter with a funnel, evaporate the solvent under reduced pressure. The product was purified by column chromatography using silica gel as the stationary phase. The product was collected and spin-dried, and dried in vacuum at 80°C for 24 hours to obtain 2.5 g of 3,6-bis(4-nitrophenoxy)-9H-carbazole as a light yellow solid. The yield was was 71.5%. The intermediate structure is as follows:

[0104]

[0105] Synthesis of 4,4'-((9H-carbazole-3,6-diyl)bis(...

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Abstract

The invention discloses a diamine monomer containing a carbazole structure and having a high planarity, a synthetic method and an application thereof. In the method, the diamine is directly prepared from dihalogenated carbazole through ammoniation by liquid ammonia; or is directly prepared through a Suzuki reaction; or is directly prepared by performing cyanidation, hydrolysis and acylating chlorination to the dihalogenated carbazole to synthesize diacyl chlorocarbazole and then performing a reaction to the diacyl chlorocarbazole with a hydroxyl group or an amino group to form an ester bond or an amido bond; or is prepared by performing a Ullmann coupling reaction with the halogen atoms in the dihalogenated carbazole to form an ether bond, secondary amine or the like and finally reducing the dinitro group. The diamine synthetic process is simple, is simple in purification and is suitable for industrial production. A minimum energy state 3D molecular structure of the diamine monomer is high in planarity so that the diamine monomer can be used for preparing a high barrier polymer which is strong in interaction force among molecular chains and is small in free volume. The diamine monomer can be used for preparing high-performance and functionalized polyamides, polyimides, polyamideimides, polyesterimides and such polymers.

Description

technical field [0001] The invention relates to the field of material science, in particular to a highly planar diamine monomer containing a carbazole structure and a synthesis method thereof. This monomer can be used to synthesize polymers such as polyamide, polyimide, polyamideimide and polyesterimide with high barrier and functionalization. Background technique [0002] The most promising new generation of information display technology at present - organic electroluminescent device (OLED), which has all solid state, active light emission, high brightness, high contrast, ultra-thin, low power consumption, no viewing angle limit, fast response speed , wide operating temperature range and flexible display and many other incomparable advantages are considered to be the focus of the development of the world's information industry in the next 30 years. The key to OLED industrialization lies in "expanding size, reducing cost, increasing lifespan, and improving color". Only b...

Claims

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Application Information

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IPC IPC(8): C07D209/88C08G73/14C08G73/16C08G73/10C08G69/00
CPCC07D209/88C08G69/00C08G73/10C08G73/14C08G73/16
Inventor 刘亦武黄杰谭井华曾义张海良刘跃军魏珊珊向贤伟
Owner HUNAN UNIV OF TECH
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