A novel structural diamine monomer, a polymer material based on the monomer, and a preparation method and application thereof

Abstract

The invention discloses a novel structural diamine monomer, a polymer material based on the monomer, and a preparation method and application thereof, and relates to the technical field of polymer materials. The invention prepares a novel functional diamine monomer of bio-based origin, and at the same time, based on the novel diamine monomer, a novel polyimide polymer material is prepared by a mixed polycondensation or co-polycondensation method. Such polyimide material can simply and economically interact with the rigid dicyclopentane structure on the main chain and the hydrogen bond between the chains, so that the polyimide film has excellent mechanical strength, low thermal expansion coefficient, good solution processing performance, good colorless transparency and high thermal stability, has the application potential of realizing sustainable development in electronic equipment, and meets the requirements of environmental sustainable development.

Description

Technical Field

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

[0002] As a product of high technology, polymer materials have greatly enriched people's lives. Their importance in people's food, clothing, housing and transportation has become increasingly prominent. Plastics, rubber, fibers, adhesives and polymer-based composite materials have become one of the important pillars of modern life. This linear economic model cannot solve the problem of post-consumer polymer waste scrapping, which not only quickly depletes limited natural resources, but also suffers huge economic losses and exacerbates the consequences of worsening plastic pollution on a global scale.

[0003] In order to achieve sustainable economic development, people are committed to the research of green and sustainable polymer materials, such as polyurethane, polycarbonate, polyester and polyamide. However, the poor thermal stability of these bio-sourced polymers limits their application in electronic devices. Among a large number of polymers, polyimide (PI) films have attracted great attention from scientific researchers due to their excellent comprehensive properties, including high thermal properties and ultra-high tensile strength, chemical resistance, low linear expansion coefficient and relatively low dielectric constant. Nevertheless, when traditional PI films are used in the fields of microelectronics and optoelectronics, the first thing to consider is the darker color, poor optical transmittance and difficulty in processing of traditional PI films.

[0004] Introducing alicyclic structures into traditional PI can be used to prepare colorless and transparent PI films. This is because the alicyclic structure can destroy the conjugated structure on the aromatic PI chain segment, reduce the interaction force between molecular chains, increase the free volume between chains, and reduce the formation of CTC, thereby improving the transparency and solubility of PI films. Unfortunately, in the above case, their coefficient of thermal expansion (CTE) will increase significantly. On the other hand, the introduction of highly conjugated, rigid aromatic groups, highly polar groups or cross-linkable groups can significantly improve the thermal stability of PI, while the synthesized PI will inevitably present a darker color. Therefore, it is still a challenge to strike a balance between colorless transparency, mechanical properties and dimensional thermal stability.

[0005] Among renewable natural resources, polyacids stand out because they are very abundant and easy to obtain, and provide a large variety of functional groups. In the recently reported literature, people have been increasingly studying polymers based on polyacid derivatives. Citric acid is converted into monomers containing dicyclopentane structures, namely octahydro-2,5-pentanediol, octahydro-2,5-pentanediamine, octahydro-2,5-glutaryl chloride and octahydro-2,5-pentanecarboxylic acid alcohol, by Weiss-Cook condensation and reduction reaction. The monomer containing dicyclopentane structure is a completely biorenewable monomer. Compared with isosorbide (ISB), the monomer containing dicyclopentane structure has perfect rigidity and higher thermal stability. Moreover, the monomer containing dicyclopentane structure has been used as a structural monomer for synthesizing bio-based polyesters or polyurethanes. Summary of the invention

[0006] The purpose of the present invention is to provide a novel structural diamine monomer, a polymer material based on the monomer, and a preparation method and application thereof, so as to solve the problems existing in the above-mentioned prior art, ensure that the polymer material has both excellent light transmittance and thermal stability, and excellent mechanical properties, so as to meet the application requirements of electronic equipment.

[0007] To achieve the above object, the present invention provides the following solutions:

[0008] One of the purposes of the present invention is to provide a diamine monomer, the general structural formula of which is shown in formula (I):

[0009]

[0010] Wherein, R1 and R2 are the same or different, and R1 and R2 are selected from any one of the following structures:

[0011]

[0012] Ar1 is selected from any one of the following structures:

[0013]

[0014] Furthermore, the compound represented by the chemical formula (I) is selected from the chemical group represented by the following chemical formula:

[0015]

[0016] The second object of the present invention is to provide a method for preparing the above-mentioned diamine monomer, comprising the following steps:

[0017] A disubstituted nitro compound is prepared by any one of methods 1 to 4, and then a reduction reaction is performed to obtain the diamine monomer;

[0018] Method 1: using octahydro-2,5-pentanediol as a raw material to react with an isocyanate-substituted nitrobenzene compound, a halogen-substituted nitrobenzene compound or an acyl chloride-substituted nitrobenzene compound to obtain the disubstituted nitro compound;

[0019] Method 2: using octahydro-2,5-pentanediamine as a raw material to react with an isocyanate-substituted nitrobenzene compound or an acyl chloride-substituted nitrobenzene compound to obtain the disubstituted nitro compound;

[0020] Method 3: using octahydro-2,5-pentanedicarboxylic acid chloride as a raw material to react with an isocyanate-substituted nitrobenzene compound or an amine-substituted nitrobenzene compound to obtain the disubstituted nitro compound;

[0021] Method 4: using octahydro-2,5-pentanecarboxylic acid alcohol as a raw material and reacting with an isocyanate-substituted nitrobenzene compound, a halogen-substituted nitrobenzene compound, an acyl chloride-substituted nitrobenzene compound or an amino-substituted nitrobenzene compound to obtain the disubstituted nitro compound;

[0022] The general structural formula of the disubstituted nitro compound is as follows:

[0023]

[0024] Specifically, octahydro-2,5-pentanediol, octahydro-2,5-pentanediamine, octahydro-2,5-glutaryl chloride and octahydro-2,5-pentanecarboxylic acid alcohol react with 1.5-3 times equivalent of nitrobenzene isocyanate, nitrobenzene chloride, halogen-containing nitrobenzene and nitroaniline in an organic solvent to obtain the disubstituted nitro compound.

[0025] The reaction raw materials include 4-nitroisocyanate, 4-fluoronitrobenzene, 4-nitrobenzoyl chloride, m-nitrobenzoyl chloride, 5-nitro-2-pyridinecarbonyl chloride, 1-fluoro-5-nitronaphthalene, p-nitroaniline, etc. The reaction temperature of the process for preparing the disubstituted nitro compound is between 0°C and 150°C, and the reaction time is 6-8h. The reduction reaction adopts hydrogen reduction method.

[0026] The structures of the octahydro-2,5-pentanediol, octahydro-2,5-pentanediamine, octahydro-2,5-pentanecarboxylic acid alcohol and octahydro-2,5-glutaryl dicarboxylic acid chloride are as follows:

[0027]

[0028] The diamine monomer of the present invention can be used to prepare functional polymers such as polyimide and polyamide-imide.

[0029] The third object of the present invention is to provide a polymer prepared from the above diamine monomer, wherein the polymer has a general structural formula as shown in formula (III):

[0030]

[0031] Among them, m is an integer of 5 to 10000, n is an integer of 0 to 10000, X is a tetravalent aromatic hydrocarbon group, Y is the above-mentioned diamine monomer; R is an aromatic diamine monomer, including 2,2'-bis(trifluoromethyl)diaminobiphenyl, 4,4'-diaminodiphenyl ether, 4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 9,9-bis(4-aminophenyl)fluorene, etc.

[0032] Furthermore, the polymer is polyimide.

[0033] The fourth object of the present invention is to provide a method for preparing the above polymer, comprising the following steps: preparing the polymer by reacting the above diamine monomer with a dianhydride compound, or preparing the polymer by reacting the above diamine monomer with the above aromatic diamine monomer and a dianhydride compound. The reaction conditions are: reacting at room temperature for 36-48 hours.

[0034] The fifth object of the present invention is to provide application of the above polymer in electronic devices.

[0035] The inherent rigidity, non-toxicity and biodegradability of the monomer containing the dicyclopentane structure enable the dicyclopentane structure in the PI chain to weaken the cohesion between molecules and hinder the CTC interaction, while improving the light transmittance and solubility of the polyimide film without affecting the thermal and mechanical properties. The bio-based PI of the present invention has potential sustainable economic applications in electronic devices and can meet the requirements of environmental sustainability.

[0036] The present invention discloses the following technical effects:

[0037] The present invention prepares a novel functional diamine monomer of bio-based origin, and simultaneously based on the novel diamine monomer, a novel polyimide polymer material is prepared by a mixed polycondensation or co-polycondensation method. The polyimide material can simply and economically interact with the rigid dicyclopentane structure on the main chain and the hydrogen bonds between the chains, so that the polyimide film has excellent mechanical strength, low thermal expansion coefficient, good solution processing performance, good colorless transparency and high thermal stability, has the application potential to achieve sustainable development in electronic equipment, and meets the requirements of environmental sustainable development. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0039] Figure 1 The infrared spectra of the polyimide films prepared by polymer examples 1-10 of the present invention;

[0040] Figure 2 The ultraviolet transmission spectra of the polyimide films prepared by polymer examples 1-10 of the present invention;

[0041] Figure 3 The thermogravimetric graphs of the polyimide films prepared by polymer examples 1-10 of the present invention;

[0042] Figure 4 The biodegradation diagrams of the polyimide films prepared from polymer Examples 2 and 6 of the present invention and Comparative Example PI (TFMB-6FDA), the degradation environments are pH = 2.0 (red), pH = 7.0 (blue) and buffer solution containing porcine pancreatic enzyme pH = 7.0 (black). (a), (b), (c) and (d) are respectively the graphs of the changes in mass, number average molecular weight, weight average molecular weight and dispersion coefficient. DETAILED DESCRIPTION

[0043] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0044] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0045] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0046] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are exemplary only.

[0047] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0048] In the embodiments of the present invention, octahydro-2,5-pentanediol, octahydro-2,5-pentanediamine, octahydro-2,5-glutaryl chloride and octahydro-2,5-pentanecarboxylic acid alcohol are prepared by reacting citric acid with glyoxal through Weiss-Cook condensation and reduction reaction. The preparation method is well known to those skilled in the art and will not be described in detail herein.

[0049]

[0050] Preparation Example of the novel structural diamine monomer of the present invention:

[0051] Monomer Example 1 Synthesis of a novel structural diamine monomer

[0052]

[0053] Octahydro-2,5-pentanediol (2.84 g, 0.02 mol), 4-nitrobenzene isocyanate (6.57 g, 0.041 mol) and dibutyltin dilaurate (1 ml) were transferred to a 100 mL three-necked flask equipped with a magnetic stirrer, a nitrogen inlet and a reflux condenser. Then 40 mL of tetrahydrofuran was added at one time. The mixture was ventilated three times with nitrogen to remove residual air and reacted at 150 ° C for about 8 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to room temperature and slowly poured into rapidly stirred ethanol for precipitation. The resulting precipitate was collected by filtration, and the intermediate product I was washed with ethanol, and then the intermediate product I was vacuum dried to obtain a light yellow nitro product I.

[0054]

[0055] In the presence of Pd / C (0.42 g) catalyst, DMAc (30 mL) and intermediate product I (4.23 g, 0.009 mol) were added to the flask, hydrogen was added at room temperature, the flask was evacuated, and then refilled with H2. The gas in the flask was ventilated at least three times to ensure that the atmosphere in the flask became pure H2. After the reaction was completed, the reaction solution was filtered to remove Pd / C. The obtained mixture was poured into water for precipitation to obtain a white powder, which was vacuum dried at 80°C for 8 h to obtain the product diamine A. 1H NMR (400MHz, DMSO-d6), δ (ppm): 8.96 (s, 2H, NH), 7.07 (d, J = 8.1, 4H, Ph-H), 6.48 (dd, J = 8.8, 2.5, 4H, Ph-H), 4.88 (t ,J=6.9,2H,CH),4.79(s,4H,NH2),2.40(t,J=5.4,2H,CH),2.17(dt,J=13.5,6.6,4H,CH2),1.65–1.54(m,4H,CH2).

[0056] Monomer Example 2 Synthesis of Novel Structural Diamine Monomer

[0057]

[0058] In the structural formula of intermediate II, R can be H, CH3 or CF3, taking R as H as an example. Octahydro-2,5-pentanediol (2.84 g, 0.02 mol) and 4-fluoronitrobenzene (7.06 g, 0.05 mol) were dissolved in DMF (50 mL) at room temperature. Cesium fluoride (7.6 g, 0.05 mol) was added to the solution as a catalyst. The solution was ventilated three times with nitrogen to remove residual air. The reaction was carried out at 150°C for 8 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to room temperature and slowly poured into rapidly stirred ethanol for precipitation. The resulting precipitate was collected by filtration and washed with ethanol to produce a yellow precipitate. The light yellow product was filtered and dried in vacuo at 120°C for 24 hours.

[0059]

[0060] Using intermediate product II as the starting material, diamine B was prepared by high-pressure hydrogen reduction method. In the presence of Pd / C (0.3g) catalyst, intermediate product II (3g, 0.008mol) was added to DMAc (20mL) to react with H2, the reaction flask was evacuated, and then refilled with H2, and the gas in the flask was replaced at least three times to ensure that the gas atmosphere in the flask became pure H2. After the reaction, the reaction solution was filtered to remove Pd / C. The filtrate was poured into water for precipitation, and a white powder was obtained by filtration, which was vacuum dried at 80°C for 24h to obtain the product diamine B. 1 H NMR (400MHz, DMSO-d6), δ (ppm): 6.70–6.60 (m, 4H, Ph-H), 6.50 (t, J=6.4, 4H, Ph-H), 4.60 (d, J=8.5, 4H, NH2 ),4.52(p,J=6.0,2H,NH),2.44(d,J=6.0,2H,CH),2.15–2.02(m,4H,CH2),1.68(dt,J=12.2,5.9,4H,CH2).

[0061] Monomer Example 3 Synthesis of New Structure Diamine Monomer

[0062]

[0063] Octahydro-2,5-pentanediol (7.1 g, 0.05 mol) and 15 mL of triethylamine solution were added to a flask containing 40 mL of CHCl3, and the flask containing the mixture was stirred in ice water. 4-Nitrobenzoyl chloride (19 g, 0.1 mol) was dissolved in 40 mL of CHCl3 and added dropwise to the mixture. The mixture was reacted at room temperature for 6 h. After the reaction was completed, the mixture was rinsed with 200 mL of water. The organic phase was separated and the obtained organic phase was rotary evaporated to obtain a white solid, which was then washed with hot ethanol. It was vacuum dried at 100 ° C for 24 hours.

[0064]

[0065] Using intermediate III as the starting material, diamine C was prepared by high-pressure hydrogen reduction method. In the presence of Pd / C (0.34 g) catalyst, intermediate III (3.4 g, 0.009 mol) was added to DMAc (25 mL) to react with H2. The gas in the flask was evacuated and refilled with H2. The gas atmosphere in the flask was replaced at least three times to ensure that the atmosphere in the flask became pure H2. After the reaction was completed, the reaction solution was filtered to remove Pd / C. The filtrate was poured into water for precipitation to obtain a white powder, which was vacuum dried at 80°C for 24 hours. 1 H NMR (400MHz, DMSO-d6) δ7.88–7.73(m,4H),6.75–6.60(m,4H),5.43(s,4H),5.07(p,J=5.4Hz,2 H),2.32–2.19(m,2H),1.91(ddd,J=12.5,5.6,4.7Hz,4H),1.81(ddd,J=12.5,5.6,4.7Hz,4H).

[0066] Monomer Example 4 Synthesis of Novel Structural Diamine Monomer

[0067]

[0068] Octahydro-2,5-pentanediol (7.1 g, 0.05 mol) and 15 mL of triethylamine solution were added to a flask containing 40 mL of CHCl3, and the flask containing the mixture was stirred in ice water. m-Nitrobenzoyl chloride (19 g, 0.1 mol) was dissolved in 40 mL of CHCl3 and added dropwise to the mixture. The mixture was reacted at room temperature for 6 h. After the reaction was completed, the mixture was rinsed with 200 mL of water. The organic phase was separated and the obtained organic phase was rotary evaporated to obtain a white solid, which was then washed with hot ethanol. It was vacuum dried at 100 °C for 24 hours.

[0069]

[0070] Using intermediate product IV as the starting material, diamine D was prepared by high-pressure hydrogen reduction method. In the presence of Pd / C (0.34 g) catalyst, intermediate product IV (3.4 g, 0.009 mol) was added to DMAc (25 mL) to react with H2. The gas in the flask was evacuated and refilled with H2. The gas atmosphere in the flask was replaced at least three times to ensure that the atmosphere in the flask became pure H2. After the reaction was completed, the reaction solution was filtered to remove Pd / C. The obtained filtrate was poured into water for precipitation to obtain a white powder, which was vacuum dried at 80°C for 24 hours. 1 H NMR (400MHz, DMSO-d6) δ7.69(ddd,J=8.2,2.1,1.3Hz,2H),7.57(t,J=2.1Hz,2H),7.32(t,J=7.9Hz,2H),6.83(ddd,J=7.9,2.1,1.1Hz,2H),5.28(d,J =5.6Hz,2H),5.21(d,J=5.3Hz,2H),5.08(p,J=5.5Hz,2H),2.29–2.20(m,2 H), 1.91 (ddd, J=12.5, 5.6, 4.7Hz, 4H), 1.81 (ddd, J=12.5, 5.6, 4.7Hz, 4H).

[0071] Monomer Example 5 Synthesis of Novel Structural Diamine Monomer

[0072]

[0073] Taking 5-nitro-2-pyridinecarbonyl chloride as an example, octahydro-2,5-pentanediol (7.1 g, 0.05 mol) and 15 mL of triethylamine solution were added to a flask containing 40 mL of CHCl3, and the flask containing the mixture was stirred in ice water. 5-nitro-2-pyridinecarbonyl chloride (18.7 g, 0.1 mol) was dissolved in 40 mL of CHCl3 and added dropwise to the mixture. The reaction was allowed to proceed for 6 h at room temperature. After the reaction was completed, the mixture was rinsed with 200 mL of water. The liquid was separated, and the obtained organic phase was rotary evaporated to obtain a white solid, which was then washed with hot ethanol. It was vacuum dried at 100 ° C for 24 hours.

[0074]

[0075] Using intermediate product V as the starting material, diamine E was prepared by high-pressure hydrogen reduction method. In the presence of Pd / C (0.34 g) catalyst, intermediate product V (3.4 g, 0.009 mol) was added to DMAc (25 mL) to react with H2. The gas in the flask was evacuated and refilled with H2. The gas atmosphere in the flask was replaced at least three times to ensure that the atmosphere in the flask became pure H2. After the reaction was completed, the reaction solution was filtered to remove Pd / C. The filtrate was poured into water for precipitation to obtain a white powder, which was vacuum dried at 80°C for 24 hours. 1 H NMR (400MHz, DMSO-d6) δ8.53(d,J=2.1Hz,2H),7.90(d,J=8.1Hz,2H),7.35(dd,J=8.3,2.1Hz,2H),5.26(d, J=7.2Hz,2H),5.19–5.10(m,4H),2.29–2.20(m,2H),1.91(ddd,J=12.5,5.6,4.7Hz,4H),1.86–1.78(m,4H).

[0076] Monomer Example 6 Synthesis of Novel Structural Diamine Monomer

[0077]

[0078] Octahydro-2,5-pentanediol (2.84 g, 0.02 mol) and 1-fluoro-5-nitronaphthalene (9.56 g, 0.05 mol) were dissolved in DMF (50 mL) at room temperature. Cesium fluoride (7.6 g, 0.05 mol) was added to the solution as a catalyst. The solution was ventilated three times with nitrogen to remove residual air. The reaction was carried out at 150 ° C for 8 h. After the reaction was completed, the temperature of the reaction mixture was lowered to room temperature and slowly poured into rapidly stirred ethanol for precipitation. The resulting precipitate was collected by filtration and washed with ethanol to produce a yellow precipitate. The light yellow product was filtered and dried in vacuo at 120 ° C for 24 hours.

[0079]

[0080] Using intermediate product VI as the starting material, diamine F was prepared by high-pressure hydrogen reduction method. In the presence of Pd / C (0.3g) catalyst, intermediate product VI (3.88g, 0.008mol) was added to DMAc (20mL) to react with H2, the reaction flask was evacuated, and then refilled with H2, and the gas in the flask was replaced at least three times to ensure that the gas atmosphere in the flask became pure H2. After the reaction, the reaction solution was filtered to remove Pd / C. The filtrate was poured into water for precipitation, and a white powder was obtained by filtration, which was vacuum dried at 80°C for 24h to obtain the product diamine F. 1H NMR (400MHz, DMSO-d6) δ7.96(d,J=9.0Hz,2H),7.32(t,J=1.9Hz,2H),7.22–7.11(m,4H),6.86(dd,J=9.0,1.9Hz,2H),6.64(dd,J=7.5,1. 5Hz,2H),5.41(s,4H),4.76(p,J=5.6Hz,2H),2.26–2.19(m,2H),1.89(ddd,J=12.5,5.3,4.4Hz,4H),1.79(ddd,J=12.5,5.4,4.5Hz,4H).

[0081] Monomer Example 7 Synthesis of Novel Structural Diamine Monomer

[0082]

[0083] Dissolve octahydro-2,5-pentanedicarbonyl chloride (4.68 g, 0.02 mol) and p-nitroaniline (4.14 g, 0.03 mol) in DMF (50 mL) at room temperature. Ventilate with nitrogen three times to remove residual air. React at room temperature for 8 hours. After the reaction is completed, slowly pour the reaction mixture into rapidly stirred ethanol to precipitate. The resulting precipitate is collected by filtration and washed with ethanol to produce a yellow precipitate. Filter to obtain a light yellow product, which is vacuum dried at 120°C for 24 hours.

[0084]

[0085] Using intermediate product Ⅶ as the starting material, diamine G was prepared by high-pressure hydrogen reduction method. In the presence of Pd / C (0.3g) catalyst, intermediate product Ⅶ (3.03g, 0.008mol) was added to DMAc (20mL) to react with H2, the reaction flask was evacuated, and then refilled with H2, and the gas in the flask was replaced at least three times to ensure that the gas atmosphere in the flask became pure H2. After the reaction, the reaction solution was filtered to remove Pd / C. The filtrate was poured into water for precipitation, and a white powder was obtained by filtration, which was vacuum dried at 80°C for 24h to obtain the product diamine G. 1 H NMR(400MHz,DMSO-d6)δ9.71(s,2H),7.44–7.37(m,4H),6.61–6.51(m,4H),5.07(s,4H),2.77(p,J=6 .2Hz,2H),2.34–2.24(m,2H),1.87(ddd,J=12.5,6.2,5.0Hz,4H),1.57(ddd,J=12.1,6.2,4.8Hz,4H).

[0086] Monomer Example 8 Synthesis of Novel Structural Diamine Monomer

[0087]

[0088] Dissolve octahydro-2,5-pentanediamine (2.80 g, 0.02 mol), p-nitroisocyanate (8.2 g, 0.05 mol) and dibutyltin dilaurate (1 mL) in THF (50 mL) at room temperature. Ventilate with nitrogen three times to remove residual air. React at room temperature for 8 h. After the reaction is completed, slowly pour the reaction mixture into rapidly stirred ethanol to precipitate. The resulting precipitate is collected by filtration and washed with ethanol to produce a yellow precipitate. Filter to obtain a light yellow product, which is vacuum dried at 120 ° C for 24 hours.

[0089]

[0090] Using intermediate product VIII as the starting material, diamine H was prepared by high-pressure hydrogen reduction method. In the presence of Pd / C (0.33 g) catalyst, intermediate product VIII (3.26 g, 0.008 mol) was added to DMAc (20 mL) to react with H2, the reaction flask was evacuated, and then refilled with H2, and the gas in the flask was replaced at least three times to ensure that the gas atmosphere in the flask became pure H2. After the reaction, the reaction solution was filtered to remove Pd / C. The filtrate was poured into water for precipitation, and a white powder was obtained by filtration, which was vacuum dried at 80°C for 24 hours to obtain the product diamine H. 1 H NMR (400MHz, DMSO-d6) δ8.32(s,2H),7.42–7.33(m,4H),6.63–6.56(m,4H),6.18(d,J=7.8Hz,2H),5.07(s,4H),3.75( dq,J=7.5,5.3Hz,2H),2.17(h,J=3.6Hz,2H),1.73(ddd,J=12.4,5.3,4.4Hz,4H),1.54(ddd,J=12.4,5.3,4.4Hz,4H).

[0091] Monomer Example 9 Synthesis of Novel Structural Diamine Monomer

[0092]

[0093] At room temperature, octahydro-2,5-pentanecarboxylic acid alcohol (3.40g, 0.02mol) and p-aminonitrobenzene (4.14g, 0.03mol) were added to a 100mL two-necked bottle, and the solution was ventilated with nitrogen three times to remove residual air. 4-Dimethylaminopyridine (0.24g, 0.002mol) was dissolved in CH2Cl2 (40mL). 40mL of the mixed solution CH2Cl2 was added dropwise to the two-necked bottle at 0℃. Subsequently, 1-ethyl-(3-dimethylaminopropyl)carbodiimide (4.23g, 0.022mol) was dissolved in 20mL CH2Cl2, and 20mL of the mixed solution CH2Cl2 was added dropwise to the two-necked bottle at 0℃. After the addition was completed, the reaction bottle was stirred at 25℃ for 12h. After the reaction was completed, the reaction mixture was slowly poured into rapidly stirred water to quench. Extract with CH2Cl2 (3·20mL), remove water with anhydrous sodium sulfate, and obtain a solid by rotary evaporation, which is vacuum dried at 100℃ for 24h. The obtained solid (5.8g, 0.02mol) and 4-fluoronitrobenzene (4.23g, 0.03mol) are dissolved in DMF (50mL) at room temperature. Cesium fluoride (7.6g, 0.05mol) is added to the solution as a catalyst. The solution is ventilated three times with nitrogen to remove residual air. The reaction is carried out at 150℃ for 8h. After the reaction is completed, the temperature of the reaction mixture is lowered to room temperature and slowly poured into rapidly stirred ethanol for precipitation. The obtained precipitate is collected by filtration and washed with ethanol to produce a yellow precipitate. The light yellow product is filtered and vacuum dried at 120℃ for 24h.

[0094]

[0095] Using the intermediate product IX as the starting material, diamine I was prepared by high-pressure hydrogen reduction method. In the presence of Pd / C (0.32g) catalyst, the intermediate product IX (3.29g, 0.008mol) was added to DMAc (20mL) to react with H2, the reaction flask was evacuated, and then refilled with H2, and the gas in the flask was replaced at least three times to ensure that the gas atmosphere in the flask became pure H2. After the reaction was completed, the reaction solution was filtered to remove Pd / C. The filtrate was poured into water for precipitation, and a white powder was obtained by filtration, which was vacuum dried at 80°C for 24h to obtain the product diamine I. 1H NMR(400MHz,DMSO-d6)δ9.71(s,1H),7.44–7.35(m,2H),6.82–6.71(m,2H),6.6 0–6.52(m,4H),5.07(s,2H),4.76(p,J=5.4Hz,3H),2.76(p,J=6.2Hz,1H),2.30 –2.21(m,2H),1.93(ddd,J=12.5,5.4,4.5Hz,2H),1.84(ddd,J=12.5,6.2,4.7H z,2H),1.73(ddd,J=12.1,5.4,4.5Hz,2H),1.58(ddd,J=12.5,6.2,4.7Hz,2H).

[0096] Monomer Example 10 Synthesis of Novel Structural Diamine Monomer

[0097]

[0098] At room temperature, add octahydro-2,5-pentanecarboxylic acid alcohol (3.40g, 0.02mol) and p-aminonitrobenzene (4.14g, 0.03mol) into a 100mL two-necked bottle, and ventilate with nitrogen three times to remove residual air. Dissolve 4-dimethylaminopyridine (0.24g, 0.002mol) in CH2Cl2 (40mL). Add 40mL of the mixed solution CH2Cl2 dropwise into the two-necked bottle at 0℃. After the addition is complete, dissolve 1-ethyl-(3-dimethylaminopropyl)carbodiimide (4.23g, 0.022mol) in 20mL CH2Cl2, and add 20mL of the mixed solution CH2Cl2 dropwise into the two-necked bottle at 0℃. After the addition is complete, place the two-necked bottle at room temperature and stir for 12h. After the reaction is complete, slowly pour the reaction mixture into rapidly stirred water to quench. Extract with CH2Cl2 (3·20mL), remove water with anhydrous sodium sulfate, and obtain solid by rotary evaporation, which is vacuum dried at 100℃ for 24h. The obtained solid (5.8g, 0.02mol), 4-nitrobenzene isocyanate (6.57g, 0.041mol) and dibutyltin dilaurate (1mL) are transferred to a 100mL three-necked flask equipped with a magnetic stirrer, a nitrogen inlet and a reflux condenser. Then 40mL of tetrahydrofuran is added at one time. Ventilate with nitrogen three times to remove residual air, and react at 150℃ for about 8h. After the reaction is completed, the temperature of the reaction mixture is lowered to room temperature and slowly poured into rapidly stirred ethanol for precipitation. The obtained precipitate is collected by filtration, and the intermediate product X is washed with ethanol, and then the intermediate product X is vacuum dried to obtain a light yellow nitro product X.

[0099]

[0100] Using intermediate product X as the starting material, diamine J was prepared by high-pressure hydrogen reduction method. In the presence of Pd / C (0.32g) catalyst, intermediate product X (3.15g, 0.008mol) was added to DMAc (20mL) to react with H2, the reaction flask was evacuated, and then refilled with H2, and the gas in the flask was replaced at least three times to ensure that the gas atmosphere in the flask became pure H2. After the reaction, the reaction solution was filtered to remove Pd / C. The filtrate was poured into water for precipitation, and a white powder was obtained by filtration, which was vacuum dried at 80°C for 24h to obtain product diamine J. 1 H NMR(400MHz,DMSO-d6)δ9.71(s,1H),8.97(s,1H),7.48–7.37(m,4H),6.64–6.51(m,4H),5.07(s,4H),4.95(q, J=5.4Hz,1H),2.76(p,J=6.2Hz,1H),2.29–2.21(m,2H),1.96–1.79(m,6H),1.58(ddd,J=12.5,6.2,4.7Hz,2H).

[0101] Preparation Example of the polymer of the present invention:

[0102] Polymer Example 1 Preparation of polyimide film

[0103]

[0104] Under nitrogen protection, diamine A (4.10 g, 10 mmol) and N,N-dimethylacetamide DMAc (39.9 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA, 2.94 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (20 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide A was obtained after drying. The obtained polyimide A was dissolved in DMAc to prepare a glue solution with a solid content of 10%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent at a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0105] Polymer Example 2 Preparation of polyimide film

[0106]

[0107] Under nitrogen protection, diamine A (4.10 g, 10 mmol) and N,N-dimethylacetamide DMAc (48.4 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 4,4'-hexafluoroisopropylphthalic anhydride (6FDA, 4.44 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (20 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide B was obtained after drying. The obtained polyimide B was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0108] Polymer Example 3 Preparation of polyimide film

[0109]

[0110] Under nitrogen protection, diamine A (4.10 g, 10 mmol) and N,N-dimethylacetamide DMAc (28.7 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then hydrogenated biphenyltetracarboxylic dianhydride (HBPDA, 3.06 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (20 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide C was obtained after drying. The obtained polyimide C was dissolved in DMAc to prepare a glue solution with a solid content of 25%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0111] Polymer Example 4 Preparation of polyimide film

[0112]

[0113] Under nitrogen protection, diamine A (2.05 g, 5 mmol) and N, N-dimethylacetamide DMAc (7.4 mL) were added to the reaction flask, and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (HPMDA, 1.12 g, 5 mmol) was slowly added after stirring at room temperature until diamine A was completely dissolved. After stirring at room temperature for 4 hours, N, N-dimethylacetamide DMAc (6.3 mL) was added. 2,2'-bis(trifluoromethyl)diaminobiphenyl (TFMB, 1.60 g, 5 mmol) was added to the reaction flask, and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (HPMDA, 1.12 g, 5 mmol) was slowly added after stirring at room temperature until TFMB was completely dissolved. After stirring at room temperature for 20 hours, acetic anhydride (40 mL) and pyridine (2 mL) were added, and then stirred at room temperature for 12 hours, and slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide D was obtained after drying. The obtained polyimide D was dissolved in DMAc to prepare a glue solution with a solid content of 30%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0114] Polymer Example 5 Preparation of polyimide film

[0115]

[0116] Under nitrogen protection, diamine B (3.24 g, 10 mmol) and N,N-dimethylacetamide DMAc (43.5 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 4,4'-hexafluoroisopropylphthalic anhydride (6FDA, 4.44 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (20 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide E was obtained after drying. The obtained polyimide E was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0117] Polymer Example 6 Preparation of Polyimide Film

[0118]

[0119] Under nitrogen protection, diamine B (3.24 g, 10 mmol) and N,N-dimethylacetamide DMAc (18.9 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then hydrogenated biphenyltetracarboxylic dianhydride (HBPDA, 3.06 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (20 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide F was obtained after drying. The obtained polyimide F was dissolved in DMAc to prepare a glue solution with a solid content of 25%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0120] Polymer Example 7 Preparation of Polyimide Film

[0121]

[0122] Under nitrogen protection, diamine B (3.24 g, 10 mmol) and N,N-dimethylacetamide DMAc (12.8 mL) were added to the reaction bottle, and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA, 2.24 g, 10 mmol) was slowly added after stirring at room temperature until the diamine was completely dissolved. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (2 mL) were added, followed by stirring at room temperature for 12 h, and the mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, which was then dried to obtain polyimide G. The obtained polyimide G was dissolved in DMAc to prepare a glue solution with a solid content of 30%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0123] Polymer Example 8 Preparation of Polyimide Film

[0124]

[0125] Under nitrogen protection, diamine C (3.80 g, 10 mmol) and N,N-dimethylacetamide DMAc (38.2 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA, 2.94 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (20 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide H was obtained after drying. The obtained polyimide H was dissolved in DMAc to prepare a glue solution with a solid content of 10%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0126] Polymer Example 9 Preparation of Polyimide Film

[0127]

[0128] Under nitrogen protection, diamine E (3.24 g, 10 mmol) and N,N-dimethylacetamide DMAc (36.7 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 4,4'-hexafluoroisopropylphthalic anhydride (6FDA, 2.22 g, 5 mmol) was slowly added, followed by benzoyl chloride (TC, 1.01 g, 5 mmol). After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (2 mL) were added, and then stirred at room temperature for 12 h, and slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, which was dried to obtain polyimide I. The obtained polyimide I was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0129] Polymer Example 10 Preparation of polyimide film

[0130]

[0131] Under nitrogen protection, diamine F (4.24 g, 10 mmol) and N,N-dimethylacetamide DMAc (40.7 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA, 2.94 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (20 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide J was obtained after drying. The obtained polyimide J was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0132] Polymer Example 11 Preparation of polyimide film

[0133]

[0134] Under nitrogen protection, diamine G (3.78 g, 10 mmol) and N,N-dimethylacetamide DMAc (46.6 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 4,4'-hexafluoroisopropylphthalic anhydride (6FDA, 4.44 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (20 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide K was obtained after drying. The obtained polyimide K was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0135] Polymer Example 12 Preparation of polyimide film

[0136]

[0137] Under nitrogen protection, diamine H (4.08 g, 10 mmol) and N,N-dimethylacetamide DMAc (48.3 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 4,4'-hexafluoroisopropylphthalic anhydride (6FDA, 4.44 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (20 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide L was obtained after drying. The obtained polyimide L was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0138] Polymer Example 13 Preparation of polyimide film

[0139]

[0140] Under nitrogen protection, diamine J (3.94 g, 10 mmol) and N,N-dimethylacetamide DMAc (47.5 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 4,4'-hexafluoroisopropylphthalic anhydride (6FDA, 4.44 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (20 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide M was obtained after drying. The obtained polyimide M was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0141] Polymer Comparative Example

[0142] Polymer Comparative Example 1 Preparation of Polyimide Film

[0143]

[0144] Under nitrogen protection, ISB diamine 1 (3.84 g, 10 mmol) and N,N-dimethylacetamide DMAc (38.4 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA, 2.94 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (2 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide K was obtained after drying. The obtained polyimide K was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0145] Polymer Comparative Example 2 Preparation of Polyimide Film

[0146]

[0147] Under nitrogen protection, ISB diamine 2 (5.20 g, 10 mmol) and N,N-dimethylacetamide DMAc (54.8 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 4,4'-(hexafluoroisopropylene) diphthalic anhydride (6FDA, 4.44 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (2 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide L was obtained after drying. The obtained polyimide L was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0148] Polymer Comparative Example 3 Preparation of Polyimide Film

[0149]

[0150] Under nitrogen protection, ISB diamine 3 (4.12 g, 10 mmol) and N,N-dimethylacetamide DMAc (48.5 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 4,4'-(hexafluoroisopropylene) diphthalic anhydride (6FDA, 4.44 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (2 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide M was obtained after drying. The obtained polyimide M was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0151] Polymer Comparative Example 4 Preparation of Polyimide Film

[0152]

[0153] Under nitrogen protection, ISB diamine 4 (3.28 g, 10 mmol) and N,N-dimethylacetamide DMAc (43.7 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 4,4'-(hexafluoroisopropylene) diphthalic anhydride (6FDA, 4.44 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (2 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide N was obtained after drying. The obtained polyimide N was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0154] Preparation of Comparative Example (PI(TFMB-6FDA))

[0155]

[0156] Under nitrogen protection, 2,2'-bis(trifluoromethyl)diaminobiphenyl (TFMB, 3.20 g, 10 mmol) and N,N-dimethylacetamide DMAc (43.3 mL) were added to the reaction bottle, and the mixture was stirred at room temperature until the diamine was completely dissolved, and then 4,4'-(hexafluoroisopropylene)diphthalic anhydride (6FDA, 4.44 g, 10 mmol) was slowly added. After stirring at room temperature for 24 h, acetic anhydride (40 mL) and pyridine (2 mL) were added, and then stirred at room temperature for 12 h. The mixture was slowly poured into ethanol with high-speed stirring to obtain a fibrous polyimide precipitate, and polyimide P was obtained after drying. The obtained polyimide P was dissolved in DMAc to prepare a glue solution with a solid content of 15%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven to remove the solvent by a certain temperature increase program (80°C, 1h; 150°C, 1h; 200°C, 1h; 250°C, 1h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a film thickness of about 25μm was measured by a step profiler.

[0157] The performance data of the polymer examples of the present invention and the comparative examples are shown in Table 1. The temperature range of the CTE test is 50°C-300°C.

[0158] Table 1

[0159]

[0160]

[0161] It can be seen that the optical properties, mechanical properties and thermal properties of the polyimide film introduced with bio-renewable diamine in the present invention are improved compared with the polyimide film containing ISB diamine, and the CTE is significantly reduced, thereby achieving the goal of the present invention to design a new bio-based renewable polyimide material with low thermal expansion coefficient and good transparency (the main reason why some properties of Examples 3, 4, 7, and 8 are worse than those of the comparative example is that the anhydride selected is fatty anhydride, while the anhydrides selected in the comparative example are all aromatic anhydrides).

[0162] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A diamine monomer, characterized in that Selected from the group of chemicals represented by the following chemical formulas:

2. The method for preparing a diamine monomer according to claim 1, wherein Prepared by any of methods 1 to 4: Method 1: Compound 1 is used as a raw material, reacted with an isocyanate-substituted nitrobenzene compound, a halogen-substituted nitrobenzene compound or an acyl chloride-substituted nitrobenzene compound to introduce a corresponding nitrobenzene group, and then subjected to a reduction reaction to obtain the diamine monomer; Method 2: Compound 2 is used as a raw material, reacted with an isocyanate-substituted nitrobenzene compound or an acyl chloride-substituted nitrobenzene compound to introduce a corresponding nitrobenzene group, and then subjected to a reduction reaction to obtain the diamine monomer; Method 3: Compound 3 is used as a raw material, reacted with an isocyanate-substituted nitrobenzene compound or an amine-substituted nitrobenzene compound to introduce a corresponding nitrobenzene group, and then subjected to a reduction reaction to obtain the diamine monomer; Method 4: using compound 4 as a raw material, reacting with an isocyanate-substituted nitrobenzene compound, a halogen-substituted nitrobenzene compound, an acyl chloride-substituted nitrobenzene compound or an amine-substituted nitrobenzene compound to introduce the corresponding nitrobenzene group, and then performing a reduction reaction to obtain the diamine monomer; The structures of Compound 1, Compound 2, Compound 3 and Compound 4 are as follows:

3. A polymer for electronic devices, characterized in that: Prepared from the diamine monomer of claim 1 and a dianhydride compound, or prepared from the diamine monomer of claim 1, an aromatic diamine monomer and a dianhydride compound; The general structure of the polymer is shown in formula (III): Wherein, m is an integer of 5 to 10,000, n is an integer of 0 to 10,000, X is a tetravalent aromatic hydrocarbon group, Y is a group obtained by removing the amino group from the diamine monomer, and R is an aromatic diamine group.

4. The polymer according to claim 3, characterized in that The polymer is polyimide.

5. Use of the polymer as claimed in claim 3 in electronic devices.

Images