Alkyl substituent-containing alicyclic dianhydride compound and polyimide prepared by same

Abstract

The invention discloses an alkyl substituent-containing alicyclic dianhydride compound and a polyimide prepared by same. The structure formula of the polyimide is shown by formula III. The polymer is prepared by taking the alkyl substituent-containing alicyclic dianhydride compound and aromatic diamine compound as raw materials through two-step chemical imide method. The polyimide provided by the invention contains alicyclic component and aromatic component as well as flexible ether chain link, which have an important function for improving thermal resistance stability, optical transparency and dissolubility in organic solvent. Such material can be used as assembly of liquid crystal alignment film for photoelectric devices such as TFT-LCD and the like and also can be used as coating for use in the fields such as optical fiber communication, solar cell and the like.

Description

technical field

[0001] The invention belongs to the field of functional polyimide materials, and relates to an alkyl-substituted alicyclic dianhydride compound and a polyimide prepared therefrom. Background technique

[0002] In recent years, polyimide (PI) films containing alicyclic structures have received extensive attention in the field of optoelectronics. Different from the traditional all-aromatic PI film, the alicyclic PI film has excellent optical transparency, high dimensional stability, low dielectric constant and other characteristics, so in recent years, it has been used in advanced optoelectronic fields such as liquid crystal display, solar cells, and optical fiber communications. Both have been extensively studied (Matsumoto T, et al. Alicyclic polyimides-a colorless and thermally stable polymer for optoelectronic devices. J Phys: Conf ser, 2009, 187: 012005).

[0003] Although important progress has been made in the basic and applied research of alicyclic PI,...

Examples

Embodiment 1

[0039] Embodiment 1, dianhydride compound 3, the synthesis of 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (TDA)

[0040] Add 250 g (2.55 mol) of maleic anhydride into a 250 mL three-necked flask equipped with a mechanical stirrer, a thermometer, and a gas inlet, and raise the temperature to blow nitrogen. After all of the solution was dissolved, 0.57 g (2.55 mmol) of a polymerization inhibitor 2,5-di-tert-butylhydroquinone was added. Add 398.1 g (3.82 mol) of styrene at one time. Change the nitrogen gas to nitrogen monoxide gas, raise the temperature to 115°C for reaction, and a precipitate appears after 1 hour. After reacting for 5 hours, cool down to 60°C, add 180ml of acetonitrile, reflux for 0.5h to dissolve the reaction system into a clear liquid, cool down slightly, add 200mL of toluene, and cool down. A large number of crystals were precipitated, filtered and washed three times with toluene to obtain loose white crystals with a yield of 90%.

[...

Embodiment 2

[0050] Embodiment 2, the synthesis of dianhydride compound 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride (MTDA)

[0051] Add 43.75g (0.446mol) maleic anhydride, 80.60g (0.682mol) 4-methylstyrene, 0.1g (0.446mmol) ) 2,5-di-tert-butylhydroquinone, the temperature was raised to 120° C. under the catalysis of nitric oxide gas, and the reaction was maintained at constant temperature for 6 hours, and a large amount of orange solid was precipitated. Add 60 mL of acetonitrile, reflux for 0.5 h to dissolve the reaction system into a clear liquid, add 60 mL of toluene, and cool. A large number of crystals were precipitated, filtered, washed with toluene three times, and turned from orange to white. After washing with petroleum ether three times, loose white crystals were obtained with a yield of 89%.

[0052] The structure of this compound is shown in formula I, wherein R 1 =-H;R 2 =-CH 3 (m=1):

[0053]

[0054] The detection data are as follows ...

Embodiment 3

[0061] Embodiment 3, the synthesis of dianhydride compound 3,4-dicarboxy-1,2,3,4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride (TTDA)

[0062] Add 64.13g (0.654mol) maleic anhydride, 160.26g (1mol) 4-tert-butylstyrene, 0.22g (1mmol) 2 , 5-Di-tert-butyl hydroquinone, the temperature was raised to 120°C under the catalysis of nitric oxide gas, and the reaction was maintained at a constant temperature for 5 hours, and the system changed from a liquid phase to a solid phase. Add 250mL of acetonitrile, reflux until completely dissolved, and drop to room temperature. Add 200 mL of toluene, stand still to crystallize, and obtain a flocculent precipitate. After filtering and washing with toluene three times, the solid powder changed from orange to white. After washing with petroleum ether three times, a white powdery solid was obtained with a yield of 89%.

[0063] The structure of this compound is shown in formula I, wherein R 1 =-H;R 2 =-C 4 h 9 (m=4):

[0064] ...

technical field

[0001] The invention belongs to the field of functional polyimide materials, and relates to an alkyl-substituted alicyclic dianhydride compound and a polyimide prepared therefrom. Background technique

[0002] In recent years, polyimide (PI) films containing alicyclic structures have received extensive attention in the field of optoelectronics. Different from the traditional all-aromatic PI film, the alicyclic PI film has excellent optical transparency, high dimensional stability, low dielectric constant and other characteristics, so in recent years, it has been used in advanced optoelectronic fields such as liquid crystal display, solar cells, and optical fiber communications. Both have been extensively studied (Matsumoto T, et al. Alicyclic polyimides-a colorless and thermally stable polymer for optoelectronic devices. J Phys: Conf ser, 2009, 187: 012005).

[0003] Although important progress has been made in the basic and applied research of alicyclic PI,...

Examples

Embodiment 1

[0039] Embodiment 1, dianhydride compound 3, the synthesis of 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (TDA)

[0040] Add 250 g (2.55 mol) of maleic anhydride into a 250 mL three-necked flask equipped with a mechanical stirrer, a thermometer, and a gas inlet, and raise the temperature to blow nitrogen. After all of the solution was dissolved, 0.57 g (2.55 mmol) of a polymerization inhibitor 2,5-di-tert-butylhydroquinone was added. Add 398.1 g (3.82 mol) of styrene at one time. Change the nitrogen gas to nitrogen monoxide gas, raise the temperature to 115°C for reaction, and a precipitate appears after 1 hour. After reacting for 5 hours, cool down to 60°C, add 180ml of acetonitrile, reflux for 0.5h to dissolve the reaction system into a clear liquid, cool down slightly, add 200mL of toluene, and cool down. A large number of crystals were precipitated, filtered and washed three times with toluene to obtain loose white crystals with a yield of 90%.

[...

Embodiment 2

[0050] Embodiment 2, the synthesis of dianhydride compound 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride (MTDA)

[0051] Add 43.75g (0.446mol) maleic anhydride, 80.60g (0.682mol) 4-methylstyrene, 0.1g (0.446mmol) ) 2,5-di-tert-butylhydroquinone, the temperature was raised to 120° C. under the catalysis of nitric oxide gas, and the reaction was maintained at constant temperature for 6 hours, and a large amount of orange solid was precipitated. Add 60 mL of acetonitrile, reflux for 0.5 h to dissolve the reaction system into a clear liquid, add 60 mL of toluene, and cool. A large number of crystals were precipitated, filtered, washed with toluene three times, and turned from orange to white. After washing with petroleum ether three times, loose white crystals were obtained with a yield of 89%.

[0052] The structure of this compound is shown in formula I, wherein R 1 =-H;R 2 =-CH 3 (m=1):

[0053]

[0054] The detection data are as follows ...

Embodiment 3

[0061] Embodiment 3, the synthesis of dianhydride compound 3,4-dicarboxy-1,2,3,4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride (TTDA)

[0062] Add 64.13g (0.654mol) maleic anhydride, 160.26g (1mol) 4-tert-butylstyrene, 0.22g (1mmol) 2 , 5-Di-tert-butyl hydroquinone, the temperature was raised to 120°C under the catalysis of nitric oxide gas, and the reaction was maintained at a constant temperature for 5 hours, and the system changed from a liquid phase to a solid phase. Add 250mL of acetonitrile, reflux until completely dissolved, and drop to room temperature. Add 200 mL of toluene, stand still to crystallize, and obtain a flocculent precipitate. After filtering and washing with toluene three times, the solid powder changed from orange to white. After washing with petroleum ether three times, a white powdery solid was obtained with a yield of 89%.

[0063] The structure of this compound is shown in formula I, wherein R 1 =-H;R 2 =-C 4 h 9 (m=4):

[0064] ...

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