CN1259305C - Fluorine-aromatic diamine with side chain having methyltrifluoride substituted benzene and diphenyl ether and preparation process and use thereof - Google Patents

Abstract

The fluorine-containing aromatic diamine with trifluoromethyl-substituted benzene and diphenyl ether in the side chain of the present invention is prepared according to the following steps: (1) by weight, 1-100 parts of trifluoromethyl-substituted aniline and 1 -100 parts of 2,4-dinitrochlorobenzene are reacted in 1-500 parts of dehydrated alcohol to make R ¹ be the dinitro compound of-NH-divalent organic group; (2) 1-100 parts of three Fluoromethyl-substituted aniline reacts with 1-100 parts of 3,5-dinitrobenzoyl chloride in 1-60 parts of N,N-dimethylacetamide (DMAc) to prepare R ¹ as -CONH-divalent organic (3) mix 1-100 parts of the above-mentioned dinitro compound with 1-10 parts of Pd/C and 1-20 parts of hydrazine hydrate, and obtain the side chain of the present invention with trifluoro The fluorine-containing aromatic diamine of methyl-substituted benzene and diphenyl ether, the fluorine-containing aromatic diamine with trifluoromethyl-substituted benzene and diphenyl ether in the side chain of the present invention is used to synthesize polyimide liquid crystal alignment agent.

Description

A fluorine-containing aromatic diamine with trifluoromethyl-substituted benzene and diphenyl ether in its side chain, its preparation method and use

technical field

The invention relates to a class of fluorine-containing aromatic diamines with trifluoromethyl-substituted benzene and diphenyl ether in their side chains, as well as their preparation and application.

Background technique

Aromatic diamines are widely used in the synthesis of polyimides. In recent years, with the rapid development of the microelectronics industry, the demand for functional polyimide materials has become more and more extensive. Standard polyimide materials are generally insoluble and infusible due to their rigid backbone structure. Therefore, in practical applications, it is mostly used in the form of its precursor, that is, polyamic acid (Edited by Ding Mengxian and He Tianbai, New Polyimide Materials, Science Press, 1998, 1). Polyamic acid can be converted into polyimide after imidization at high temperature. The imidization temperature is usually 250-300°C. Such a high temperature is unbearable for many temperature-sensitive fields in the microelectronics industry. . In view of this, extensive modification work has been carried out on standard polyimide materials. Among them, the preparation of organic soluble polyimides by synthesizing novel monomers is a hot topic of current research (Huang S.J., Hoyt A.E., The synthesis of soluble polyimides, TRIP, 1995, 3(8), 262-271).

There are a wide variety of diamine monomers used to synthesize soluble polyimides, among which introducing fluorine-containing substituents in diamines is one of the most effective means for synthesizing soluble polyimides (Ghosh M.K., Mittal K.L, Polyimide: fundamentals and applications, Marcel Dekker, 1996, p71). There are many reports about fluorine-containing diamine monomers in the literature. For example, Ichino et al. reported fluorine-containing diamine monomers with long fluoroalkyl side chains (Ichino T., Sasaki S., Matsuura T. and Nishi S., J. Polym. Sci., Part A: Polym Chem., 1990, 28, p323). The people such as Auman have synthesized the fluorine-containing diamine monomer (Auman B.C., Higley D.P., Scherer K.V., Polym.Prepr., 1993,34 (1) that side chain has two (trifluoromethyl) heptafluoroalkyl substituents , p389). Yusa et al studied the polymerization behavior of diamine monomers with perfluorononenyl ether in the side chain (Yusa M., Takeda S., and Miyadera Y, Polym.Prepr.Japan, 1990, 39, p897) and so on .

Although the above-mentioned fluorine-containing monomers are used in the synthesis of polyimides, the synthesis routes of these fluorine-containing diamines are relatively complicated, and the raw materials are not easy to obtain, especially the purification of the monomers is relatively difficult, and it is difficult to obtain high-purity products and achieve mass production. purpose, which largely limits the application.

Contents of the invention

The invention provides a fluorine-containing aromatic diamine with trifluoromethyl-substituted benzene and diphenyl ether in its side chain, its preparation method and application. The synthetic route of this monomer is simple, the raw material is easy to obtain, and it is easy to purify, so it can be produced in large quantities.

The side chain of the present invention has a trifluoromethyl-substituted benzene and diphenyl ether fluorine-containing aromatic diamine having the general formula

The structure shown in (1):

Wherein, R ¹ is a divalent organic group selected from -NH- or -CONH-;

^R2 is: or

Wherein, R _f is: -CF ₃ or -(CF ₃ ) ₂ .

The fluorine-containing aromatic diamine represented by the general formula (1) particularly includes a diamine monomer of the following structure:

The fluorine-containing aromatic diamine with trifluoromethyl-substituted diphenyl ether in the side chain of the present invention is synthesized according to the following steps:

(1) In parts by weight, dissolve 1-100 parts of trifluoromethyl-substituted aniline in 1-500 parts of absolute ethanol, and react with 1-100 parts of 2,4-dinitrochlorobenzene at 25°C for 1-12 After hours, make R ¹ be the dinitro compound of-NH-divalent organic group;

(2) Dissolve 1-100 parts of trifluoromethyl-substituted aniline in 1-60 parts of N,N-dimethylacetamide (DMAc), and mix with 1-100 parts of 3,5-dinitrate at 0-70°C After base benzoyl chloride reaction 1-24 hour, make R ^It is the dinitro compound of-CONH-divalent organic group;

(3) Mix 1-100 parts of the dinitro compound prepared by (1) or (2) with 1-10 parts of Pd/C and 1-20 parts of hydrazine hydrate, reflux for 1-48 hours, and filter while hot to remove the insoluble After cooling and crystallizing the filtrate, the fluorine-containing aromatic diamine with trifluoromethyl-substituted diphenyl ether in the side chain is precipitated.

The fluorine-containing aromatic diamine with trifluoromethyl-substituted diphenyl ether in the side chain of the present invention is subjected to Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), mass spectrometry (MS), elemental analysis, chromatography-mass spectrometry, etc. The analysis means test confirmed the structure of the diamine of the present invention, and its purity can reach 99.5%. The ion analysis test shows that the ion content of the monomer of this structure is as follows: Na ⁺ <2ppm, Cl ^- <2ppm, K ⁺ <1ppm . In addition, the raw materials of this type of monomer are easy to obtain, and the yield is as high as 80-85%, which is suitable for large-scale production.

The fluorine-containing aromatic diamine with trifluoromethyl-substituted diphenyl ether in the side chain of the present invention is used for preparing polyimide liquid crystal aligning agent.

Detailed ways

Example 1 Add 2.026g (10.0mmol) 2,4-dinitrochlorobenzene, 2.53g (10.0mmol) 4-(4'-trifluoromethyl ) phenoxyaniline and 50ml absolute ethanol. The system was stirred and reacted at room temperature for 12 hours to obtain a yellow suspension, and the resulting yellow precipitate was collected by filtration, washed repeatedly with cold water, and dried in vacuum. The crude product was recrystallized from ethanol to obtain 2,4-dinitro-1-[(4'-trifluoromethylphenoxy)phenyl]aniline as a yellow solid powder, yield 2.85 g (68%). FT-IR (KBr, cm ^-1 ): 3332.7; 1328.2. ¹ H-NMR (300MHz, DMSO-d ₆ , ppm): 7.11-7.19 (m; 5H); 7.70-7.73 (d; 2H); 7.84- 7.87(d; 2H); 8.99(s; 1H); 9.16(s; 1H); 10.92(s; 1H). ¹⁹ F-NMR (300MHz, DMSO-d ₆ , ppm): 18.18(-CF ₃ ). Mass Spectrum (EI): 419 (M+, 100). Elemental Analysis C ₁₉ H ₁₂ F ₃ N ₃ O: Calculated: C, 54.42%; H, 2.88%; N, 10.02%. Found: C, 54.35%; H, 2.78%; N, 9.95%.

Add 4.183g (10mmol) 2,4-dinitro-1-[(4'-trifluoromethylphenoxy)phenyl]aniline in a 500ml three-necked flask equipped with mechanical stirring, thermometer and nitrogen inlet, 25ml ethanol and 0.5g 5% Pd/C. The temperature was raised to reflux, and 15ml of NH ₂ NH ₂ ·H ₂ O was added dropwise. After the dropwise addition was completed, the reaction was refluxed for 24 hours, and the Pd/C was removed by filtration while hot, and the filtrate cooled and crystallized to precipitate colorless needle crystals. It was collected by filtration and dried in vacuo to give 2,4-diamino-1-[(4'-trifluoromethylphenoxy)phenyl]aniline in a yield of 3.41 g (95%). Its structure is shown in formula (2). FT-IR (KBr, cm ^-1 ): 3446.8, 3343.3, 1324.7. ¹ H-NMR (300MHz, DMSO-d, ppm): 4.60(s; 2H); 5.84-5.88(q; 1H); 6.02(d ; 1H); 6.56-6.59(d; 2H); 6.63-6.66(d; 2H); 6.86-6.88(d; 2H); 7.00-7.03(d; 2H); 7.65-7.67(d; 2H). (EI): 359 (M+, 100). Elemental Analysis C ₁₉ H ₁₆ F ₃ N ₃ O: Calculated: C, 63.51%; H, 4.49%; N, 11.70%. Found: C, 63.49%; H , 4.47%; N, 11.67%.

Example 2 Add 25.32g (100mmol) 4-(4'-trifluoromethyl)phenoxyaniline, 60ml N,N-dimethylethane to a 250ml three-neck flask equipped with mechanical stirring, thermometer and nitrogen inlet Amide (DMAc) and 10.12 g (100 mmol) of dry triethylamine. Cool in ice water under electromagnetic stirring, and add dropwise a solution of 23.06 g (100 mmol) of 3,5-dinitrobenzoyl chloride in DMAc (60 ml). After the dropwise addition, the temperature was raised to 80° C., and the reaction was maintained at a constant temperature overnight. The reaction system was poured into ice water to obtain light yellow solid powder, which was collected by filtration and dried in vacuo. The crude product was recrystallized from ethanol to give 3,5-dinitro-1-[(4'-trifluoromethylphenoxy)phenyl]benzamide as pale yellow crystals, yield 38.44g (86%). FT-IR (KBr, cm ^-1 ): 3290.9; 1653.0, 1328.4. ¹ H-NMR (300MHz, DMSO-d ₆ , ppm): 7.10-7.14 (m; 2H); 7.18-7.25 (m; 2H); 7.43-7.45(d; 2H); 7.73-7.76(d; 2H); 8.19-8.23(d; 2H); 10.13(s; 1H). ¹⁹ F-NMR (300MHz, DMSO-d ₆ , ppm): 18.13 (-CF ₃ ). Mass Spectrum (EI): 447 (M+, 100). Elemental Analysis C ₂₀ H ₁₂ F ₃ N ₃ O ₆ : Calculated: C, 53.70%; H, 2.70%; N, 9.40%. Found Values: C, 53.49%; H, 2.61%; N, 9.38%.

Add 4.47g (100mmol) 3,5-dinitro-1-[(4'-trifluoromethylphenoxy)phenyl]benzene to a 100ml three-neck flask equipped with mechanical stirring, thermometer and nitrogen inlet Amide, 25ml ethanol and 0.5g 5% Pd/C. The temperature was raised to reflux, and 15ml of NH ₂ NH ₂ ·H ₂ O was added dropwise. After the dropwise addition was completed, the reaction was refluxed for 24 hours, and the Pd/C was removed by filtration while hot, and the filtrate cooled and crystallized to precipitate colorless needle crystals. It was collected by filtration and dried in vacuo to give 3,5-diamino-1-[(4'-trifluoromethylphenoxy)phenyl]benzamide in a yield of 3.17 g (82%). Its structure is shown in formula (3). FT-IR (KBr, cm ^-1 ): 3436.6, 3338.0, 3281.8; 1329.7. ¹ H-NMR (300MHz, DMSO-D ₆ , ppm) 4.95(s; 4H); 6.01(s; 1H); 6.30(s 2H); 7.10(m; 2H); 7.12(m; 2H); 7.70-7.73(d; 2H); 7.82-7.85(d; 2H); 10.05(s; 1H). M+, 38.0). Elemental analysis C ₂₀ H ₁₆ F ₃ N ₃ O ₂ : Calculated: C, 62.01%; H, 4.16%; N, 10.85%. Found: C, 60.39%; H, 3.98%; N , 10.62%.

Example 3 Add 32.13g (100mmol) 4-(3',5'-bistrifluoromethyl)phenoxyaniline, 60ml DMAc and 10.12g to a 250ml three-neck flask equipped with mechanical stirring, thermometer and nitrogen inlet (100 mmol) dry triethylamine. Cool in ice water under electromagnetic stirring, and add dropwise a solution of 23.06 g (100 mmol) of 3,5-dinitrobenzoyl chloride in DMAc (60 ml). After the dropwise addition, the temperature was raised to 80° C., and the reaction was maintained at a constant temperature overnight. The reaction system was poured into ice water to obtain light yellow solid powder, which was collected by filtration and dried in vacuo. The crude product was recrystallized from ethanol to give 3,5-dinitro-1-[(3',5'-bistrifluoromethylphenoxy)phenyl]benzamide as pale yellow crystals, yield 42.77g (83%) . FT-IR (KBr, cm ⁻¹ ): 3290.9; 1653.0, 1328.4. Mass spectrum (MS): 515 (M+, 100). Elemental analysis for C ₂₁ H ₁₁ F ₆ N ₃ O ₆ : Calculated: C, 48.95%; H, 2.15%; N, 8.15%. Found: C, 48.92% ; H, 2.13%; N, 8.22%.

Add 5.15g (10mmol) 3,5-dinitro-1-[(3',5'-bistrifluoromethylphenoxy)benzene to a 100ml three-neck flask equipped with mechanical stirring, thermometer and nitrogen inlet Base] benzamide, 25ml ethanol and 0.5g 5% Pd/C. The temperature was raised to reflux, and 15ml of NH ₂ NH ₂ ·H ₂ O was added dropwise. After the dropwise addition was completed, the reaction was refluxed for 24 hours, and the Pd/C was removed by filtration while hot, and the filtrate cooled and crystallized to precipitate colorless needle crystals. Collected by filtration and dried in vacuo to obtain 3,5-diamino-1-[(3',5'-bistrifluoromethylphenoxy)phenyl]benzamide, yield 4.37g (96%), its structure is Formula (4) shown. FT-IR (KBr, cm ^-1 ): 3436.6, 3338.0, 3281.8; 1329.7. ¹ H-NMR (300MHz, DMSO-d ₆ , ppm) 4.96(s; 4H); 5.96(s; 1H); 6.25(s ; 2H); 7.13-7.16(d; 2H); 7.39(s; 2H); 7.79(m; 2H); 7.81-7.84(m; 1H); 10.08(s; 1H). M+, 38.0). Elemental analysis C ₂₁ H ₁₅ F ₆ N ₃ O ₂ ; Calculated: C, 55.39%; H, 3.32%; N, 9.23%. Found: C, 55.32%; H, 3.28%; N , 9.26%.

Example 4 22.91g (100mmol) of 3,5-bistrifluoromethylaniline, 60ml of DMAc and 10.12g (100mmol) of dry triethylamine were added to a 250ml three-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen inlet. Cool in ice water under electromagnetic stirring, and add dropwise a solution of 23.06 g (100 mmol) of 3,5-dinitrobenzoyl chloride in DMAc (60 ml). After the dropwise addition, the temperature was raised to 80° C., and the reaction was maintained at a constant temperature overnight. The reaction system was poured into ice water to obtain light yellow solid powder, which was collected by filtration and dried in vacuo. The crude product was recrystallized from ethanol to give 3,5-dinitro-1-[(3,5'-bistrifluoromethyl)phenyl]benzamide as pale yellow crystals, yield 35.97 g (85%). FT-IR (KBr, cm ^-1 ): 3289.4; 1650.2, 1326.7. Mass spectrum (MS): 423 (M+, 100). Elemental analysis for C ₁₅ H ₇ F ₆ N ₃ O ₅ : Calculated: C, 42.57%; H, 1.67%; N, 9.93%. Found: C, 42.54% ; H, 1.69%; N, 9.89%.

Add 4.23g (10mmol) 3,5-dinitro-1-[(3',5'-bistrifluoromethyl)phenyl]benzene to a 100ml three-neck flask equipped with mechanical stirring, thermometer and nitrogen inlet Formamide, 25ml ethanol and 0.5g 5% Pd/C. The temperature was raised to reflux, and 15ml of NH ₂ NH ₂ ·H ₂ O was added dropwise. After the dropwise addition was completed, the reaction was refluxed for 24 hours, and the Pd/C was removed by filtration while hot, and the filtrate cooled and crystallized to precipitate colorless needle crystals. Collect by filtration and dry in vacuo to obtain 3,5-diamino-1-[(3',5'-bistrifluoromethyl)phenyl]benzamide, yield 3.45g (95%), and its structure is as in formula (5 ) shown. FT-IR (KBr, cm ^-1 ): 3434.2, 3334.3, 3285.4; 1326.7. ¹ H-NMR (300MHz, DMSO-d ₆ , ppm) 4.94(s; 4H); 5.97(s; 1H); 6.26(s ; 2H); 7.49(s; 2H); 7.81-7.84(m; 1H); 10.11(s; 1H). Mass spectrum (MS): 363 (M+, 38.0). Elemental analysis C ₁₅ H ₁₁ F ₆ N _3O : Calculated: C, 49.60%; H, 3.05%; N, 11.57%. Found: C, 49.58%; H, 3.08%; N, 11.54%.

Claims (4)

1. a kind of side chain has the fluorine-containing aromatic diamine of trifluoromethyl-substituted diphenyl ether, it is characterized in that described fluorine-containing aromatic diamine general formula is as follows: Wherein, R ¹ is a divalent organic group selected from -NH- or -CONH-; ^R2 is:

Wherein, R _f is: -CF ₃ or -(CF ₃ ) ₂ . 2. the fluorine-containing aromatic diamine with trifluoromethyl-substituted diphenyl ether in the side chain according to claim 1, characterized in that the fluorine-containing aromatic diamine with trifluoromethyl-substituted diphenyl ether in the described side chain Diamines are:

or

3. side chain according to claim 1 has the preparation method of the fluorine-containing aromatic diamine of trifluoromethyl substituted diphenyl ether, it is characterized in that carry out in the following sequential steps: (1) In parts by weight, dissolve 1-100 parts of trifluoromethyl-substituted aniline in 1-500 parts of absolute ethanol, and react with 1-100 parts of 2,4-dinitrochlorobenzene at 25°C for 1-12 After hours, make R ¹ be the dinitro compound of-NH-divalent organic group; (2) Dissolve 1-100 parts of trifluoromethyl-substituted aniline in 1-60 parts of N,N-dimethylacetamide, and mix with 1-100 parts of 3,5-dinitrobenzyl at 0-70°C After acid chloride reaction 1-24 hour, make R ¹ be the dinitro compound of-CONH-divalent organic group; (3) Mix 1-100 parts of the dinitro compound prepared by (1) or (2) with 1-10 parts of Pd/C and 1-20 parts of hydrazine hydrate, reflux for 1-48 hours, and filter while hot to remove the insoluble After cooling and crystallizing the filtrate, the fluorine-containing aromatic diamine with trifluoromethyl-substituted diphenyl ether in the side chain is separated out. 4. The use of the fluorine-containing aromatic diamine with trifluoromethyl-substituted diphenyl ether in the side chain according to claim 1, characterized in that it is used to prepare polyimide liquid crystal aligning agent.