Fluorine-containing functional diamine monomer with large conjugated structure as well as synthesis method and application thereof

Abstract

The invention discloses a fluorine-containing functional diamine monomer with a large conjugated structure as well as a synthesis method and an application thereof. The synthesis method comprises the following steps of: firstly allowing di-halogenated fluorine to react with halogenated nitrobenzene, linking halogen atoms with other chemical groups to form a large conjugated system, and finally reducing binitro into diamine; or firstly carrying out a chemical coupling reaction between two active hydrogen atoms in fluorine to form the large conjugated structure, carrying out a Suzuki reaction on the large conjugated structure and two halogen atoms to obtain the diamine, and finally obtaining the novel fluorine-containing functional diamine monomer. By means of the specific structure of the diamine monomer, the polymer obtained by the diamine monomer has the advantage of good solubility, and the diamine monomer and the polymer can also achieve certain photoelectric properties; and the synthesis method has the advantages of simple process and easy purification procedure, thus being applicable to industrial production. The fluorine-containing functional diamine monomer has obvious characteristics of luminescence aggregation and induction, thus the diamine monomer can be used for synthesizing high-performance functional polymers such as polyamide, polyimide, polyamideimide, polyesterimide and the like.

Description

technical field

[0001] The invention relates to the field of material science, in particular to a fluorene-containing functional diamine monomer with a large conjugated system and a synthesis method thereof. The diamine monomer can be used to synthesize such as polyamide, polyimide, polyamideimide High performance, functional polymers such as amines and polyesterimides. technical background

[0002] Polyimide is one of the best heat-resistant varieties among engineering plastics that have been industrialized at present. It has outstanding properties unmatched by other materials, such as high mechanical strength, good high and low temperature resistance, excellent dielectric properties, and film-forming properties. OK wait. Since the development and industrialization of DuPont in the United States in the 1960s, it has been applied in various fields, especially in aerospace, aviation, microelectronics and military fields. Since polyimide is generally insoluble in organic sol...

Examples

Embodiment 1

[0044] Synthesis of 4,4'-(2,7-bis(4-(trifluoromethyl)phenyl)-9H-fluorene-9,9-diyl)dianiline:

[0045]

[0046] (1) Synthesis of intermediate 2,7-dibromo-9,9-bis(4-nitrophenyl)-9H-fluorene:

[0047] 32.401g (0.1mol) of 2,7-dibromofluorene (2,7-dibromo-9H-fluorene), 11.2g (0.1mol) of potassium tert-butoxide (t-BuOK) and 42.33g (0.3mol) of Add fluoronitrobenzene (1-fluoro-4-nitrobenzene) into a 500ml three-necked flask, use N,N-dimethylformamide (DMF) as a solvent, stir magnetically and pass argon gas, heat and reflux in an oil bath at 110°C for 24h , Pour the reaction solution into ice water, let it stand for 3h, and obtain a yellow solid by suction filtration, dissolve the yellow solid in absolute ethanol, and then crystallize at low temperature, filter the crystallized solid with suction to obtain a light yellow crystal, and in vacuo at 60°C After drying for 10 h, 51.5 g of the light yellow intermediate product 2,7-dibromo-9,9-bis(4-nitrophenyl)-9H-fluorene was obtained, w...

Embodiment 2

[0055] Synthesis of 4,4'-(9,9-bis(4-aminophenyl)-9H-fluorene-2,7-diyl)diphenol:

[0056]

[0057] (1) Synthesize intermediate 2,7-dibromo-9,9-bis(4-nitrophenyl)-9H-fluorene according to Example 1;

[0058] (2) Synthesis of intermediate 4,4'-(9,9-bis(4-nitrophenyl)-9H-fluorene-2,7-diyl)diphenol:

[0059] Add 11.124g (0.02mol) 2,7-dibromo-9,9-bis(4-nitrophenyl)-9H-fluorene and 6.8965g (0.05mol) 4-hydroxyphenylboronic acid to a 500ml three-necked flask Add 250ml of tetrahydrofuran (THF), and then add 75ml of 2mol / L potassium carbonate solution, stir magnetically and pass argon, heat the oil bath to 70°C, add 0.02g tetrakistriphenylpalladium, and reflux for 24h. The reaction liquid was poured into water for extraction, a large amount of precipitates precipitated out, filtered through a funnel, and the precipitates were collected, then the filter cake was washed three times with dichloromethane, and a yellow solid was obtained after suction filtration, which was dried in vacuum...

Embodiment 3

[0064] Synthesis of 4,4'-(2,7-bis(4-((E)-1,2-diphenylvinyl)phenyl)-9H-fluorene-9,9-diyl) dianiline:

[0065]

[0066] (1) Synthesize intermediate 2,7-dibromo-9,9-bis(4-nitrophenyl)-9H-fluorene according to Example 1;

[0067] (2) Synthesis of intermediate (E)-l-bromo-4-(1,2-diphenylvinyl)benzene:

[0068] Add 11.6ml (0.1mol) of benzyl chloride and 52.2ml (0.3mol) of triethyl phosphite into a 500ml three-neck flask, magnetically stir and pass argon, heat and reflux in an oil bath at 150°C for 24h, cool to room temperature, and pour Add 300ml of tetrahydrofuran (THF) into the three-neck flask, then add 16.82g of potassium tert-butoxide (t-BuOK 0.15mol) and 20.9g of monobromobenzophenone ((4-bromophenyl)(phenyl)methanone 0.08mol), and magnetically stir for 24h , after the reaction stopped, the reaction solution was poured into water for extraction, and a large amount of white precipitates precipitated out, filtered through a funnel, collected the precipitates, washed 3 times ...

technical field

[0001] The invention relates to the field of material science, in particular to a fluorene-containing functional diamine monomer with a large conjugated system and a synthesis method thereof. The diamine monomer can be used to synthesize such as polyamide, polyimide, polyamideimide High performance, functional polymers such as amines and polyesterimides. technical background

[0002] Polyimide is one of the best heat-resistant varieties among engineering plastics that have been industrialized at present. It has outstanding properties unmatched by other materials, such as high mechanical strength, good high and low temperature resistance, excellent dielectric properties, and film-forming properties. OK wait. Since the development and industrialization of DuPont in the United States in the 1960s, it has been applied in various fields, especially in aerospace, aviation, microelectronics and military fields. Since polyimide is generally insoluble in organic sol...

Examples

Embodiment 1

[0044] Synthesis of 4,4'-(2,7-bis(4-(trifluoromethyl)phenyl)-9H-fluorene-9,9-diyl)dianiline:

[0045]

[0046] (1) Synthesis of intermediate 2,7-dibromo-9,9-bis(4-nitrophenyl)-9H-fluorene:

[0047] 32.401g (0.1mol) of 2,7-dibromofluorene (2,7-dibromo-9H-fluorene), 11.2g (0.1mol) of potassium tert-butoxide (t-BuOK) and 42.33g (0.3mol) of Add fluoronitrobenzene (1-fluoro-4-nitrobenzene) into a 500ml three-necked flask, use N,N-dimethylformamide (DMF) as a solvent, stir magnetically and pass argon gas, heat and reflux in an oil bath at 110°C for 24h , Pour the reaction solution into ice water, let it stand for 3h, and obtain a yellow solid by suction filtration, dissolve the yellow solid in absolute ethanol, and then crystallize at low temperature, filter the crystallized solid with suction to obtain a light yellow crystal, and in vacuo at 60°C After drying for 10 h, 51.5 g of the light yellow intermediate product 2,7-dibromo-9,9-bis(4-nitrophenyl)-9H-fluorene was obtained, w...

Embodiment 2

[0055] Synthesis of 4,4'-(9,9-bis(4-aminophenyl)-9H-fluorene-2,7-diyl)diphenol:

[0056]

[0057] (1) Synthesize intermediate 2,7-dibromo-9,9-bis(4-nitrophenyl)-9H-fluorene according to Example 1;

[0058] (2) Synthesis of intermediate 4,4'-(9,9-bis(4-nitrophenyl)-9H-fluorene-2,7-diyl)diphenol:

[0059] Add 11.124g (0.02mol) 2,7-dibromo-9,9-bis(4-nitrophenyl)-9H-fluorene and 6.8965g (0.05mol) 4-hydroxyphenylboronic acid to a 500ml three-necked flask Add 250ml of tetrahydrofuran (THF), and then add 75ml of 2mol / L potassium carbonate solution, stir magnetically and pass argon, heat the oil bath to 70°C, add 0.02g tetrakistriphenylpalladium, and reflux for 24h. The reaction liquid was poured into water for extraction, a large amount of precipitates precipitated out, filtered through a funnel, and the precipitates were collected, then the filter cake was washed three times with dichloromethane, and a yellow solid was obtained after suction filtration, which was dried in vacuum...

Embodiment 3

[0064] Synthesis of 4,4'-(2,7-bis(4-((E)-1,2-diphenylvinyl)phenyl)-9H-fluorene-9,9-diyl) dianiline:

[0065]

[0066] (1) Synthesize intermediate 2,7-dibromo-9,9-bis(4-nitrophenyl)-9H-fluorene according to Example 1;

[0067] (2) Synthesis of intermediate (E)-l-bromo-4-(1,2-diphenylvinyl)benzene:

[0068] Add 11.6ml (0.1mol) of benzyl chloride and 52.2ml (0.3mol) of triethyl phosphite into a 500ml three-neck flask, magnetically stir and pass argon, heat and reflux in an oil bath at 150°C for 24h, cool to room temperature, and pour Add 300ml of tetrahydrofuran (THF) into the three-neck flask, then add 16.82g of potassium tert-butoxide (t-BuOK 0.15mol) and 20.9g of monobromobenzophenone ((4-bromophenyl)(phenyl)methanone 0.08mol), and magnetically stir for 24h , after the reaction stopped, the reaction solution was poured into water for extraction, and a large amount of white precipitates precipitated out, filtered through a funnel, collected the precipitates, washed 3 times ...

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