Diamine monomer for synthesizing photosensitive polyimide and preparation method thereof

Abstract

The invention discloses a diamine monomer for synthesizing photosensitive polyimide and a preparation method of the diamine monomer, and aims to provide the diamine monomer for synthesizing the photosensitive polyimide, which is good in storage stability, has a photosensitive wave band matched with the industrial exposure wavelength, and can realize industrial stable mass production. The structural formula of the diamine monomer is as shown in formula 1: # imgabs0 #, and belongs to the field of organic synthesis.

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and in particular relates to a novel diamine monomer for synthesizing photosensitive polyimide. The invention also relates to a preparation method of the diamine monomer. Background Art

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

[0003] The traditional polyimide circuit board preparation process is to first coat the polyimide into a film, then coat a layer of photoresist film on the surface of the polyimide film, pattern it through processes such as exposure and development, and then treat the polyimide film through methods such as chemical etching to transfer the pattern on the photoresist to the polyimide layer. However, this process is relatively cumbersome and will cause a certain degree of damage to the pattern quality, resulting in a decrease in pattern resolution and distortion of the graphic contour, thus limiting its development.

[0004] In order to solve the above problems, researchers developed and synthesized photosensitive polyimide (PSPI), which directly gave the polyimide film photosensitivity. Through the photolithography process, the pattern on the mask is directly transferred to the polyimide layer. PSPI not only plays the role of photoresist, but also realizes the function of dielectric insulation layer, realizing self-patterning. Photosensitive polyimide can achieve self-patterning without the help of other photoresists, which not only greatly simplifies the chip manufacturing process and saves costs, but also greatly improves the accuracy and yield of the pattern, which has greatly promoted the development of the field of electronic devices. Although the synthesis research of photosensitive polyimide is very active, the supply in industry is very limited, resulting in a situation where all photosensitive polyimides need to be imported from abroad. The reason is due to the stringent requirements of the purity of photosensitive polyimide products, storage stability, repeatability of photosensitivity, and matching of photosensitive bands. Summary of the invention

[0005] In order to solve the above deficiencies in the prior art, the purpose of the present invention is to provide a diamine monomer for synthesizing photosensitive polyimide which has good storage stability, a photosensitivity band that matches the industrial exposure wavelength (365nm), and can be industrially and stably produced in large quantities.

[0006] The second object of the present invention is to provide a method for preparing a diamine monomer for synthesizing photosensitive polyimide, which has a simple synthesis route, high reaction yield and strong stability of the intermediate product.

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

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

[0009]

[0010] Wherein, R can be selected from one of the following monomers:

[0011]

[0012] The second technical solution provided by the present invention is a method for preparing the above-mentioned diamine monomer for synthesizing photosensitive polyimide, which uses 5-hydroxy-2-nitrobenzaldehyde, aliphatic diamino-substituted diol, dihalogenated straight-chain alkane, methyl acetoacetate, and a nitrogen source as raw materials, and obtains the diamine monomer by 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.

[0013] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing the photosensitive polyimide comprises the following steps:

[0014] S1. Under nitrogen protection, a Lewis base catalyzes a halogenation reaction between an aliphatic diamino-substituted diol and a dihalogenated straight-chain alkane to generate a halogenated aliphatic diamine;

[0015] S2. Under nitrogen protection, Lewis base catalyzes 5-hydroxy-2-nitrobenzaldehyde and the halogenated aliphatic diamine prepared in step 1) to undergo nucleophilic substitution to generate aliphatic diamine nucleophilic products;

[0016] S3. Under nitrogen protection, methyl acetoacetate, the fatty diamine nucleophilic product prepared in step 2) and a nitrogen source undergo a condensation reaction to obtain a condensation product, which is filtered and recrystallized to obtain a diamine monomer for synthesizing a photosensitive polyimide.

[0017] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide, wherein:

[0018] The molar ratio of the fatty diamino-substituted diol and the dihalogenated straight-chain alkane in step S1) is 1.0:(1.1-2.0); the reaction temperature in step S1) is 30-80° C. and the reaction time is 10-15 hours;

[0019] The molar ratio of 5-hydroxy-2-nitrobenzaldehyde described in S2) to the halogenated fatty diamine prepared in S1) is 1.0:(1.1-2.0); the reaction temperature of S2) is 0-50° C., and the reaction time is 10-15 h;

[0020] S3) the molar ratio of methyl acetoacetate, the fatty diamine nucleophilic product prepared in S2) and the nitrogen source is 1.0:(1.1-2.0):(2.0-2.5); the reaction temperature of S3) is 30-80°C and the reaction time is 10-15h.

[0021] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing the photosensitive polyimide comprises the following steps:

[0022] S1. dissolving 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate and a nitrogen source in an organic solvent to obtain a photosensitive substance containing a hydroxyl group through a condensation reaction;

[0023] S2. Under nitrogen protection, a Lewis base catalyzes a halogenated straight-chain alkane and a hydroxyl-containing photosensitive substance prepared in step 1) in an organic solvent to generate a halogenated hydroxyl-containing photosensitive substance;

[0024] S3. Under nitrogen protection, a Lewis base catalyzes a nucleophilic reaction of aliphatic diamino-substituted diol and the halogenated photosensitive substance containing hydroxyl groups prepared in step 2) in an organic solvent to obtain a nucleophilic product, and the nucleophilic product is filtered and recrystallized to obtain a diamine monomer for synthesizing photosensitive polyimide.

[0025] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide, wherein:

[0026] The molar ratio of 5-hydroxy-2-nitrobenzaldehyde to methyl acetoacetate in step S1) is 1.0:(2.0-3.0); the reaction temperature in step S1) is 0-50° C., and the reaction time is 10-15 h;

[0027] The molar ratio of the photosensitivity containing hydroxyl group prepared in step 1) described in S2) to the dihalogenated straight-chain alkane is 1.0:(1.1-2.0); the reaction temperature of S2) is 30-80°C, and the reaction time is 10-15h; the molar ratio of the fatty diamino-substituted diol described in S3) to the halogenated photosensitivity containing hydroxyl group prepared in step 2) is (1.1-2.0):1.0; the reaction temperature of S3) is 30-80°C, and the reaction time is 10-15h.

[0028] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing the photosensitive polyimide comprises the following steps:

[0029] S1. Under nitrogen protection, 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate, and a nitrogen source are catalyzed by a Lewis base to undergo a condensation reaction in an organic solvent to obtain a photosensitive substance containing a hydroxyl group;

[0030] S2. Under nitrogen protection, aliphatic diamino-substituted diol reacts with dihalogenated straight-chain alkane to form a halogenated product;

[0031] S3. Under nitrogen protection, the photosensitive substance containing hydroxyl groups prepared by S1 and the halogenated product prepared by S1 undergo nucleophilic reaction catalyzed by Lewis base to generate nucleophilic products. The nucleophilic products are filtered and recrystallized to obtain diamine monomers for synthesizing photosensitive polyimide.

[0032] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide, wherein:

[0033] The molar ratio of 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate and nitrogen source in S1) is 1.0:(2.0-3.0):(1.1-1.5); the reaction temperature in S1) is 0-50° C. and the reaction time is 12 h;

[0034] S2) The molar ratio of the fatty diamino-substituted diol and the dihalogenated straight-chain alkane prepared in step 1) is 1.0:(1.1-1.5); the reaction temperature of S2) is 30-80° C. and the reaction time is 12 h;

[0035] The molar ratio of the fatty diamino-substituted diol in step S3) to the halogenated photosensitive substance containing hydroxyl groups prepared in step 2) is (1.1-2.0):1.0; the reaction temperature in step S3) is 30-80° C., and the reaction time is 12 hours;

[0036] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide, wherein:

[0037] The nitrogen source is selected from any one of ammonium acetate, ammonium bicarbonate, ammonium carbonate, ammonium chloride, glacial acetic acid, the reaction product of pyridine-catalyzed ammonia water and acetic acid, and ammonium bisulfate;

[0038] The organic solvent is any one of methanol, ethanol, isopropanol, dioxane, tetrahydrofuran, chloroform, acetone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide;

[0039] 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.

[0040] Furthermore, the above-mentioned method for preparing the diamine monomer for synthesizing photosensitive polyimide, wherein:

[0041] The fatty diamino

[0042]

[0043] One of them;

[0044] The dihalogenated straight-chain alkane is

[0045]

[0046] One of them.

[0047] Compared with the prior art, the technical solution provided by the present invention has the following technical advantages:

[0048] 1. The diamine monomer for synthesizing photosensitive polyimide provided by the present invention has the advantages of excellent stability, photosensitivity band and matching industrial exposure.

[0049] 2. The preparation method of the diamine monomer for synthesizing photosensitive polyimide provided by the present invention is simple, time-saving, mild reaction conditions, simple post-reaction treatment, wide versatility, strong designability, and high process yield; it effectively solves the problems of low purity of commercial photosensitive polyimide, poor storage stability, and mismatch between the photosensitive band and the industrial exposure wavelength (365nm). BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 is the H NMR spectrum of compound A2 in Example 2 of the present invention;

[0051] Figure 2 is the H NMR spectrum of compound C2 in Example 2 of the present invention;

[0052] Figure 3 This is the ultraviolet absorption spectrum of compound C2 in Example 2 of the present invention before and after 365nm light irradiation.

[0053] Figure 4 This is a photograph of compound C2 in Example 2 of the present invention being used to prepare photosensitive polyimide and then applied to a copper-clad circuit board. DETAILED DESCRIPTION

[0054] The preferred embodiments of the present invention are described below in conjunction with the accompanying drawings. It should be understood that the preferred embodiments described herein are only used to illustrate and understand the present invention, and are not used to limit the present invention.

[0055] Example 1

[0056] The synthesis route of a diamine monomer for synthesizing photosensitive polyimide provided in this embodiment is as follows:

[0057]

[0058] The preparation method comprises the following steps:

[0059] S1. The synthesis of compound A1 specifically comprises the following steps:

[0060] 1) Add 4.5 g of 1,4-diamino-2,3-butanediol and 25 ml of anhydrous tetrahydrofuran into a two-necked flask, and add 5.4 g of potassium carbonate into the reaction flask under stirring;

[0061] 2) Under nitrogen protection, 8.6 g of 1,4-dibromobutane was slowly added dropwise to the reaction solution for 1 hour. After the addition was completed, the solution was heated to 65° C. and refluxed for 12 hours.

[0062] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected by suction filtration, and the filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound A1, and its yield was calculated to be 96.8%.

[0063] S2. The synthesis of compound B1 specifically comprises the following steps:

[0064] 1) Add 2.6 g of 5-hydroxy-2-nitrobenzaldehyde, 20 ml of anhydrous tetrahydrofuran and 4.5 g of compound A1 into a two-necked flask, and add 1.8 g of potassium carbonate into the reaction flask under stirring; heat to 50° C. and react for 12 h under nitrogen protection;

[0065] 2) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected by suction filtration, and the filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound B1, and its yield was calculated to be 98.7%.

[0066] S3. The synthesis of compound C specifically comprises the following steps:

[0067] 1) 0.8 g of methyl acetoacetate, 40 ml of anhydrous ethanol and 9.2 g of compound B1 were added to a two-necked flask, and 3.7 g of ammonium bicarbonate was added to the reaction flask under stirring;

[0068] 2) Under nitrogen protection, heat to 80°C and reflux for 12 hours;

[0069] 3) After the reaction was completed, the reaction solution was cooled to room temperature, filtered and the filtrate was spin-dried, and the solid was recrystallized from ethanol to obtain a yellow solid (Compound C1), and the yield was measured to be 97.4%.

[0070] Example 2

[0071] The synthesis path of the diamine monomer used to synthesize the photosensitive polyimide in this embodiment is as follows:

[0072]

[0073] S1. Synthesis of Compound A2

[0074] 1) Add 5.2 g of 5-hydroxy-2-nitrobenzaldehyde and 10 ml of anhydrous ethanol into a two-necked flask, and add 5.3 g of methyl acetoacetate, 0.1 g of pyridine and 0.1 g of glacial acetic acid into the reaction flask in sequence under stirring;

[0075] 2) Under nitrogen protection, 8.6 g of aqueous ammonia (mass fraction 20%) was slowly added dropwise to the reaction solution for 1 hour. After the addition was completed, the temperature was kept at 0°C for 12 hours.

[0076] 3) After the reaction is completed, heating is stopped and the reaction solution is cooled to room temperature. A large amount of solid is precipitated. The reaction solution is filtered and the filter cake is collected; the filter cake is placed in a vacuum oven and dried at 50°C for 24 hours to obtain compound A2, and its yield is calculated to be 97.6%; the H NMR spectrum of compound A2 can be found at Figure 1 ,pass Figure 1 From the integrated area and peak position in the spectrum, it can be seen that compound A2 is the target product of the synthesis.

[0077] S2. Synthesis of Compound B

[0078] 1) Add 4.5 g of compound A2 and 20 ml of anhydrous tetrahydrofuran into a reaction flask, and then add 3.2 g of anhydrous potassium carbonate into the reaction flask in sequence under stirring;

[0079] 2) Under nitrogen protection, 4.8 g of 1,4-dibromobutane was slowly added dropwise to the reaction solution for 1 hour. After the addition was completed, the solution was heated to 60° C. and refluxed for 12 hours.

[0080] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected after suction filtration, placed in a vacuum oven, and dried at 60° C. for 24 h to obtain compound B2, and its yield was measured to be 98.5%.

[0081] S3. Synthesis of Compound C2

[0082] 1) Add 1.1 g of 1,6-diamino-2,5-hexanediol, 50 ml of anhydrous tetrahydrofuran and 7.3 g of compound B2 into a two-necked flask, and add 8.4 g of anhydrous potassium carbonate into the reaction flask while stirring;

[0083] 2) Under nitrogen protection, the mixture was heated to 50°C for 12 hours. After the reaction, the reaction solution was cooled to room temperature, filtered and the filtrate was dried by spin drying. The solid was recrystallized from ethanol to obtain a yellow solid (Compound C2). The yield was 98.1%. The H NMR spectrum of Compound C2 can be found at Figure 2 ,pass Figure 2 The integrated area and peak position in the spectrum confirmed that compound C2 was the target product of the synthesis.

[0084] The UV absorption spectrum of compound C2 before and after 365nm light irradiation is shown in the figure below: Figure 3 ,pass Figure 3 It can be seen that after exposure to light, the absorption peak of compound C2 originally at 350 nm red-shifts to 400 nm, indicating that compound C2 has good photosensitivity (photosensitive wavelength is 365 nm).

[0085] Example 3

[0086] The synthesis path of the diamine monomer used to synthesize the photosensitive polyimide in this embodiment is as follows:

[0087]

[0088] The preparation method is carried out in the following steps:

[0089] S1. Synthesis of Compound A3

[0090] 1) Add 5.2 g of 5-hydroxy-2-nitrobenzaldehyde and 10 ml of anhydrous ethanol into a two-necked flask, and add 5.5 g of methyl acetoacetate and 4.7 g of ammonium acetate into the reaction flask in sequence under stirring;

[0091] 2) Under nitrogen protection, heat to 50°C and react for 12 hours;

[0092] 3) After the reaction is completed, heating is stopped and the reaction solution is cooled to room temperature, and a large amount of solid is precipitated;

[0093] 4) filtering the reaction solution and collecting the filter cake;

[0094] 5) The filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound A3, with a calculated yield of 98.4%.

[0095] S2. Synthesis of Compound B3

[0096] 1) Add 2.3 g of 1,8-diamino-2,7-octanediol and 20 ml of anhydrous tetrahydrofuran into a two-necked flask, and add 2.1 g of sodium carbonate into the reaction flask under stirring;

[0097] 2) Under nitrogen protection, 6.7 g of 1,4-dibromobutane was slowly added to the reaction solution for 1 hour. After the addition was completed, the solution was heated to 45°C and reacted for 12 hours.

[0098] 3) After the reaction is completed, the reaction solution is cooled to room temperature, a large amount of solid is precipitated, and then the reaction solution is filtered to collect the filter cake; the filter cake is placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound B3, and its yield is calculated to be 97.9%.

[0099] S3. Synthesis of Compound C3

[0100] 1) Add 6.4 g of compound A, 40 ml of anhydrous tetrahydrofuran and 4.0 g of compound B3 into a two-necked flask, and add 7.2 g of sodium carbonate into the reaction flask while stirring;

[0101] 2) Under nitrogen protection, heat to 55°C and react for 12 hours;

[0102] 3) After the reaction was completed, the reaction solution was cooled to room temperature, filtered and the filtrate was spin-dried, and the solid was recrystallized from ethanol to obtain a yellow solid (Compound C3), and the yield was measured to be 98.7%.

[0103] Example 4

[0104] The synthesis route of a diamine monomer for synthesizing photosensitive polyimide provided in this embodiment is as follows:

[0105]

[0106] The preparation method is carried out in the following steps:

[0107] S1. Synthesis of Compound A4

[0108] 1) Add 5.2 g of 5-hydroxy-2-nitrobenzaldehyde and 10 ml of anhydrous ethanol into a two-necked flask, and add 5.4 g of methyl acetoacetate and 6.5 g of ammonium bisulfate into the reaction flask in sequence under stirring;

[0109] 2) Under nitrogen protection, heat to 30°C and react for 12 hours;

[0110] 3) After the reaction is completed, heating is stopped and the reaction solution is cooled to room temperature. A large amount of solid precipitates. The reaction solution is then filtered and the filter cake is collected. The filter cake is placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound A4, and its yield is calculated to be 97.6%.

[0111] S2. Synthesis of Compound B4

[0112] 1) Add 3.2g 1,8-diamino-3,6-octanediol and 20ml anhydrous tetrahydrofuran into a two-necked flask, and add 2.1g potassium carbonate into the reaction flask under stirring;

[0113] 2) Under nitrogen protection, 6.7 g of 1,4-dibromobutane was slowly added to the reaction solution for 1 hour. After the addition was completed, the solution was heated to 60°C and refluxed for 12 hours.

[0114] 3) After the reaction is completed, the reaction solution is cooled to room temperature, and a large amount of solid is precipitated; the reaction solution is filtered and the filter cake is collected; the filter cake is placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound B4, and its yield is calculated to be 98.3%.

[0115] S3. Synthesis of Compound C4

[0116] 1) Add 6.4 g of compound A4 and 4.0 g of compound B4 into a two-necked flask, and add 7.2 g of potassium carbonate into the reaction flask while stirring;

[0117] 2) Under nitrogen protection, the mixture was heated to 40° C. for 24 h. After the reaction, the reaction solution was cooled to room temperature. The filtrate was filtered and dried by rotary filtration. The solid was recrystallized from ethanol to obtain a yellow solid (Compound C4). The yield was 97.9%.

[0118] Example 5

[0119] The synthesis route of a diamine monomer for synthesizing photosensitive polyimide provided in this embodiment is as follows:

[0120]

[0121] The preparation method is carried out in the following steps:

[0122] S1. The synthesis of compound A5 specifically comprises the following steps:

[0123] 1) Add 5.0 g of 1,5-diamino-2,3-pentanediol and 25 ml of anhydrous tetrahydrofuran into a two-necked flask, and add 5.6 g of potassium carbonate into the reaction flask under stirring;

[0124] 2) Under nitrogen protection, 8.7 g of 1,4-dibromobutane was slowly added to the reaction solution for 1 hour. After the addition was completed, the solution was heated to 65°C and refluxed for 12 hours.

[0125] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected by suction filtration, and the filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound A5, and its yield was calculated to be 97.2%.

[0126] S2. The synthesis of compound B5 specifically comprises the following steps:

[0127] 1) Add 2.8 g of 5-hydroxy-2-nitrobenzaldehyde, 20 ml of anhydrous tetrahydrofuran and 4.7 g of compound A5 into a two-necked bottle, and add 2.0 g of potassium carbonate into the reaction bottle under stirring; heat to 50° C. and react for 12 h under nitrogen protection;

[0128] 2) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected by suction filtration, and the filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound B5, and its yield was calculated to be 98.1%.

[0129] S3. The synthesis of compound C5 specifically comprises the following steps:

[0130] 1) Add 1.0 g of methyl acetoacetate, 40 ml of anhydrous ethanol and 9.4 g of compound B5 into a two-necked flask, and add 4.0 g of ammonium bicarbonate into the reaction flask while stirring;

[0131] 2) Under nitrogen protection, heat to 80°C and reflux for 12 hours;

[0132] 3) After the reaction, the reaction solution was cooled to room temperature, filtered and the filtrate was spin-dried, and the solid was recrystallized from ethanol to obtain a yellow solid (Compound C5), and the yield was measured to be 96.9%.

[0133] Example 6

[0134] The synthesis route of a diamine monomer for synthesizing photosensitive polyimide provided in this embodiment is as follows:

[0135]

[0136] The preparation method is carried out in the following steps:

[0137] S1. The synthesis of compound A6 specifically comprises the following steps:

[0138] 1) Add 7.6 g of 1,8-diamino-2,7-octanediol and 25 ml of anhydrous tetrahydrofuran into a two-necked flask, and add 5.9 g of potassium carbonate into the reaction flask under stirring;

[0139] 2) Under nitrogen protection, 9.1 g of 1,4-dibromobutane was slowly added dropwise to the reaction solution for 1 hour. After the addition was completed, the solution was heated to 75°C and refluxed for 12 hours.

[0140] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected by suction filtration, and the filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound A6, and its yield was calculated to be 98.3%.

[0141] S2. The synthesis of compound B6 specifically comprises the following steps:

[0142] 1) Add 2.5 g of 5-hydroxy-2-nitrobenzaldehyde, 20 ml of anhydrous tetrahydrofuran and 6.9 g of compound A6 into a two-necked flask, and add 1.8 g of potassium carbonate into the reaction flask under stirring; heat to 40° C. and react for 12 h under nitrogen protection;

[0143] 2) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected by suction filtration, and the filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound B6, and its yield was calculated to be 97.9%.

[0144] S3. The synthesis of compound C6 specifically comprises the following steps:

[0145] 1) Add 1.2 g of methyl acetoacetate, 40 ml of anhydrous ethanol and 15.6 g of compound B6 into a two-necked flask, and add 4.0 g of ammonium bicarbonate into the reaction flask while stirring;

[0146] 2) Under nitrogen protection, heat to 75°C and reflux for 12 hours;

[0147] 3) After the reaction was completed, the reaction solution was cooled to room temperature, filtered and the filtrate was spin-dried, and the solid was recrystallized from ethanol to obtain a yellow solid (Compound C6), and the yield was measured to be 98.9%.

[0148] Example 7

[0149] The synthesis route of a diamine monomer for synthesizing photosensitive polyimide provided in this embodiment is as follows:

[0150]

[0151] The preparation method is carried out in the following steps:

[0152] S1. The synthesis of compound A7 specifically comprises the following steps:

[0153] 1) Add 7.6 g of 1,8-diamino-2,7-octanediol and 25 ml of anhydrous tetrahydrofuran into a two-necked flask, and add 5.9 g of potassium carbonate into the reaction flask under stirring;

[0154] 2) Under nitrogen protection, 8.0 g of 1,4-dibromobutane was slowly added dropwise to the reaction solution for 1 hour. After the addition was completed, the solution was heated to 75°C and refluxed for 12 hours.

[0155] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected by suction filtration, and the filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound A7, and its yield was calculated to be 97.6%.

[0156] S2. The synthesis of compound B7 specifically comprises the following steps:

[0157] 1) Add 2.5 g of 5-hydroxy-2-nitrobenzaldehyde, 20 ml of anhydrous tetrahydrofuran and 6.6 g of compound A7 into a two-necked flask, and add 1.8 g of potassium carbonate into the reaction flask under stirring; heat to 40° C. and react for 12 h under nitrogen protection;

[0158] 2) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected by suction filtration, and the filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound B7, and its yield was calculated to be 98.1%.

[0159] S3. The synthesis of compound C7 specifically comprises the following steps:

[0160] 1) Add 1.1 g of methyl acetoacetate, 40 ml of anhydrous ethanol and 15.2 g of compound B7 into a two-necked flask, and add 4.0 g of ammonium bicarbonate into the reaction flask while stirring;

[0161] 2) Under nitrogen protection, heat to 75°C and reflux for 12 hours;

[0162] 3) After the reaction was completed, the reaction solution was cooled to room temperature, filtered and the filtrate was spin-dried, and the solid was recrystallized from ethanol to obtain a yellow solid (Compound C7), and the yield was measured to be 98.5%.

[0163] Example 8

[0164] The synthesis route of a diamine monomer for synthesizing photosensitive polyimide provided in this embodiment is as follows:

[0165]

[0166] The preparation method is carried out in the following steps:

[0167] S1. The synthesis of compound A8 comprises the following steps:

[0168] 1) Add 7.6 g of 1,8-diamino-2,7-octanediol and 25 ml of anhydrous tetrahydrofuran into a two-necked flask, and add 5.9 g of potassium carbonate into the reaction flask under stirring;

[0169] 2) Under nitrogen protection, 10.5 g of 1,7-dibromoheptane was slowly added dropwise to the reaction solution for 1 hour. After the addition was completed, the solution was heated to 75° C. and refluxed for 12 hours.

[0170] 3) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected by suction filtration, and the filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound A8, and its yield was calculated to be 97.9%.

[0171] S2. The synthesis of compound B8 specifically comprises the following steps:

[0172] 1) Add 2.7 g of 5-hydroxy-2-nitrobenzaldehyde, 20 ml of anhydrous tetrahydrofuran and 7.5 g of compound A8 into a two-necked flask, and add 1.8 g of potassium carbonate into the reaction flask under stirring; heat to 40° C. and react for 12 h under nitrogen protection;

[0173] 2) After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of solid precipitated; the filter cake was collected by suction filtration, and the filter cake was placed in a vacuum oven and dried at 50° C. for 24 h to obtain compound B8, and its yield was calculated to be 98.8%.

[0174] S3. The synthesis of compound C8 specifically comprises the following steps:

[0175] 1) Add 1.6 g of methyl acetoacetate, 40 ml of anhydrous ethanol and 17.8 g of compound B8 into a two-necked flask, and add 4.0 g of ammonium bicarbonate into the reaction flask while stirring;

[0176] 2) Under nitrogen protection, heat to 75°C and reflux for 12 hours;

[0177] 3) After the reaction, the reaction solution was cooled to room temperature, filtered and the filtrate was spin-dried, and the solid was recrystallized from ethanol to obtain a yellow solid (Compound C8), and the yield was measured to be 97.4%.

[0178] Application examples:

[0179] (1) 91.3 g of 4,4'-diaminodiphenyl ether and 47.2 g of photosensitive diamine monomer were weighed and added to a reactor equipped with a stirrer. After being mixed evenly, the reactor was placed in a 15° C. water bath. 1820.3 g of N,N-dimethylacetamide was added to the reactor and stirred for 10 minutes until the diamine monomer was completely dissolved. 50.3 g of 5,5'-(propane-2,2-diylbis(4,1-phenylene)bis(oxy)bis(isobenzofuran-1,3-dione) was added to the reaction solution and the reaction was continued with stirring for 10 hours to obtain a photosensitive polyamic acid solution. Under room temperature and light-proof conditions, the polyamic acid solution was filtered through a 0.22 mesh filter membrane to defoam and then uniformly cast on a glass sheet. The polyamic acid film was placed in a nitrogen environment and maintained at 60° C. for 100 minutes and 120° C. for 100 minutes. The polyamic acid film was heated in stages for imidization. The solvent was evaporated to obtain a 20 μm self-supporting photosensitive polyimide film.

[0180] (2) The photosensitive polyamic acid film filtered and defoamed in step (1) was dried in a blast heating device at 70° C. for 5 h, and then sent to an ultraviolet exposure device capable of emitting a wavelength of 200 nm for exposure. The total exposure time was 1.2×10 2 s;

[0181] (3) Immersing the photosensitive polyamic acid film after exposure in step (2) in a developer at room temperature for 60 seconds, then rinsing with ethanol and drying with cold air. Subsequently, in a nitrogen atmosphere, first maintaining at 60° C. for 100 minutes, and then maintaining at 120° C. for 100 minutes, to obtain a photosensitive polyimide film with a Ag metal catalyst pattern on the surface;

[0182] Wherein: the developer is prepared by dissolving 50 g of silver nitrate in 1 liter of ethanol solvent and mixing evenly.

[0183] (4) immersing the photosensitive polyimide film with a Ag metal catalyst pattern on the surface prepared in step (3) into a metal 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 It can be seen that the feasibility of applying photosensitive polyimide to copper-clad circuit boards is confirmed.

[0184] The metal copper plating solution is obtained by uniformly mixing 10 g / L of copper sulfate pentahydrate aqueous solution, 15 g of potassium sodium tartrate, and 10 mL of formaldehyde, 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 structural formula is shown in Formula 1: Wherein, R can be selected from one of the following monomers:

2. The method for preparing a diamine monomer for synthesizing a photosensitive polyimide according to claim 1, characterized in that: 5-hydroxy-2-nitrobenzaldehyde, aliphatic diamino-substituted diol, dihalogenated straight-chain alkane, methyl acetoacetate and a nitrogen source are used as raw materials, and a diamine monomer is obtained by a halogenation reaction, a nucleophilic substitution reaction and a condensation reaction between different raw materials; the order of the halogenation reaction, the nucleophilic substitution reaction and the condensation reaction can be interchanged arbitrarily.

3. The method for preparing a diamine monomer for synthesizing photosensitive polyimide according to claim 2, characterized in that: The following steps are involved: S1. Under nitrogen protection, a Lewis base catalyzes a halogenation reaction between an aliphatic diamino-substituted diol and a dihalogenated straight-chain alkane to generate a halogenated aliphatic diamine; S2. Under nitrogen protection, Lewis base catalyzes 5-hydroxy-2-nitrobenzaldehyde and the halogenated aliphatic diamine prepared in step 1) to undergo nucleophilic substitution to generate aliphatic diamine nucleophilic products; S3. Under nitrogen protection, methyl acetoacetate, the fatty diamine nucleophilic product prepared in step 2) and a nitrogen source undergo a condensation reaction to obtain a condensation product, and the condensation product is filtered and recrystallized to obtain a diamine monomer for synthesizing a photosensitive polyimide.

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

5. The method for preparing a diamine monomer for synthesizing photosensitive polyimide according to claim 2, characterized in that: The following steps are involved: S1. dissolving 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate and a nitrogen source in an organic solvent to obtain a photosensitive substance containing a hydroxyl group through a condensation reaction; S2. Under nitrogen protection, a Lewis base catalyzes a halogenated straight-chain alkane and a hydroxyl-containing photosensitive substance prepared in step 1) in an organic solvent to generate a halogenated hydroxyl-containing photosensitive substance; S3. Under nitrogen protection, a Lewis base catalyzes a nucleophilic reaction of aliphatic diamino-substituted diol and the halogenated photosensitive substance containing hydroxyl groups prepared in step 2) in an organic solvent to obtain a nucleophilic product, and the nucleophilic product is filtered and recrystallized to obtain a diamine monomer for synthesizing photosensitive polyimide.

6. The method for preparing a diamine monomer for synthesizing photosensitive polyimide according to claim 5, characterized in that: The molar ratio of 5-hydroxy-2-nitrobenzaldehyde to methyl acetoacetate in step S1) is 1.0:(2.0-3.0); the reaction temperature in step S1) is 0-50° C., and the reaction time is 10-15 h; S2) The molar ratio of the photosensitive substance containing hydroxyl group prepared in step 1) to the dihalogenated straight-chain alkane is 1.0:(1.1-2.0); the reaction temperature of S2) is 30-80° C., and the reaction time is 10-15 h; The molar ratio of the fatty diamino-substituted diol described in step S3) to the halogenated photosensitive substance containing hydroxyl groups prepared in step 2) is (1.1-2.0):1.0; the reaction temperature of step S3) is 30-80° C., and the reaction time is 10-15 hours.

7. The method for preparing a diamine monomer for synthesizing photosensitive polyimide according to claim 2, characterized in that: The following steps are involved: S1. Under nitrogen protection, 5-hydroxy-2-nitrobenzaldehyde, methyl acetoacetate, and a nitrogen source are catalyzed by a Lewis base to undergo a condensation reaction in an organic solvent to obtain a photosensitive substance containing a hydroxyl group; S2. Under nitrogen protection, aliphatic diamino-substituted diol reacts with dihalogenated straight-chain alkane to form a halogenated product; S3. Under nitrogen protection, the photosensitive substance containing hydroxyl groups prepared by S1 and the halogenated product prepared by S1 are catalyzed by Lewis base to undergo a nucleophilic reaction to generate a nucleophilic product. The nucleophilic product is filtered and recrystallized to obtain a diamine monomer for synthesizing photosensitive polyimide.

8. The method for preparing a 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 S1) is 1.0:(2.0-3.0):(1.1-1.5); the reaction temperature in S1) is 0-50° C. and the reaction time is 10-15 h; S2) The mass ratio of the fatty diamino-substituted diol and the dihalogenated straight-chain alkane prepared in step 1) is 1.0:(1.1-1.5); the reaction temperature of S2) is 30-80° C. and the reaction time is 10-15 h; The molar ratio of the fatty diamino-substituted diol described in step S3) to the halogenated photosensitive substance containing hydroxyl groups prepared in step 2) is (1.1-2.0):1.0; the reaction temperature of step S3) is 30-80° C., and the reaction time is 10-15 hours.

9. The method for preparing a diamine monomer for synthesizing photosensitive polyimide according to any one of claims 3, 5 and 7, characterized in that: The nitrogen source is selected from any one of ammonium acetate, ammonium bicarbonate, ammonium carbonate, ammonium chloride, glacial acetic acid, the reaction product of pyridine-catalyzed ammonia water and acetic acid, and ammonium bisulfate; 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.

10. The method for preparing a diamine monomer for synthesizing photosensitive polyimide according to any one of claims 3, 5 and 7, characterized in that: The fatty diamino One of them; The dihalogenated straight-chain alkane is One of them.

Images