A diamine monomer for synthesizing a photosensitive polyimide and a method for preparing the same

Abstract

The application discloses a diamine monomer for synthesizing photosensitive polyimide and a preparation method thereof, and aims to provide the diamine monomer for synthesizing photosensitive polyimide which has good storage stability, a matching photosensitive wavelength and an industrial exposure wavelength, and can realize stable mass production in industry. The structural formula of the diamine monomer is shown in formula 1.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, specifically relating to a novel diamine monomer for synthesizing photosensitive polyimide, and also to a method for preparing the diamine monomer. Background Technology

[0002] Polyimide (PI) is often used as a buffer layer and protective layer in integrated circuits due to its excellent temperature resistance, high mechanical strength, and superior dielectric properties. To achieve these applications, PI thin film materials need to be patterned to connect certain specific areas of the semiconductor chip.

[0003] Traditional polyimide circuit board fabrication involves first coating polyimide into a film, then coating the polyimide film with a photoresist film. After patterning through exposure and development, the polyimide film is then treated with chemical etching to transfer the pattern from the photoresist onto the polyimide layer. However, this process is cumbersome and can compromise pattern quality, resulting in decreased pattern resolution and distorted graphic outlines, thus limiting its development.

[0004] To address the aforementioned issues, researchers developed and synthesized photosensitive polyimide (PSPI), which directly imparts photosensitivity to polyimide films. Through photolithography, patterns from a photomask are directly transferred onto the polyimide layer. PSPI functions as both a photoresist and a dielectric insulating layer, achieving self-patterning. Photosensitive polyimide can achieve self-patterning without the need for other photoresists, significantly simplifying chip manufacturing processes, saving costs, and greatly improving pattern accuracy and yield, thus powerfully driving the development of the electronic device field. Despite active research into the synthesis of photosensitive polyimide, its industrial supply is extremely limited, resulting in the reliance on imports. This is due to the stringent requirements regarding the purity, storage stability, repeatability of photosensitivity, and matching of photosensitive wavelengths for commercially available photosensitive polyimide. Summary of the Invention

[0005] To address the aforementioned shortcomings in the existing technology, the present invention aims to provide a diamine monomer for the synthesis of photosensitive polyimide that has good storage stability, a photosensitive wavelength that matches the industrial exposure wavelength (365nm), and can be stably mass-produced industrially.

[0006] The second objective of this invention is to provide a method for preparing diamine monomers for synthesizing photosensitive polyimides. This method has a simple synthetic route, high reaction yield, and strong stability of intermediate products.

[0007] Therefore, the first technical solution provided by this invention is as follows:

[0008] A diamine monomer for synthesizing photosensitive polyimide, wherein the diamine monomer has the structural formula shown in Formula 1:

[0009]

[0010] Formula 1.

[0011] Wherein, R is selected from one of the following aliphatic diamino-substituted diol compound fragments;

[0012]

[0013] The second technical solution provided by this invention is the above-mentioned method for preparing diamine monomers for synthesizing photosensitive polyimide. Using 5-hydroxy-2-nitrobenzaldehyde, aliphatic diamino-substituted diols, dihalogenated straight-chain alkanes, methyl acetoacetate, and a nitrogen source as raw materials, the diamine monomer is obtained through halogenation, nucleophilic substitution, and condensation reactions between different raw materials. The order of the halogenation, nucleophilic substitution, and condensation reactions can be arbitrarily interchanged.

[0014] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide includes the following steps:

[0015] S1. Under nitrogen protection, Lewis bases catalyze the halogenation reaction of aliphatic diamino-substituted diols with dihalo-substituted straight-chain alkanes to generate haloaliphatic diamines.

[0016] S2. Under nitrogen protection, Lewis base catalyzes the nucleophilic substitution of 5-hydroxy-2-nitrobenzaldehyde and the haloallodiamine prepared in step S1 to generate an aliphatic diamine nucleophilic product.

[0017] S3. Under nitrogen protection, methyl acetoacetate, the aliphatic diamine nucleophilic product prepared in step S2, and a nitrogen source undergo a condensation reaction to obtain a condensation product. The condensation product is then filtered and recrystallized to obtain a diamine monomer for the synthesis of photosensitive polyimide.

[0018] Furthermore, in the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide, wherein:

[0019] S1. The molar ratio of the aliphatic diamino-substituted diol and the dihalo-substituted straight-chain alkane is 1.0:(1.1-2.0); the reaction temperature of step S1 is 30-80℃, and the reaction time is 10-15h;

[0020] The molar ratio of 5-hydroxy-2-nitrobenzaldehyde in S2 to the haloalloalicylic diamine prepared in S1 is 1.0:(1.1-2.0); the reaction temperature in S2 is 0-50℃, and the reaction time is 10-15h;

[0021] The molar ratio of S3. methyl acetoacetate, S2. the prepared aliphatic diamine nucleophilic product, and the nitrogen source is 1.0:(1.1-2.0):(2.0-2.5); the reaction temperature described in S3 is 30-80℃, and the reaction time is 10-15h.

[0022] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide includes the following steps:

[0023] S1. Dissolve 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate, and a nitrogen source in an organic solvent and obtain a photosensitive substance containing hydroxyl groups through a condensation reaction;

[0024] S2. Under nitrogen protection, Lewis base catalyzes the halogenation reaction of dihalogenated straight-chain alkanes and the hydroxyl-containing photosensitive substance prepared in step S1 in an organic solvent to generate a halogenated hydroxyl-containing photosensitive substance.

[0025] S3. Under nitrogen protection, a Lewis base catalyzes aliphatic diamino-substituted diols and the halogenated photosensitive substance containing hydroxyl groups prepared in step S2 to undergo a nucleophilic reaction in an organic solvent to obtain a nucleophilic product. The nucleophilic product is then filtered and recrystallized to obtain a diamine monomer used for the synthesis of photosensitive polyimide.

[0026] Furthermore, in the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide, wherein:

[0027] S1. The molar ratio of 5-hydroxy-2-nitrobenzaldehyde and methyl acetoacetate is 1.0:(2.0-3.0); the reaction temperature of step S1 is 0-50℃, and the reaction time is 10-15h;

[0028] S2. The molar ratio of the hydroxyl-containing photosensitive substance prepared in step S1 to the dihalo-substituted straight-chain alkane is 1.0:(1.1-2.0); the reaction temperature in S2 is 30-80℃, and the reaction time is 10-15h; S3. The molar ratio of the aliphatic diamino-substituted diol to the halogenated hydroxyl-containing photosensitive substance prepared in step S2 is (1.1-2.0):1.0; the reaction temperature in S3 is 30-80℃, and the reaction time is 10-15h.

[0029] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide includes the following steps:

[0030] S1. Under nitrogen protection, 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate, and a nitrogen source are condensed in an organic solvent via an East base catalysis to obtain a photosensitive substance containing hydroxyl groups;

[0031] S2. Under nitrogen protection, aliphatic diamino-substituted diols react with dihalo-substituted straight-chain alkanes to generate halogenated products;

[0032] S3. Under nitrogen protection, the photosensitive substance containing hydroxyl groups prepared in S1 and the halogenated product prepared in S1 undergo a nucleophilic reaction catalyzed by the Lewis base to generate a nucleophilic product. The nucleophilic product is then filtered and recrystallized to obtain a diamine monomer for the synthesis of photosensitive polyimide.

[0033] Furthermore, in the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide, wherein:

[0034] S1. The molar ratio of 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate, and nitrogen source is 1.0:(2.0-3.0):(1.1-1.5); the reaction temperature in step S1 is 0-50℃, and the reaction time is 12h.

[0035] S2. The molar ratio of the aliphatic diamino-substituted diol and the dihalo-substituted straight-chain alkane prepared in step S1 is 1.0:(1.1-1.5); the reaction temperature in S2 is 30-80℃, and the reaction time is 12h;

[0036] S3. The molar ratio of the aliphatic diamino-substituted diol to the halogenated photosensitive substance containing hydroxyl groups prepared in step S2 is (1.1-2.0):1.0; the reaction temperature in S3 is 30-80℃, and the reaction time is 12h;

[0037] Furthermore, in the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide, wherein:

[0038] The nitrogen source is selected from any one of ammonium acetate, ammonium bicarbonate, ammonium carbonate, ammonium chloride, glacial acetic acid, and ammonium bisulfate;

[0039] The organic solvent is any one of methanol, ethanol, isopropanol, dioxane, tetrahydrofuran, chloroform, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0040] The Lewis base is selected from any one of sodium hydride, calcium hydride, lithium carbonate, potassium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, and barium carbonate.

[0041] Furthermore, in the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide, wherein:

[0042] The aliphatic diamino group is

[0043]

[0044] One of them;

[0045] The dihalogenated straight-chain alkane is

[0046]

[0047] One of them.

[0048] Compared with the prior art, the technical solution provided by the present invention has the following technical advantages:

[0049] 1. The diamine monomer for synthesizing photosensitive polyimide provided by this invention has the advantages of excellent stability, photosensitive wavelength, and matching with industrial exposure.

[0050] 2. The method for preparing diamine monomers for synthesizing photosensitive polyimide provided by this invention is simple, time-saving, mild in reaction conditions, simple in post-reaction processing, widely applicable, highly designable, and has a high process yield; it effectively solves the problems of low purity, poor storage stability, and mismatch between photosensitive polyimide commercial products and industrial exposure wavelength (365nm). Attached Figure Description

[0051] Figure 1 The 1H NMR spectrum of compound A2 in Example 2 of this invention;

[0052] Figure 2 The 1H NMR spectrum of compound C2 in Example 2 of this invention;

[0053] Figure 3 This is the ultraviolet absorption spectrum of compound C2 in Example 2 of the present invention before and after irradiation with 365nm light.

[0054] Figure 4 This is a photograph of compound C2 used in Example 2 of the present invention to prepare photosensitive polyimide, which is then applied to a copper-clad circuit board. Detailed Implementation

[0055] The preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for illustrative and understanding purposes only and are not intended to limit the scope of the invention.

[0056] Example 1

[0057] The following is a synthetic route for synthesizing a diamine monomer for photosensitive polyimide provided in this embodiment:

[0058]

[0059] Its preparation method includes the following steps:

[0060] The synthesis of compound A1, S1, specifically includes the following steps:

[0061] 1) Add 4.5g of 1,4-diamino-2,3-butanediol and 25ml of anhydrous tetrahydrofuran to a double-necked flask, and add 5.4g of potassium carbonate to the reaction flask while stirring;

[0062] 2) Under nitrogen protection, 8.6 g of 1,4-dibromobutane was slowly added dropwise to the reaction solution over a period of 1 hour. After the addition was complete, the mixture was heated to 65°C and refluxed for 12 hours.

[0063] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered, the filter cake was collected, and the filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound A1. The yield was calculated to be 96.8%.

[0064] The synthesis of compound B1, S2, specifically includes the following steps:

[0065] 1) Add 2.6g of 5-hydroxy-2-nitrobenzaldehyde, 20ml of anhydrous tetrahydrofuran and 4.5g of compound A1 to a double-necked flask, and add 1.8g of potassium carbonate to the reaction flask while stirring; under nitrogen protection, heat to 50℃ and react for 12h.

[0066] 2) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered, the filter cake was collected, and the filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound B1. The yield was calculated to be 98.7%.

[0067] The synthesis of compound C, S3, specifically includes the following steps:

[0068] 1) Add 0.8g of methyl acetoacetate, 40ml of anhydrous ethanol and 9.2g of compound B1 to a two-necked flask, and add 3.7g of ammonium bicarbonate to the reaction flask while stirring;

[0069] 2) Under nitrogen protection, heat to 80°C and reflux for 12 hours;

[0070] 3) After the reaction was completed, the reaction solution was cooled to room temperature, filtered, and the filtrate was dried by rotary evaporation. The solid was recrystallized from ethanol to obtain a yellow solid (compound C1), and its yield was measured to be 97.4%.

[0071] Example 2

[0072] The synthetic route for the diamine monomer used to synthesize the photosensitive polyimide in this embodiment is as follows:

[0073]

[0074] S1. Synthesis of compound A2

[0075] 1) Add 5.2g of 5-hydroxy-2-nitrobenzaldehyde and 10ml of anhydrous ethanol to a two-necked flask, and while stirring, add 5.3g of methyl acetoacetate, 0.1g of pyridine, and 0.1g of glacial acetic acid to the reaction flask in sequence;

[0076] 2) Under nitrogen protection, 8.6 g of ammonia water (20% by mass) was slowly added dropwise to the reaction solution over 1 hour. After the addition was complete, the mixture was kept at 0°C for 12 hours.

[0077] 3) After the reaction is complete, stop heating and cool the reaction solution to room temperature, resulting in the precipitation of a large amount of solid. Filter the reaction solution and collect the filter cake; place the filter cake in a vacuum oven and dry it at 50°C for 24 hours to obtain compound A2, with a calculated yield of 97.6%; the 1H NMR spectrum of compound A2 is shown in [reference needed]. Figure 1 ,pass Figure 1 The integral area and peak position in the spectrum indicate that compound A2 is the target product for synthesis.

[0078] S2. Synthesis of Compound B

[0079] 1) Add 4.5g of compound A2 and 20ml of anhydrous tetrahydrofuran to the reaction flask, and add 3.2g of anhydrous potassium carbonate to the reaction flask in sequence while stirring;

[0080] 2) Under nitrogen protection, 4.8 g of 1,4-dibromobutane was slowly added dropwise to the reaction solution over a period of 1 hour. After the addition was complete, the mixture was heated to 60°C and refluxed for 12 hours.

[0081] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. After filtration, the filter cake was collected and placed in a vacuum oven to dry at 60°C for 24 hours to obtain compound B2. The yield was measured to be 98.5%.

[0082] S3. Synthesis of compound C2

[0083] 1) Add 1.1g of 1,6-diamino-2,5-hexanediol, 50ml of anhydrous tetrahydrofuran and 7.3g of compound B2 to a double-necked flask, and add 8.4g of anhydrous potassium carbonate to the reaction flask while stirring;

[0084] 2) Under nitrogen protection, the reaction was heated to 50°C for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, filtered, and the filtrate was evaporated to dryness. The solid was recrystallized from ethanol to give a yellow solid (compound C2), with a yield of 98.1%. The 1H NMR spectrum of compound C2 is shown in the attached image. Figure 2 ,pass Figure 2 The integral area and peak position in the spectrum confirm that compound C2 is the target product for synthesis.

[0085] See the UV absorption spectra of compound C2 before and after 365nm light irradiation. Figure 3 ,pass Figure 3 It can be seen that after being exposed to light, the absorption peak of compound C2, which was originally at 350 nm, red-shifted to 400 nm, indicating that compound C2 has good photosensitivity (photosensitive wavelength is 365 nm).

[0086] Example 3

[0087] The synthetic route for the diamine monomer used to synthesize the photosensitive polyimide in this embodiment is as follows:

[0088]

[0089] The preparation method is carried out in the following steps in sequence:

[0090] S1. Synthesis of compound A3

[0091] 1) Add 5.2g of 5-hydroxy-2-nitrobenzaldehyde and 10ml of anhydrous ethanol to a two-necked flask, and while stirring, add 5.5g of methyl acetoacetate and 4.7g of ammonium acetate to the reaction flask in sequence;

[0092] 2) Under nitrogen protection, heat to 50℃ and react for 12 hours;

[0093] 3) After the reaction is complete, stop heating and cool the reaction solution to room temperature, whereupon a large amount of solid will precipitate.

[0094] 4) Filter the reaction solution and collect the filter cake;

[0095] 5) The filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound A3, with a yield of 98.4%.

[0096] S2. Synthesis of compound B3

[0097] 1) Add 2.3g of 1,8-diamino-2,7-octanediol and 20ml of anhydrous tetrahydrofuran to a two-necked flask, and add 2.1g of sodium carbonate to the reaction flask while stirring;

[0098] 2) Under nitrogen protection, 6.7 g of 1,4-dibromobutane was slowly added dropwise to the reaction solution over a period of 1 hour. After the addition was complete, the mixture was heated to 45°C and reacted for 12 hours.

[0099] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. Then the reaction solution was filtered and the filter cake was collected. The filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound B3. The yield was calculated to be 97.9%.

[0100] S3. Synthesis of compound C3

[0101] 1) Add 6.4g of compound A, 40ml of anhydrous tetrahydrofuran and 4.0g of compound B3 to a double-necked flask, and add 7.2g of sodium carbonate to the reaction flask while stirring;

[0102] 2) Under nitrogen protection, heat to 55℃ and react for 12 hours;

[0103] 3) After the reaction was completed, the reaction solution was cooled to room temperature, filtered, and the filtrate was dried by rotary evaporation. The solid was recrystallized from ethanol to obtain a yellow solid (compound C3), and its yield was measured to be 98.7%.

[0104] Example 4

[0105] The following is a synthetic route for a diamine monomer used to synthesize photosensitive polyimide, provided in this embodiment:

[0106]

[0107] The preparation method is carried out in the following steps in sequence:

[0108] S1. Synthesis of compound A4

[0109] 1) Add 5.2g of 5-hydroxy-2-nitrobenzaldehyde and 10ml of anhydrous ethanol to a two-necked flask, and while stirring, add 5.4g of methyl acetoacetate and 6.5g of ammonium bisulfate to the reaction flask in sequence;

[0110] 2) Under nitrogen protection, heat to 30℃ and react for 12 hours;

[0111] 3) After the reaction is complete, stop heating and cool the reaction solution to room temperature. A large amount of solid precipitates out. Then filter the reaction solution and collect the filter cake. Place the filter cake in a vacuum oven and dry it at 50°C for 24 hours to obtain compound A4. The yield is calculated to be 97.6%.

[0112] S2. Synthesis of compound B4

[0113] 1) Add 3.2g of 1,8-diamino-3,6-octanediol and 20ml of anhydrous tetrahydrofuran to a double-necked flask, and add 2.1g of potassium carbonate to the reaction flask while stirring;

[0114] 2) Under nitrogen protection, 6.7 g of 1,4-dibromobutane was slowly added dropwise to the reaction solution over a period of 1 hour. After the addition was complete, the mixture was heated to 60 °C and refluxed for 12 hours.

[0115] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. The reaction solution was filtered and the filter cake was collected. The filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound B4. The yield was calculated to be 98.3%.

[0116] S3. Synthesis of compound C4

[0117] 1) Add 6.4g of compound A4 and 4.0g of compound B4 to a double-necked flask, and add 7.2g of potassium carbonate to the reaction flask while stirring;

[0118] 2) Under nitrogen protection, the reaction was heated to 40°C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, filtered, and the filtrate was dried by rotary evaporation. The solid was recrystallized from ethanol to obtain a yellow solid (compound C4). The yield was 97.9%.

[0119] Example 5

[0120] The following is a synthetic route for a diamine monomer used to synthesize photosensitive polyimide, provided in this embodiment:

[0121]

[0122] The preparation method is carried out in the following steps in sequence:

[0123] The synthesis of compound A5, S1, specifically includes the following steps:

[0124] 1) Add 5.0g of 1,5-diamino-2,3-pentanediol and 25ml of anhydrous tetrahydrofuran to a double-necked flask, and add 5.6g of potassium carbonate to the reaction flask while stirring;

[0125] 2) Under nitrogen protection, 8.7 g of 1,4-dibromobutane was slowly added dropwise to the reaction solution over a period of 1 hour. After the addition was complete, the mixture was heated to 65°C and refluxed for 12 hours.

[0126] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered, the filter cake was collected, and the filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound A5. The yield was calculated to be 97.2%.

[0127] The synthesis of compound B5, S2, specifically includes the following steps:

[0128] 1) Add 2.8 g of 5-hydroxy-2-nitrobenzaldehyde, 20 ml of anhydrous tetrahydrofuran and 4.7 g of compound A5 to a double-necked flask, and add 2.0 g of potassium carbonate to the reaction flask while stirring; under nitrogen protection, heat to 50 °C and react for 12 h.

[0129] 2) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered, the filter cake was collected, and the filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound B5. The yield was calculated to be 98.1%.

[0130] The synthesis of compound C5 (S3) specifically includes the following steps:

[0131] 1) Add 1.0g of methyl acetoacetate, 40ml of anhydrous ethanol and 9.4g of compound B5 to a double-necked flask, and add 4.0g of ammonium bicarbonate to the reaction flask while stirring;

[0132] 2) Under nitrogen protection, heat to 80°C and reflux for 12 hours;

[0133] 3) After the reaction was completed, the reaction solution was cooled to room temperature, filtered, and the filtrate was dried by rotary evaporation. The solid was recrystallized from ethanol to obtain a yellow solid (compound C5), and its yield was measured to be 96.9%.

[0134] Example 6

[0135] The following is a synthetic route for a diamine monomer used to synthesize photosensitive polyimide, provided in this embodiment:

[0136]

[0137] The preparation method is carried out in the following steps in sequence:

[0138] The synthesis of compound A6, S1, specifically includes the following steps:

[0139] 1) Add 7.6g of 1,8-diamino-2,7-octanediol and 25ml of anhydrous tetrahydrofuran to a double-necked flask, and add 5.9g of potassium carbonate to the reaction flask while stirring;

[0140] 2) Under nitrogen protection, 9.1 g of 1,4-dibromobutane was slowly added dropwise to the reaction solution over a period of 1 hour. After the addition was complete, the mixture was heated to 75°C and refluxed for 12 hours.

[0141] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered, the filter cake was collected, and the filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound A6. The yield was calculated to be 98.3%.

[0142] The synthesis of compound B6, S2, specifically includes the following steps:

[0143] 1) Add 2.5g of 5-hydroxy-2-nitrobenzaldehyde, 20ml of anhydrous tetrahydrofuran and 6.9g of compound A6 to a double-necked flask, and add 1.8g of potassium carbonate to the reaction flask while stirring; under nitrogen protection, heat to 40℃ and react for 12h.

[0144] 2) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered, the filter cake was collected, and the filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound B6. The yield was calculated to be 97.9%.

[0145] The synthesis of compound C6 (S3) specifically includes the following steps:

[0146] 1) Add 1.2g of methyl acetoacetate, 40ml of anhydrous ethanol and 15.6g of compound B6 to a two-necked flask, and add 4.0g of ammonium bicarbonate to the reaction flask while stirring;

[0147] 2) Under nitrogen protection, heat to 75°C and reflux for 12 hours;

[0148] 3) After the reaction was completed, the reaction solution was cooled to room temperature, filtered, and the filtrate was dried by rotary evaporation. The solid was recrystallized from ethanol to obtain a yellow solid (compound C6), and its yield was measured to be 98.9%.

[0149] Example 7

[0150] The following is a synthetic route for a diamine monomer used to synthesize photosensitive polyimide, provided in this embodiment:

[0151]

[0152] The preparation method is carried out in the following steps in sequence:

[0153] The synthesis of compound A7, S1, specifically includes the following steps:

[0154] 1) Add 7.6g of 1,8-diamino-2,7-octanediol and 25ml of anhydrous tetrahydrofuran to a double-necked flask, and add 5.9g of potassium carbonate to the reaction flask while stirring;

[0155] 2) Under nitrogen protection, 8.0 g of dibromoethane was slowly added dropwise to the reaction solution over 1 hour. After the addition was complete, the mixture was heated to 75°C and refluxed for 12 hours.

[0156] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered, the filter cake was collected, and the filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound A7. The yield was calculated to be 97.6%.

[0157] The synthesis of compound B7 (S2) specifically includes the following steps:

[0158] 1) Add 2.5g of 5-hydroxy-2-nitrobenzaldehyde, 20ml of anhydrous tetrahydrofuran and 6.6g of compound A7 to a double-necked flask, and add 1.8g of potassium carbonate to the reaction flask while stirring; under nitrogen protection, heat to 40℃ and react for 12h.

[0159] 2) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered, the filter cake was collected, and the filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound B7. The yield was calculated to be 98.1%.

[0160] The synthesis of compound C7 (S3) specifically includes the following steps:

[0161] 1) Add 1.1g of methyl acetoacetate, 40ml of anhydrous ethanol and 15.2g of compound B7 to a two-necked flask, and add 4.0g of ammonium bicarbonate to the reaction flask while stirring;

[0162] 2) Under nitrogen protection, heat to 75°C and reflux for 12 hours;

[0163] 3) After the reaction was completed, the reaction solution was cooled to room temperature, filtered, and the filtrate was dried by rotary evaporation. The solid was recrystallized from ethanol to obtain a yellow solid (compound C7), and its yield was measured to be 98.5%.

[0164] Example 8

[0165] The following is a synthetic route for a diamine monomer used to synthesize photosensitive polyimide, provided in this embodiment:

[0166]

[0167] The preparation method is carried out in the following steps in sequence:

[0168] The synthesis of compound A8, S1, specifically includes the following steps:

[0169] 1) Add 7.6g of 1,8-diamino-2,7-octanediol and 25ml of anhydrous tetrahydrofuran to a double-necked flask, and add 5.9g of potassium carbonate to the reaction flask while stirring;

[0170] 2) Under nitrogen protection, 10.5 g of 1,7-dibromoheptane was slowly added dropwise to the reaction solution over a period of 1 hour. After the addition was complete, the mixture was heated to 75°C and refluxed for 12 hours.

[0171] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated out. The solid was filtered, the filter cake was collected, and the filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound A8. The yield was calculated to be 97.9%.

[0172] The synthesis of compound B8, S2, specifically includes the following steps:

[0173] 1) Add 2.7g of 5-hydroxy-2-nitrobenzaldehyde, 20ml of anhydrous tetrahydrofuran and 7.5g of compound A8 to a double-necked flask, and add 1.8g of potassium carbonate to the reaction flask while stirring; under nitrogen protection, heat to 40℃ and react for 12h.

[0174] 2) After the reaction was completed, the reaction solution was cooled to room temperature and a large amount of solid precipitated out. The solid was filtered and the filter cake was collected. The filter cake was placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound B8. The yield was calculated to be 98.8%.

[0175] The synthesis of compound C8 (S3) specifically includes the following steps:

[0176] 1) Add 1.6g of methyl acetoacetate, 40ml of anhydrous ethanol and 17.8g of compound B8 to a two-necked flask, and add 4.0g of ammonium bicarbonate to the reaction flask while stirring;

[0177] 2) Under nitrogen protection, heat to 75°C and reflux for 12 hours;

[0178] 3) After the reaction was completed, the reaction solution was cooled to room temperature, filtered, and the filtrate was dried by rotary evaporation. The solid was recrystallized from ethanol to obtain a yellow solid (compound C8), and its yield was measured to be 97.4%.

[0179] Application example:

[0180] (1) Weigh 91.3g of 4,4'-diaminodiphenyl ether and 47.2g of photosensitive diamine monomer and add them to a reactor equipped with a stirrer. After mixing evenly, place the reactor in a 15°C water bath. Then add 1820.3g of N,N-dimethylacetamide to the reactor and stir for 10 minutes until the diamine monomer is completely dissolved. Continue to add 50.3g of 5,5'- (Propyl-2,2-dimethylbis(4,1-phenylene)bis(oxy)bis(isobenzofuran-1,3-dione), continued stirring for 10 hours to obtain a photosensitive polyamic acid solution; under room temperature and light-protected conditions, the polyamic acid solution was filtered through a 0.22-mesh filter to remove bubbles, and then uniformly cast onto a glass slide. The polyamic acid film was placed in a nitrogen atmosphere and kept at 60°C for 100 minutes and 120°C for 100 minutes, and then imidized by segmented heating. The solvent was evaporated to obtain a 20 μm self-supporting photosensitive polyimide film;

[0181] (2) The photosensitive polyamic acid film filtered and defoamed in step (1) is dried at 70°C for 5 hours in a blower heating device, and then exposed to ultraviolet light with a wavelength of 200nm. The total exposure time is 1.2 × 10⁻⁶. 2 s;

[0182] (3) Immerse the photosensitive polyamic acid film exposed in step (2) in the developing solution at room temperature for 60 seconds, then rinse with ethanol and dry with cold air. Then, under a nitrogen atmosphere, first keep it at 60°C for 100 minutes, and then keep it at 120°C for 100 minutes to obtain a photosensitive polyimide film with Ag metal catalyst pattern on the surface;

[0183] The developing solution is obtained by dissolving 50g of silver nitrate in 1 liter of ethanol solvent and mixing them evenly.

[0184] (4) The photosensitive polyimide film with Ag metal catalyst pattern on the surface prepared in step (3) is immersed in a copper plating solution for chemical plating to obtain a polyimide resin film material with a specific conductive copper metal pattern on the surface. Figure 4 ;pass Figure 4 This demonstrates the feasibility of applying photosensitive polyimide to copper-clad laminates.

[0185] The copper plating solution is prepared by mixing 10 g / L of copper sulfate pentahydrate, 15 g of potassium sodium tartrate, and 10 mL of formaldehyde evenly, and the temperature of the chemical copper plating solution is 30°C.

Claims

1. A diamine monomer for synthesizing photosensitive polyimide, characterized in that: The diamine monomer has the structural formula shown in Formula 1: ； Formula 1 in, The structural fragment is selected from one of the following aliphatic diamino-substituted diol compound residues; ； Or the diamine monomer structure is shown in Formula 2: ； Formula 2 Or the diamine monomer structure is shown in Formula 3: ； Formula 3.

2. The method for preparing the diamine monomer for synthesizing photosensitive polyimide according to claim 1, characterized in that: The method for preparing the diamine monomer shown in Formula 1 is as follows: using 5-hydroxy-2-nitrobenzaldehyde, aliphatic diamino-substituted diol, dihalogenated straight-chain alkane, methyl acetoacetate, and a nitrogen source as raw materials, the diamine monomer is obtained through halogenation reaction, nucleophilic substitution reaction, and condensation reaction between different raw materials; the order of the halogenation reaction, nucleophilic substitution reaction, and condensation reaction can be arbitrarily interchanged. The aliphatic diamino-substituted diol is one of the compounds shown in the following structural formulas: ； The dihalo-substituted straight-chain alkane is one of the compounds shown in the following structural formulas: ； The nitrogen source is selected from any one of ammonium acetate, ammonium bicarbonate, ammonium carbonate, ammonium chloride, and ammonium bisulfate.

3. The method for preparing the diamine monomer for synthesizing photosensitive polyimide according to claim 2, characterized in that: Includes the following steps: S1. Under nitrogen protection, Lewis bases catalyze the halogenation reaction of aliphatic diamino-substituted diols with dihalo-substituted straight-chain alkanes to generate haloaliphatic diamines. S2. Under nitrogen protection, Lewis base catalyzes the nucleophilic substitution of 5-hydroxy-2-nitrobenzaldehyde and the haloallodiamine prepared in step S1 to generate an aliphatic diamine nucleophilic product. S3. Under nitrogen protection, methyl acetoacetate, the aliphatic diamine nucleophilic product prepared in step S2, and a nitrogen source undergo a condensation reaction to obtain a condensation product. The condensation product is then filtered and recrystallized to obtain a diamine monomer for the synthesis of photosensitive polyimide.

4. The method for preparing the diamine monomer for synthesizing photosensitive polyimide according to claim 3, characterized in that: The molar ratio of the aliphatic diamino-substituted diol and the dihalo-substituted straight-chain alkane in step S1 is 1.0:(1.1-2.0); the reaction temperature in step S1 is 30-80℃, and the reaction time is 10-15h. The molar ratio of 5-hydroxy-2-nitrobenzaldehyde in step S2 to the haloalloalicylic diamine prepared in step S1 is 1.0:(1.1-2.0); the reaction temperature in step S2 is 0-50℃, and the reaction time is 10-15h. The molar ratio of methyl acetoacetate in step S3, the aliphatic diamine nucleophilic product prepared in step S2, and the nitrogen source is 1.0:(1.1-2.0):(2.0-2.5); the reaction temperature in step S3 is 30-80℃ and the reaction time is 10-15h.

5. The method for preparing the diamine monomer for synthesizing photosensitive polyimide according to claim 2, characterized in that: Includes the following steps: S1. Dissolve 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate, and a nitrogen source in an organic solvent and obtain a photosensitive substance containing hydroxyl groups through a condensation reaction; S2. Under nitrogen protection, Lewis base catalyzes the halogenation reaction of dihalogenated straight-chain alkanes and the hydroxyl-containing photosensitive substance prepared in step S1 in an organic solvent to generate a halogenated hydroxyl-containing photosensitive substance. S3. Under nitrogen protection, a Lewis base catalyzes aliphatic diamino-substituted diols and the halogenated photosensitive substance containing hydroxyl groups prepared in step S2 to undergo a nucleophilic reaction in an organic solvent to obtain a nucleophilic product. The nucleophilic product is then filtered and recrystallized to obtain a diamine monomer used for the synthesis of photosensitive polyimide.

6. The method for preparing the diamine monomer for synthesizing photosensitive polyimide according to claim 5, characterized in that: The molar ratio of 5-hydroxy-2-nitrobenzaldehyde and methyl acetoacetate in step S1 is 1.0:(2.0-3.0); the reaction temperature in step S1 is 0-50℃, and the reaction time is 10-15h. In step S2, the molar ratio of the hydroxyl-containing photosensitive substance prepared in step S1 to the dihalogenated straight-chain alkane is 1.0:(1.1-2.0); the reaction temperature in step S2 is 30-80℃, and the reaction time is 10-15h. The molar ratio of the aliphatic diamino-substituted diol in step S3 to the halogenated photosensitive substance containing hydroxyl groups prepared in step S2 is (1.1-2.0):1.0; the reaction temperature in step S3 is 30-80℃, and the reaction time is 10-15h.

7. The method for preparing the diamine monomer for synthesizing photosensitive polyimide according to claim 2, characterized in that: Includes the following steps: S1. Under nitrogen protection, a Lewis base catalyzes the condensation reaction of 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate, and a nitrogen source in an organic solvent to obtain a photosensitive substance containing hydroxyl groups; S2. Under nitrogen protection, aliphatic diamino-substituted diols react with dihalo-substituted straight-chain alkanes to generate halogenated products; S3. Under nitrogen protection, the photosensitizing substance containing hydroxyl groups prepared in step S1 and the halogenated product prepared in step S1 undergo a nucleophilic reaction to generate a nucleophilic product. The nucleophilic product is filtered and recrystallized to obtain a diamine monomer for the synthesis of photosensitive polyimide.

8. The method for preparing the diamine monomer for synthesizing photosensitive polyimide according to claim 7, characterized in that: The molar ratio of 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate, and nitrogen source in step S1 is 1.0:(2.0-3.0):(1.1-1.5); the reaction temperature in step S1 is 0-50℃, and the reaction time is 10-15h. The mass ratio of the aliphatic diamino-substituted diol and the dihalo-substituted straight-chain alkane prepared in step S1 in S2 is 1.0:(1.1-1.5); the reaction temperature in S2 is 30-80℃, and the reaction time is 10-15h. The molar ratio of the aliphatic diamino-substituted diol in step S3 to the halogenated photosensitive substance containing hydroxyl groups prepared in step S2 is (1.1-2.0):1.0; the reaction temperature in step S3 is 30-80℃, and the reaction time is 10-15h.

9. The method for preparing the diamine monomer for synthesizing photosensitive polyimide according to any one of claims 5 and 7, characterized in that: The organic solvent is any one of methanol, ethanol, isopropanol, dioxane, tetrahydrofuran, chloroform, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. The Lewis base is selected from any one of sodium hydride, calcium hydride, lithium carbonate, potassium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, and barium carbonate.

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