TWI790043B - Preparation method of dinitro compound, diamine and preparation method thereof, and polyimide - Google Patents

Abstract

A dinitro formula (2) and a preparation method thereof are provided,

. The dinitro formula (2) is reduced to form a diamine (3),

Description

Preparation method of dinitrogen compound, diamine monomer and preparation method thereof, and polyamide imine

This disclosure relates to compounds useful in forming polyimides, particularly dinitro compounds and diamine monomers formed therefrom, and polyimides formed therefrom.

Flexible electronics are widely used, such as flexible display, flexible solar cell, flexible lighting and so on. The upstream key material for the development of flexible electronics: optical-grade flexible substrate materials, its material design and acquisition, material characteristics and related surface coating process technology are key factors that affect the entire flexible electronics process. Therefore, in addition to the optical properties, heat resistance and chemical resistance of the flexible substrate material, the surface hardness, scratch resistance, gas barrier and electrical conductivity of the substrate material will determine the future development of flexible electronic components and related manufacturing processes. Operability and affect the use characteristics and life of the product. For example, displays have been developed into various forms of curved surface (Curved), bendable (Bendable), foldable (Foldable), and rollable (Rollable). The most important substrate for flexible electronic applications is polyimide (polyimide, PI), because polyimide has high heat resistance, chemical resistance and good electrical properties, it is unmatched by many other polymer materials at present, so it is very suitable as a substrate material such as a flexible display.

Aromatic polyimide is a well-known high-performance polymer material, widely used in semiconductor and electronic packaging processes due to its excellent thermal and chemical stability, good insulation properties and low dielectric constant, and excellent mechanical properties . However, one of the problems with most polyimides is their insolubility in most organic solvents and high glass transition temperature (Tg) or melting temperature caused by high intermolecular interactions and rigidity of the polymer backbone. These reasons make direct processing of most polyimides impossible in their imidized form. Therefore, the application of polyimide is limited in some fields. Formable processable plastics with moderately high softening temperatures and/or solubility in some organic solvents are required for practical applications.

Furthermore, in present-day technology, when polyimide films are closely bonded to inorganic substrates (metals, semiconductors, and ceramics) at elevated temperatures and then continuously cooled to room temperature after lamination, residual The phenomenon of expansion and peeling occurs due to the occurrence of stress, which greatly reduces the flatness of the film and prevents the subsequent process from proceeding smoothly. Therefore, how to reduce the thermal expansion of materials is the key to the current research and technology development of flexible substrates. Therefore, in order to allow polyimide to have both high temperature resistance and low thermal expansion coefficient, it is necessary to design and develop new monomers to achieve this goal.

Some embodiments of the present disclosure provide a dinitrogen compound whose structure is formula (2),

Some embodiments of the present disclosure provide a method for preparing dinitro compound formula (2), comprising: performing a nucleophilic reaction between 4,4'-dihydroxybenzophenone and 4-nitrobenzoyl chloride.

In some embodiments, in the method for preparing the dinitro compound formula (2), the molar ratio of 4,4'-dihydroxybenzophenone to 4-nitrobenzoyl chloride is about 1:2.

In some embodiments, in the method for preparing the dinitro compound formula (2), the nucleophilic reaction of 4,4'-dihydroxybenzophenone and 4-nitrobenzoyl chloride comprises using triethylamine as catalyst.

式 (3)。 Some embodiments of the present disclosure provide a diamine monomer having the structure of formula (3),

Formula (3).

。 Some embodiments of the disclosure provide a method for preparing the diamine monomer formula (3), comprising: reducing the dinitro compound formula (2),

.

In some embodiments, in the method for preparing the diamine compound formula (3), the reduction reaction of the dinitro compound formula (2) comprises: a reduction reaction catalyzed by hydrogen and activated carbon/palladium.

Some embodiments of the present disclosure provide a polyimide, comprising: repeating units polymerized from diamine monomers and dianhydride monomers, wherein the structure of the diamine monomer formula (3) is as follows,

In some embodiments, in the method for preparing a dinitro compound, performing a nucleophilic reaction between 4,4'-dihydroxybenzoyl ketone and 4-nitrobenzoyl chloride comprises: preparing a first solution, wherein 4 , 4'-dihydroxybenzoyl ketone was mixed with dimethylacetamide, then triethylamine was added and mixed well under nitrogen atmosphere; a second solution was prepared in which 4-nitrobenzoyl chloride was mixed with Dimethylacetamide is mixed; and the second solution is titrated into the first solution to form a mixed solution.

In some embodiments, the method for preparing the dinitrate compound further comprises: reducing the temperature of the mixed solution to about room temperature; adding water to the mixed solution to form a precipitate; and suction filtering the precipitate.

Some embodiments of the present disclosure provide a substrate comprising a polyimide as described above and in the embodiments and examples below.

FIG. 1 is a Fourier Transform Infrared Spectroscopy (FT-IR) graph according to an embodiment.

Figure 2 is the ¹ H nuclear magnetic resonance (NMR) spectrum of the dinitro compound formula (2).

Figure 3 is the ¹³ C NMR spectrum of the dinitro compound formula (2).

Figure 4 is the C-H heteronuclear two-dimensional NMR spectrum of the dinitro compound formula (2).

Fig. 5 is the ¹ H NMR spectrum of the diamine compound formula (3).

Figure 6 is the ¹³ C NMR spectrum of the diamine compound formula (3).

Figure 7 is a C-H heteronuclear two-dimensional NMR spectrum.

Fig. 8 is the Fourier transform infrared spectrum of polyamic acid and polyimide containing diamine compound formula (3).

In order to make the description of the present disclosure more detailed and complete, the implementation modes and specific examples of the present disclosure are illustratively described below; but this is not the only form for implementing or using the specific embodiments of the present disclosure. The embodiments disclosed below can be combined or substituted for each other when beneficial, and other embodiments can also be added to one embodiment without further description or illustration. In the following description, numerous specific details will be set forth in order to enable readers to fully understand the following embodiments. However, embodiments of the present disclosure may be practiced without these specific details.

In order to achieve polyimides that are transparent and resistant to high temperatures, some embodiments of the present disclosure provide polyimides with diphenyl ketone (Benzophenone) is a diamine monomer with ester chains (ester-linkage) on both sides, which can be synthesized into polyimide with dianhydride.

Some embodiments of the present disclosure provide a dinitrogen compound having a structure of formula (2),

The dinitro compound formula (2) is 4,4'-bis(4-nitrobenzoyloxy)benzophenone (4,4'-bis(4-nitrobenzoyloxy)benzophenone), which contains diphenylmethane Ketone (benzophenone) and two ester groups.

The reaction formula of preparing dinitrogen compound formula (2) is as follows:

Using 4,4'-dihydroxybenzophenone (4,4'-dihydroxybenzophenone) formula (1) as the starting material, using a catalyst to let 4,4'-dihydroxybenzophenone and 4-nitro Benzoyl chloride (4-nitrobenzoyl chloride) undergoes a nucleophilic substitution reaction to obtain a dinitro compound formula (2) with an ester group. In some embodiments, the catalyst is triethylamine.

Afterwards, dinitrogen compound formula (2) is carried out reduction reaction, obtains a kind of diamine monomer formula (3), prepares the reaction formula of diamine monomer formula (3) as follows:

The diamine monomer formula (3) is 4,4'-bis(4-aminobenzoyloxy)benzophenone (4,4'-bis(4-aminobenzoyloxy)benzophenone).

In some embodiments, the purified dinitro compound formula (2) having an ester group is used to reduce the dinitro compound formula (2) to a diamine monomer formula (3) by a hydrogen catalyst reduction method.

In some embodiments, the dinitro compound formula (2) is reduced to the diamine monomer formula (3) by hydrogen and activated carbon/palladium-catalyzed reduction reaction.

Afterwards, the diamine monomer formula (3) is polymerized with the dianhydride monomer to form polyimide, which has the repeating unit formula.

The diamine monomer formula (3) containing diphenyl ketone and two ester groups can react with aromatic or aliphatic dianhydride to form repeating units of polyimide.

In some embodiments, polyimides can be formed via a two-step process, first producing polyamic acid, followed by cyclization of the polyamic acid to form polyimides. In other embodiments, a one-step process cyclodehydration can be used to form polyimides.

In order to make the above and other objects, features, and advantages of the present invention more comprehensible, several embodiments are described in detail below in conjunction with the accompanying drawings.

Embodiment 1: prepare dinitro compound formula (2)

The detailed steps are as follows: Place a magnet in a 1000mL three-neck bottle, first weigh 21.43g (100mmol) of 4,4'-dihydroxybenzophenone (4,4'-dihydroxybenzophenone) and add 400mL of dimethyl acetyl Amine (DMAc), then add 22.26g (220mmol) of triethylamine (triethylamine) and fully stir and mix under nitrogen atmosphere.

In addition, 38.04g (205mmol) of 4-nitrobenzoyl chloride (4-nitrobenzoyl chloride) was weighed and dissolved in 100mL of DMAc, mixed and dissolved, and then slowly dripped into the three-necked flask using an equal pressure funnel within 60 minutes. Mixture.

After the titration is completed, the mixture is stirred at 80°C for 16 hours, then the temperature is lowered to room temperature and poured into 1500mL of deionized water. The white cotton-like precipitate is filtered by suction and washed with sufficient water and methanol After drying, the yield of the initial product dinitrogen compound formula (2) is about 95%.

Then recrystallize with dimethylformamide (DMF) to obtain white fine crystals, and the yield of dinitrogen compound formula (2) is about 90%.

A thermal differential scanning calorimetry (DSC) was used to measure the melting point range of the dinitrogen compound formula (2), and the mixture was heated at a heating rate of 10° C./min. The measured melting point range of the dinitrogen compound formula (2) is 238-240°C.

Then use Fourier Transform Infrared Spectrometer for analysis. Referring to Figure 1, the Fourier Transform Infrared Spectrum (KBr, cm ^-1 ) information of the obtained dinitrogen compound formula (2) is as follows: 1739 (ester group C=O stretching vibration), 1629 (keto-based C=O stretching vibration), 1531 (asymmetric N=O stretching vibration), 1350 (symmetrical N=O stretching vibration), 1262 (ether-based CO stretching vibration), 1071 (COC stretching vibration).

Afterwards, the NMR scan is carried out. Referring to Figure 2, the NMR spectrum information of the dinitrogen compound formula (2) is as follows: ¹ H NMR (600MHz, DMSO-d6, ppm): 7.59 (Hb, J=8.6Hz, 4H), 7.93 (Ha, J=8.6Hz, 4H), 8.41 (Hc, J=9.0Hz, 4H), 8.45 (Hd, J=9.0Hz, 4H). Furthermore, referring to Figure 3, the NMR spectrum information of the dinitrogen compound formula (2) is as follows: ¹³ C NMR (150MHz, DMSO-d6, ppm): 122.19 (C4), 124.04 (C9), 131.43 (C3), 131.44 (C8), 134.21 (C2), 134.91 (C7), 150.71 (C5), 153.63 (C10), 162.85 (C6), 1193.76 (C1).

As shown in ^{the 1} H NMR, ¹³ C NMR and CH heteronuclear two-dimensional NMR spectra of the dinitro compound formula (2) shown in Fig. 2 to Fig. 4, the relative position of each hydrogen and carbon can be calibrated, and All NMR spectral data were consistent with the expected structure.

Embodiment 2: prepare diamine monomer formula (3)

After obtaining the dinitro compound formula (2) having an ester group after purification, the dinitro compound formula (2) is reduced to the diamine monomer formula (3) by a hydrogen catalyst reduction method.

The detailed steps are as follows: at room temperature, place a magnet in a 500mL three-necked bottle, first weigh 1.0g (1.95mmol) of the dinitrogen compound formula (2) and add 100mL of dimethylacetamide (DMAc) and then stir, slightly Heat to 80°C until the dinitrogen compound formula (2) dissolves and then cool down to room temperature, then weigh 0.1g of 10% Pd/C (palladium/activated carbon) and disperse it in the mixed solution, and pass it under the hydrogen gas at normal temperature Stirring is continued, and the reaction bottle continues to maintain a pressurized environment. During the process, thin layer chromatography (thin layer chromatography, TLC) is used to monitor until the retention factor (retention factor, Rf) point of the initial dinitrogen compound formula (2) disappears. , the time required to reach this stage is about 8 hours. The mixed solution was filtered to remove the activated carbon palladium catalyst, and the filtrate was poured into 2000 mL of stirred water to obtain a white cottony precipitate. Immediately carry out suction filtration, wash with sufficient water and methanol, and then dry to obtain the yield of the primary product diamine monomer (3) of about 76%.

Afterwards, it was recrystallized from dimethylformamide (DMF) and methanol to obtain fine white crystals.

The melting point range of the diamine monomer formula (3) was measured by a thermal differential scanner (DSC), and heated at a heating rate of 10° C./min. The measured melting point range of the diamine monomer formula (3) is 278-280°C.

Then use a Fourier transform infrared spectrometer to analyze. Referring to Figure 1, the Fourier transform infrared spectrum (KBr, cm ^-1 ) of the obtained diamine monomer formula (3) is as follows: 3483, 3369 (primary amine NH stretching vibration) , 1726 (ester-based C=O stretching vibration), 1630 (ketone-based C=O stretching vibration), 1267 (ether-based CO stretching vibration), 1063 (COC stretching vibration).

Please refer to Figure 1 again, the starting material 4,4'-dihydroxybenzophenone formula (1), the dinitro compound formula (2) of Example 1, and the diamine monomer formula ( The Fourier transform infrared spectrum (FT-IR) diagrams of 3) are shown respectively. The starting material 4,4'-dihydroxybenzophenone formula (1) has an obvious characteristic absorption peak of hydroxyl (OH) at 3337cm ^-1 , and a characteristic absorption peak of ketone group at 1629cm ^-1 . When triethylamine is used as a base to activate the hydroxyl group and undergo condensation reaction with 4-nitrobenzoyl chloride, the characteristic absorption peak of the hydroxyl group disappears, and two symmetrical and asymmetrical nitro groups are produced at 1531 and 1350 cm ^-1 In addition, the characteristic absorption peak of the ester group occurs at 1739cm ^-1 , and the ketone group of benzophenone still exists at 1630cm ^-1 . After being reduced by hydrogen, the characteristic absorption peak of nitro group disappears, and a pair of NH stretching absorption peaks belonging to amine group appear at the high wave number of 3483 and 3369 cm ^-1 . In addition, there is also the characteristic absorption peak of the ester group at 1726cm ^-1 , and the ketone group of benzophenone still exists at 1630cm ^-1 . In the Fourier transform infrared spectrogram of diamine monomer formula (3), the ester group characteristic absorption peak at 1726cm ^-1 place, this absorption peak is lower than the wavenumber (1739cm ^-1 ) of dinitro compound formula (2) by 13cm ^{- 1} , which is the absorption shift caused by the conjugation of the para-substituted amine group.

Referring to Figure 5, the NMR spectrum information of the diamine compound formula (3) is as follows: ¹ H NMR (600MHz, DMSO-d6, ppm): 6.22 (NH2, 4H), 6.65 (Hd, J=8.8Hz, 4H) , 7.42 (Hb, J=8.7Hz, 4H), 7.83 (Hc, J=8.7Hz, 4H), 7.85 (Ha, J=8.7Hz, 4H). Furthermore, referring to Figure 6, the NMR spectrum information of the diamine compound formula (3) is as follows: ¹³ C NMR (150MHz, DMSO-d6, ppm): 122.79 (C9), 113.89 (C2), 122.24 (C4), 131.18 (C3), 132.06 (C8), 134.10 (C7), 154.41 (C5), 154.47 (C10), 164.11 (C6), 193.76 (C1).

As shown in ^{the 1} H NMR, ¹³ C NMR and CH heteronuclear two-dimensional NMR spectra of the diamine compound formula (3) shown in Figures 5 to 7, the relative positions of each hydrogen and carbon can be calibrated, and All NMR spectral data were consistent with the expected structure.

Fig. 8 is the Fourier transform infrared spectrum of polyamic acid (PAA) and polyimide (PI) formed by the diamine compound formula (3). Therefore, it can be known that the diamine monomer formula (3) provided in the present disclosure can be used to form polyimide.

Compared with common diamine monomers, the diamine monomer formula (3) provided in this disclosure has a special molecular structure design, and uses its functional groups to allow the molecules to be arranged neatly while avoiding the charge of the polymer chain segment The generation of transfer complexes, the polyimide derived from it will have high temperature resistance properties, and due to the structural design, compared with the general polyimide polymer, its high stacking increase makes the thermal expansion coefficient of the polymer The reduction will help various related products that will be applied to the high-temperature-resistant flexible electronics industry in the future, such as: flexible displays, flexible solar cells, flexible lighting, flexible electronic tags, or the like.

While the present disclosure has been disclosed above in terms of implementations, other implementations are possible. Therefore, the concept and scope of the claims to be applied are not limited to the description contained in the embodiments herein.

Any person skilled in the art can understand that various changes and modifications can be made without departing from the idea and scope of the present disclosure. Therefore, the protection scope of the present disclosure should be defined by the claims.

Claims (7)

A method for preparing dinitrogen compound, the structure of the dinitrogen compound is formula (2),

, the method comprising: nucleophilicly reacting 4,4'-dihydroxybenzoyl ketone with 4-nitrobenzoyl chloride, comprising: preparing a first solution in which the 4,4'-dihydroxydiphenyl Dimethyl ketone was mixed with dimethyl acetamide, then triethylamine was added as a catalyst and mixed well under nitrogen atmosphere; a second solution was prepared in which 4-nitrobenzoyl chloride was mixed with dimethyl acetamide the amine; and the second solution is titrated into the first solution to form a mixture. The method for preparing dinitrogen compounds as described in Claim 1, wherein the molar ratio of the 4,4'-dihydroxybenzophenone to the 4-nitrobenzoyl chloride is about 1:2. The method for preparing dinitrogen compounds as described in claim 2, further comprising: reducing the temperature of the mixed solution to about room temperature; adding water to the mixture to form a precipitate; and filtering the precipitate with suction. A kind of diamine monomer, its structure is formula (3),

A method for preparing a diamine monomer, the structure of the diamine monomer is formula (3),

, the method comprises: performing a reduction reaction on the dinitrogen compound formula (2),

The method for preparing a diamine monomer as described in Claim 5, wherein said reducing the dinitro compound formula (2) comprises: using hydrogen and activated carbon/palladium to catalyze the reduction reaction. A polyimide, comprising: a repeating unit formed by a diamine monomer formula (3) and a dianhydride monomer, wherein the structure of the diamine monomer formula (3) is as follows:

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