Novel diamine monomer as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of functional materials, and provides a novel diamine monomer as well as a preparation method and application thereof. The structural formula of the novel diamine monomer disclosed by the invention is # imgabs0 #, in which R1 is OH, CH3, F or H, R2 is CF3, CH3 or H, and R3 is CH3 or H. The preparation method comprises the following steps: by taking 2-imidazolidinone as an initial raw material and copper salt as a catalyst, carrying out Goldberg coupling reaction on the 2-imidazolidinone and 4-halogenated aniline under an alkaline condition to obtain a diamine monomer; the diamine monomer disclosed by the invention is novel in structure, short in synthetic route, simple in process and high in application value, and only needs one-step chemical reaction.

Description

Technical Field

[0001] The invention relates to the technical field of functional materials, and in particular to a novel diamine monomer and a preparation method and application thereof. Background Art

[0002] Polyimide (abbreviated as PI) refers to a type of polymer containing an imide ring (-CO-N-CO-) on the main chain. It is one of the organic polymer materials with better comprehensive performance. Its high temperature resistance is as high as 400℃ or above, and its long-term use temperature range can be between -200 and 300℃. The dielectric constant is 4.0F / m at 103Hz, and the dielectric loss is only 0.004 to 0.007, reaching the F to H grade insulation level. As a special engineering material, polyimide has been widely used in aviation, aerospace, microelectronics, nano, liquid crystal, separation membrane and laser fields. Whether as a structural material or a functional material, the application prospects of polyimide have been fully recognized.

[0003] Polyimide is produced by the condensation reaction of dianhydride and diamine. The synthesis route is as follows:

[0004]

[0005] It can be seen that the properties of polyimide are mainly determined by the structure and properties of dianhydride and diamine. Therefore, the synthesis of new dianhydride and diamine is crucial for the development of new polyimide. Summary of the invention

[0006] The purpose of the present invention is to provide a novel diamine monomer and a preparation method and application thereof in view of the deficiencies in the prior art.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a novel diamine monomer, the structural formula of the novel diamine monomer is:

[0009]

[0010] Among them, R 1 OH, CH 3 , F or H, R 2 For CF 3 , CH 3 or H, R 3 CH 3 or H.

[0011] Preferably, the novel diamine monomer is any one of the following structural formulas:

[0012]

[0013] The present invention also provides a method for preparing the novel diamine monomer, comprising the following steps:

[0014] (1) mixing 2-imidazolidinone, 4-haloaniline, an inorganic base, a catalyst, a ligand and a solvent to carry out a Goldberg coupling reaction to obtain an intermediate;

[0015] (2) Extracting the intermediate to obtain a novel diamine monomer.

[0016] Preferably, the structural formula of the 4-haloaniline in step (1) is:

[0017] Where X is Br or I, R 1 OH, CH 3 , F or H, R 2 For CF 3 , CH 3 or H, R 3 CH 3 or H.

[0018] Preferably, the inorganic base in step (1) is NaOH, KOH, CsOH, LiOH, Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 or K 3 PO 4 ;

[0019] The catalyst is cuprous iodide, cuprous chloride, cupric acetylate or cupric acetylacetonate;

[0020] The ligand is N,N'-dimethylethylenediamine or N,N'-dimethyl-1,2-cyclohexanediamine;

[0021] The solvent is toluene, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide or n-butanol.

[0022] Preferably, in step (1), the molar ratio of the 2-imidazolidinone, 4-haloaniline, inorganic base, catalyst and ligand is 1:2-4:1-4:0.01-0.1:0.02-0.2, and the mass volume ratio of the 2-imidazolidinone and the solvent is 1 g:3-5 mL.

[0023] Preferably, the temperature of the Goldberg coupling reaction in step (1) is 90 to 120° C., and the time of the Goldberg coupling reaction is 3 to 8 hours.

[0024] Preferably, the extraction agent used in the extraction in step (2) is dichloromethane, toluene or 2-methyltetrahydrofuran, and the number of extractions is 2 to 4 times; the volume mass ratio of the extraction agent used in each extraction to 2-imidazolidinone is 3 to 5 mL: 1 g.

[0025] The invention also provides application of the novel diamine monomer in synthesizing novel polyimide.

[0026] Beneficial effects of the present invention:

[0027] The invention uses 2-imidazolidinone as a starting material and copper salt as a catalyst to carry out a Goldberg coupling reaction with 4-halogenated aniline under alkaline conditions to obtain a diamine monomer. The diamine monomer of the invention has a novel structure, a short synthesis route, requires only one chemical reaction, has a simple process, and has great application value. DETAILED DESCRIPTION

[0028] The present invention provides a novel diamine monomer, the structural formula of the novel diamine monomer is:

[0029]

[0030] Among them, R 1 OH, CH 3 , F or H, R 2 For CF 3 , CH 3 or H, R 3 CH 3 or H.

[0031] In the present invention, the novel diamine monomer is preferably any one of the following structural formulas:

[0032]

[0033] The present invention also provides a method for preparing the novel diamine monomer, comprising the following steps:

[0034] (1) mixing 2-imidazolidinone, 4-haloaniline, an inorganic base, a catalyst, a ligand and a solvent to carry out a Goldberg coupling reaction to obtain an intermediate;

[0035] (2) Extracting the intermediate to obtain a novel diamine monomer.

[0036] In the present invention, the structural formula of the 4-halogenated aniline in step (1) is:

[0037] Wherein, X is preferably Br or I, R 1 Preferably OH, CH 3 , F or H, R2 Preferably CF 3 , CH 3 or H, R 3 Preferably CH 3 or H.

[0038] In the present invention, the synthetic route of the novel diamine monomer is preferably:

[0039]

[0040] In the present invention, the inorganic base in step (1) is preferably NaOH, KOH, CsOH, LiOH, Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 or K 3 PO 4 ;

[0041] The catalyst is preferably cuprous iodide, cuprous chloride, cupric acetylate or cupric acetylacetonate;

[0042] The ligand is preferably N,N'-dimethylethylenediamine or N,N'-dimethyl-1,2-cyclohexanediamine;

[0043] The solvent is preferably toluene, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide or n-butanol.

[0044] In the present invention, the molar ratio of the 2-imidazolidinone, 4-haloaniline, inorganic base, catalyst and ligand in step (1) is preferably 1:2-4:1-4:0.01-0.1:0.02-0.2, more preferably 1:2.5-3.5:2-3:0.04-0.08:0.05-0.15, more preferably 1:3:2.5:0.06:0.1; the mass volume ratio of the 2-imidazolidinone and the solvent is preferably 1g:3-5mL, more preferably 1g:

[0045] 3.72~4.5mL, more preferably 1g:4mL.

[0046] In the present invention, the temperature of the Goldberg coupling reaction in step (1) is preferably 90-120° C., more preferably 100-110° C., and more preferably 105° C.; the time of the Goldberg coupling reaction is preferably 3-8 h, more preferably 4-7 h, and more preferably 5-6 h.

[0047] In the present invention, in step (2), the intermediate is preferably poured into water before extraction; the volume mass ratio of water to 2-imidazolidinone is preferably 30-50 mL:1 g, and more preferably 40 mL:1 g.

[0048] In the present invention, the extraction agent used in the extraction of step (2) is preferably dichloromethane, toluene or 2-methyltetrahydrofuran, and the number of extractions is preferably 2 to 4 times, more preferably 3 times; the volume mass ratio of the extraction agent used in each extraction to 2-imidazolidinone is preferably 3 to 5 mL: 1 g, more preferably 3.5 to 4.5 mL: 1 g, and more preferably 4 mL: 1 g.

[0049] In the present invention, after the extraction in step (2) is completed, an organic layer is obtained, and the organic layer is washed to obtain a novel diamine monomer; the reagent used for the washing is preferably a saturated sodium chloride solution, and the volume mass ratio of the saturated sodium chloride solution to 2-imidazolidinone is preferably 3-50 mL: 1 g, more preferably 10-40 mL: 1 g, and more preferably 20-30 mL: 1 g.

[0050] The invention also provides application of the novel diamine monomer in synthesizing novel polyimide.

[0051] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0052] Example 1

[0053]

[0054] 100mmol 2-imidazolidinone, 200mmol 4-bromoaniline, 100mmol K 2 CO 3 , 1mmol cuprous iodide, 2mmol N,N'-dimethylethylenediamine and 26mL N,N-dimethylformamide were mixed, placed in a 100mL reaction bottle, heated to 90°C for Goldberg coupling reaction for 3h to obtain an intermediate. After the intermediate was cooled to 15°C, it was poured into 260mL water, and then extracted with toluene three times to obtain an organic layer (26mL of toluene was used for each extraction), and the organic layer was washed with 26mL of saturated sodium chloride solution to obtain an organic phase, and the organic phase was placed in a rotary evaporator and concentrated at 50°C for 30min to obtain a new diamine monomer.

[0055] The new diamine monomer obtained in this example is white, has a mass of 25 g, and a yield of 93%.

[0056] 1 The H NMR data are: 1 H NMR (400 MHz, CDCl3 ): δ7.40-7.31(m,4H),7.11-7.03(m,4H),4.98(br.s,4H),3.62-3.55(m,4H); HRMS(ES + )calcd.for C 15 H 17 N 4 O[M+H] + :269.1395;found:269.1397.

[0057] Example 2

[0058]

[0059] 100mmol 2-imidazolidinone, 200mmol 2-fluoro-4-bromoaniline, 100mmol Cs 2 CO 3 , 10mmol cuprous chloride, 20mmol N,N'-dimethylethylenediamine and 32mL 1,4-dioxane were mixed and placed in a 100mL reaction bottle, heated to 90°C for Goldberg coupling reaction for 8h to obtain an intermediate. After the intermediate was cooled to 30°C, it was poured into 430mL water, and then extracted with dichloromethane three times to obtain an organic layer (43mL of dichloromethane was used for each extraction), and the organic layer was washed with 86mL saturated sodium chloride solution to obtain an organic phase, and the organic phase was placed in a rotary evaporator and concentrated at 35°C for 10min to obtain a new diamine monomer.

[0060] The new diamine monomer obtained in this example is white, has a mass of 25.3 g, and a yield of 83%.

[0061] 1 The H NMR data are: 1 H NMR (400 MHz, CDCl 3 ): δ7.60(d,J=6.8Hz,2H),6.80-6.88(m,4H),5.24(br.s,4H),3.42-3.55(m,4H); HRMS(ES+)calcd.for C 15 H 15 F 2 N 4 O[M+H] + :305.1210;found:305.1208.

[0062] Example 3

[0063]

[0064] 100mmol 2-imidazolidinone, 400mmol 2-trifluoromethyl-4-bromoaniline, 100mmol K 3 PO 4 , 10mmol acetylated copper, 20mmol N,N'-dimethyl-1,2-cyclohexanediamine and 25.8mL dimethyl sulfoxide were mixed and placed in a 100mL reaction bottle, heated to 90°C for Goldberg coupling reaction for 8h to obtain an intermediate. After the intermediate was cooled to 15°C, it was poured into 430mL water, and then extracted with toluene three times to obtain an organic layer (43mL of toluene was used for each extraction), and the organic layer was washed with 86mL of saturated sodium chloride solution to obtain an organic phase, and the organic phase was placed in a rotary evaporator and concentrated at 50°C for 30min to obtain a new diamine monomer.

[0065] The new diamine monomer obtained in this example is white, has a mass of 25.9 g, and a yield of 64%.

[0066] 1 The H NMR data are: 1 H NMR (400 MHz, CDCl 3 ): δ7.88(s,2H),7.03-7.07(m,2H),6.80-6.83(m,2H),3.42-3.56(m,4H); HRMS(ES+)calcd.for C 17 H 15 F 6 N 4 O[M+H] + :405.1140;found:405.1145.

[0067] Example 4

[0068]

[0069] 100mmol 2-imidazolidinone, 200mmol 2-hydroxy-4-bromoaniline, 200mmol NaOH, 1mmol cuprous iodide, 2mmol N,N'-dimethylethylenediamine and 26mL n-butanol were mixed and placed in a 100mL reaction bottle, heated to 100°C for Goldberg coupling reaction for 3h to obtain an intermediate. After the intermediate was cooled to 30°C, it was poured into 260mL water, and then the pH value was adjusted to 7 with 1mol / L hydrochloric acid, and then extracted with toluene 3 times to obtain an organic layer (26mL of toluene was used for each extraction), and the organic layer was washed with 26mL of saturated sodium chloride solution to obtain an organic phase, and the organic phase was placed in a rotary evaporator and concentrated at 50°C for 30min to obtain a new diamine monomer.

[0070] The new diamine monomer obtained in this example is white, has a mass of 25 g, and a yield of 93%.

[0071] 1 The H NMR data are: 1 H NMR (400 MHz, CDCl 3 ): δ10.06(s,2H),6.99(s,2H),6.70-6.73(m,2H),6.63-6.59(m,2H),4.77(br.s,4H),3.61-3.57(m,4H); HRMS(ES+)calcd.for C 15 H 17 N 4 O 3 [M+H] + :301.1290;found:301.1295.

[0072] Example 5

[0073]

[0074] 100mmol 2-imidazolidinone, 200mmol 2-methyl-4-bromoaniline, 100mmol Na 2 CO 3 , 1mmol copper acetylacetonate, 2mmol N,N'-dimethylethylenediamine and 26mL toluene were mixed, placed in a 100mL reaction bottle, heated to 120°C for Goldberg coupling reaction for 3h to obtain an intermediate. After the intermediate was cooled to 15°C, it was poured into 260mL water, and then extracted with 2-methyltetrahydrofuran for 3 times to obtain an organic layer (26mL of 2-methyltetrahydrofuran was used for each extraction), and the organic layer was washed with 26mL of saturated sodium chloride solution to obtain an organic phase, and the organic phase was placed in a rotary evaporator and concentrated at 35°C for 15min to obtain a new diamine monomer.

[0075] The new diamine monomer obtained in this example is white, has a mass of 27.3 g, and a yield of 92%.

[0076] 1 The H NMR data are: 1 H NMR (400 MHz, CDCl 3 ): δ7.50-7.57(m,2H),6.93(d,2H),6.73-6.85(m,2H),7.01(br.s,4H),3.42-3.57(m,4H),2.12(s,6H); HRMS(ES+)calcd.forC 17 H 21 N 4O[M+H] + :297.1715;found:297.1710.

[0077] Example 6

[0078]

[0079] 100mmol 2-imidazolidinone, 200mmol 3-methyl-4-bromoaniline, 100mmol Na 2 CO 3 , 1mmol copper acetylacetonate, 2mmol N,N'-dimethylethylenediamine and 26mL toluene were mixed, placed in a 100mL reaction bottle, and heated to 120°C for Goldberg coupling reaction for 3h to obtain an intermediate. After the intermediate was cooled to 15°C, it was poured into 260mL water, and then extracted with dichloromethane three times to obtain an organic layer (26mL of dichloromethane was used for each extraction), and the organic layer was washed with 26mL of saturated sodium chloride solution to obtain an organic phase, and the organic phase was placed in a rotary evaporator and concentrated at 35°C for 15min to obtain a new diamine monomer.

[0080] The new diamine monomer obtained in this example is white, has a mass of 23 g, and a yield of 77%.

[0081] 1 The H NMR data are: 1 H NMR (400 MHz, CDCl 3 ): δ7.32-7.53(m,2H),6.97(s,2H),6.12-6.33(m,2H),4.78(br.s,4H),3.42-3.57(m,4H),2.12(s,6H); HRMS(ES+)calcd.forC 17 H 21 N 4 O[M+H] + :297.1716;found:297.1710.

[0082] Example 7

[0083]

[0084] 100mmol 2-imidazolidinone, 200mmol 2,6-dimethyl-4-bromoaniline, 100mmol Na 2 CO 3, 1mmol cuprous iodide, 2mmol N,N'-dimethylethylenediamine and 26mL N,N-dimethylformamide were mixed, placed in a 100mL reaction bottle, heated to 120°C for Goldberg coupling reaction for 3h to obtain an intermediate. After the intermediate was cooled to 30°C, it was poured into 260mL water, and then extracted with dichloromethane three times to obtain an organic layer (26mL of dichloromethane was used for each extraction), and the organic layer was washed with 26mL of saturated sodium chloride solution to obtain an organic phase, and the organic phase was placed in a rotary evaporator and concentrated at 35°C for 15min to obtain a new diamine monomer.

[0085] The new diamine monomer obtained in this example is white, has a mass of 31.4 g, and a yield of 97%.

[0086] 1 The HNMR data are: 1 HNMR (400MHz, CDCl 3 ): δ7.47(s,4H),4.82(br.s,4H),3.40-3.55(m,4H),2.12(s,12H); HRMS(ES+)calcd.for C 19 H 25 N 4 O[M+H] + :325.4360;found:325.4355.

[0087] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A novel diamine monomer, characterized in that: The structural formula of the novel diamine monomer is: Among them, R 1 is OH, CH3, F or H, R 2 is CF3, CH3 or H, R 3 is CH3 or H.

2. The novel diamine monomer according to claim 1, characterized in that The novel diamine monomer is any one of the following structural formulas:

3. The method for preparing the novel diamine monomer according to claim 1 or 2, characterized in that: The following steps are included: (1) mixing 2-imidazolidinone, 4-haloaniline, an inorganic base, a catalyst, a ligand and a solvent to carry out a Goldberg coupling reaction to obtain an intermediate; (2) Extracting the intermediate to obtain a novel diamine monomer.

4. The preparation method according to claim 3, characterized in that: The structural formula of the 4-halogenated aniline in step (1) is: Where X is Br or I, R 1 is OH, CH3, F or H, R 2 is CF3, CH3 or H, R 3 is CH3 or H.

5. The preparation method according to claim 4, characterized in that: The inorganic base in step (1) is NaOH, KOH, CsOH, LiOH, Na2CO3, K2CO3, Cs2CO3 or K3PO4; The catalyst is cuprous iodide, cuprous chloride, cupric acetylate or cupric acetylacetonate; The ligand is N,N'-dimethylethylenediamine or N,N'-dimethyl-1,2-cyclohexanediamine; The solvent is toluene, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide or n-butanol.

6. The preparation method according to claim 4 or 5, characterized in that: The molar ratio of the 2-imidazolidinone, 4-halogenated aniline, inorganic base, catalyst and ligand in step (1) is 1:2-4:1-4:0.01-0.1:0.02-0.2, and the mass volume ratio of the 2-imidazolidinone and the solvent is 1g:3-5mL.

7. The preparation method according to claim 6, characterized in that: The temperature of the Goldberg coupling reaction in step (1) is 90 to 120° C., and the time of the Goldberg coupling reaction is 3 to 8 hours.

8. The preparation method according to claim 7, characterized in that: The extraction agent used in step (2) is dichloromethane, toluene or 2-methyltetrahydrofuran, and the number of extractions is 2 to 4 times; the volume mass ratio of the extraction agent used in each extraction to 2-imidazolidinone is 3 to 5 mL: 1 g.

9. Use of the novel diamine monomer according to claim 1 or 2 in the synthesis of novel polyimide.

Images