A spiroxanthine-fluorenyl hyperbranched polyimide, its preparation method and application
By introducing spiroxanthine-fluorenyl asymmetric tetraamine molecules into hyperbranched polyimide and copolymerizing them to form a twisted structure, the problem of insufficient transparency of hyperbranched polyimide materials was solved, and a high-transparency film effect was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN UNIV OF TECH
- Filing Date
- 2024-05-27
- Publication Date
- 2026-06-30
AI Technical Summary
Existing hyperbranched polyimide materials have low transparency in the ultraviolet-visible region, mainly due to the deep color and strong absorption caused by the push-pull electron effect between the repeating unit diamine and the aromatic dianhydride.
By using spiroxanthine-fluorenyl asymmetric tetraamine molecules as branch points, and copolymerizing them with diamine monomers and dianhydrides, a hyperbranched polyimide with a twisted and asymmetric structure is introduced, which increases the disorder of the molecular chain and reduces the charge transfer effect.
The transparency of hyperbranched polyimide films in the visible light range was significantly improved, with a transmittance of up to 98%, demonstrating the effectiveness of the twisted tetraamine branch points.
Smart Images
Figure CN118791458B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of hyperbranched polyimide materials technology, and specifically to a hyperbranched copolymer polyimide based on spiroxane-fluorenyltetramine and a hyperbranched copolymer polyimide with the molecular formula of spiroxane-fluorenyltetramine as the branching point, its preparation method, and its applications. Background Technology
[0002] In recent years, hyperbranched polymers have attracted widespread attention in chemistry, materials science, and biology. Hyperbranched polyimide (HBPI) is a novel polymer formed by combining hyperbranched macromolecules and linear polyimide. It possesses a unique three-dimensional molecular structure, a highly branched molecular chain distribution, and a high density of surface end-group functional groups. Its unique structure, excellent physicochemical properties, and versatility in synthesis and modification methods make HBPI a potential candidate for applications in optical materials.
[0003] Hyperbranched polymers (HBPIs) have attracted considerable attention in the field of optical devices due to their ease of preparation, good solubility, and ideal thermal and optical properties. However, the push-pull electron effect between the repeating unit diamine (electron donor) and aromatic dianhydride (electron acceptor) in the polymer results in a darker film color and strong absorption in the ultraviolet-visible region, leading to low transparency. Effectively suppressing the CTC effect and improving transmittance is a pressing issue in the field of hyperbranched polymers. Summary of the Invention
[0004] This invention provides a spiroxanthine-fluorenyl asymmetric tetraamine molecule. The synthesized asymmetric rigid twisted spirocyclic tetraamine molecule is used as the branch point of the hyperbranched polymer. A difunctional diamine monomer and dianhydride are selectively added to participate in the copolymerization to obtain a hyperbranched polyimide.
[0005] The technical solution of this invention: This invention provides a spiroxanthine-fluorenyl tetraamine monomer with the structure shown in Formula I:
[0006]
[0007] In this spiroxanthine-fluorenyl tetraamine monomer, the planes of the xanthine ring and the fluorenyl ring are perpendicular, and each ring has two amino groups. The amino groups on the xanthine ring can be located at the meta or para position of O, as shown in the following structure:
[0008]
[0009] This invention also provides a method for preparing the tetraamine monomer containing the spiroxanthine-fluorenyl structure described in the above technical solution, comprising the following steps:
[0010]
[0011] Compound 2 was synthesized using sulfuric acid as a solvent, with nitric acid used to nitrate fluorenone, and the amount of nitric acid was controlled to yield dinitrofluorenone.
[0012] Compound X-NO2: Compound 3 was synthesized by reacting compound 2 with p-toluenesulfonic acid as a solvent in a one-pot process, using m-aminophenol or p-aminophenol.
[0013] Target compound: The nitro group on compound 3 was reduced to an amino group using zinc powder to obtain target compound 4. Application of the described spirozanol-fluorenyltetramine in the preparation of hyperbranched polyimides.
[0014] A hyperbranched polyimide is obtained by polymerization of the aforementioned spiroxanthine-fluorenyltetramine, organic diamine, and organic tetracarboxylic dianhydride.
[0015] Some specific hyperbranched polyimides, wherein the organic diamine is selected from at least one of aromatic diamines comprising 1-10 benzene rings with or without substituents, and alicyclic diamines having 3-10 carbon atoms.
[0016] The organic tetracarboxylic dianhydride is selected from at least one of the following: aromatic tetracarboxylic dianhydrides containing 1-10 benzene rings with or without substituents, aliphatic tetracarboxylic dianhydrides with 4-20 carbon atoms, alicyclic tetracarboxylic dianhydrides with 3-12 carbon atoms, and heterocyclic tetracarboxylic dianhydrides with 3-12 carbon atoms.
[0017] Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect.
[0018] The substituents are each independently selected from C1-C15 alkyl groups and C1-C15 fluoroalkyl groups.
[0019] Some specific hyperbranched polyimides have the following structures:
[0020]
[0021] R1 is independently selected from arylene groups containing 1-10 benzene rings with or without substituents, or alicyclic groups with 3-10 carbon atoms.
[0022] R2 is independently selected from the parent structures of aromatic tetracarboxylic dianhydrides containing 1-10 benzene rings with or without substituents, aliphatic tetracarboxylic dianhydrides with 5-20 carbon atoms, alicyclic tetracarboxylic dianhydrides with 3-16 carbon atoms, and heterocyclic tetracarboxylic dianhydrides with 3-12 carbon atoms.
[0023] Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect.
[0024] The substituents are each independently selected from C1-C15 alkyl groups and C1-C15 fluoroalkyl groups.
[0025] n is an integer greater than 1.
[0026] In some specific hyperbranched polyimides, R1 is independently selected from arylene groups comprising 1-6 benzene rings with or without substituents, or alicyclic groups having 3-10 carbon atoms.
[0027] R2 is independently selected from the parent structures of aromatic tetracarboxylic dianhydrides containing 1-6 benzene rings with or without substituents, aliphatic tetracarboxylic dianhydrides with 5-15 carbon atoms, alicyclic tetracarboxylic dianhydrides with 3-12 carbon atoms, and heterocyclic tetracarboxylic dianhydrides with 3-10 carbon atoms.
[0028] Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect.
[0029] The substituents are each independently selected from C1-C10 alkyl groups and C1-C10 fluoroalkyl groups.
[0030] In some specific hyperbranched polyimides, R1 is independently selected from arylene groups comprising 1-6 benzene rings with or without substituents, or alicyclic groups having 3-10 carbon atoms.
[0031] R2 is independently selected from aromatic tetracarboxylic dianhydrides containing 1-6 benzene rings with or without substituents, or alicyclic tetracarboxylic dianhydrides with 3-12 carbon atoms.
[0032] Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect.
[0033] The substituents are each independently selected from C1-C5 alkyl groups and C1-C5 fluoroalkyl groups.
[0034] Some specific hyperbranched polyimides, where n is an integer from 1 to 100.
[0035] Some specific hyperbranched polyimides, where n is an integer from 1 to 50.
[0036] Some specific hyperbranched polyimides, where n is an integer from 1 to 20.
[0037] Some specific hyperbranched polyimides, where n is an integer from 1 to 10.
[0038] Some specific hyperbranched polyimides, where n is an integer from 1 to 5.
[0039] For some specific polyimides, R1 is independently selected from...
[0040]
[0041] For some specific polyimides, R2 is independently selected from...
[0042] The preparation method of the hyperbranched polyimide, including the reaction steps and reaction formula, is as follows:
[0043]
[0044] Spiroxane-fluorenyltetramine, and The hyperbranched polyimide was obtained by copolymerization in an organic solvent at 0–30°C.
[0045] The definitions of R1 and R2 are those in the above structure.
[0046] The present invention provides the specific preparation steps of the above-described spiroxanthine-fluorenyl hyperbranched polyimide as follows: N-methylpyrrolidone (NMP) is bubbled under an argon atmosphere for 30 minutes. The reaction flask and magnetic stirrer are dried in an oven beforehand to ensure the removal of moisture. The entire reaction system is evacuated and purged with argon three times to ensure the absence of oxygen in the reaction system and maintained under an argon atmosphere. NMP is placed in a two-necked reaction flask, and diamine is added, ensuring complete dissolution of the diamine in the NMP. Then, dianhydride is added and stirred to dissolve. The tetraamine monomer is dissolved in NMP and added to a constant-pressure dropping funnel. The solution is added dropwise to the reaction system. During the continuous addition, the viscosity of the solution will increase. To prevent gel formation, NMP can be added appropriately. The solid content of the reaction system is ultimately maintained at approximately 5%. The reaction is stirred at 25°C for 12 hours. Pyridine, acetic anhydride, and a trace amount of isoquinoline, an imide ring-closing catalyst, are added to the reaction solution, and then the temperature is raised to 180°C for dehydration imidization. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was added dropwise to anhydrous ethanol. The reaction product precipitated, centrifuged, and washed with anhydrous ethanol until the centrifuged liquid was clear and transparent. The substance obtained by centrifugation was repeatedly dissolved and eluted three times, and then dried under vacuum to obtain the hyperbranched polymer HBPI.
[0047] The diamine is selected from:
[0048]
[0049] The acid anhydride is selected from:
[0050]
[0051] Specifically, the diamine is selected from:
[0052] Specifically, the acid anhydride is selected from:
[0053] The present invention provides a route for preparing a transparent film comprising the following steps: at room temperature, a hyperbranched polyimide with a solid content of 5%-20% is completely dissolved in a strongly polar aprotic organic solvent; the resulting polyimide solution is left to stand in a vacuum drying phase for 1-4 hours until the air bubbles are eliminated; the film is then coated on a clean substrate; the film is first dried at 30-40°C for 1-3 hours; then the temperature is increased to 180-200°C in increments of 10-30°C, with each increment maintained for 1-120 minutes; the film is then allowed to cool naturally to room temperature, and the film is removed to obtain a transparent polyimide film.
[0054] The beneficial effects of this invention are as follows: This invention provides a spirozanol-fluorenyl asymmetric tetraamine molecule. This asymmetric, rigidly twisted spirocyclic tetraamine molecule can serve as a branching point in hyperbranched polymers. Copolymerization with diamine monomers and dianhydrides yields a highly transparent hyperbranched polyimide. This invention introduces a twisted, asymmetric structure into the polymer backbone, increasing the diversity of the molecular chain structure, increasing the disorder of the internal molecular chains, increasing the distance between polymer chains, reducing chain stacking, and decreasing the charge transfer effect between chains. This improves the transparency of the hyperbranched polyimide film in the visible light range. Experiments have demonstrated that the UV-Vis transmittance of HBPI1 material can reach up to 98%, further illustrating that introducing twisted tetraamine molecules into the linear polymer chain as branching points in hyperbranched polyimides is beneficial for improving the material's transparency. Attached Figure Description
[0055] Figure 1 The spiroxanthine-fluorenyltetramine molecule of the present invention 1 H-NMR spectrum.
[0056] Figure 2 This is the mass spectrum of the spiroxanthine-fluorenyltetramine molecule of the present invention.
[0057] Figure 3 This is the infrared spectrum of the spiroxanthine-fluorenyltetramine molecule of the present invention.
[0058] Figure 4 For HBPI1 in Embodiment 1 of the present invention 1 H-NMR spectrum.
[0059] Figure 5 This is the infrared spectrum of HBPI1 in Embodiment 1 of the present invention.
[0060] Figure 6 This is the UV-Vis absorption spectrum of HBPI1 in Example 1 of the present invention. Detailed Implementation
[0061] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.
[0062] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.
[0063] Spiroxane-fluorenyltetramine molecule
[0064]
[0065] Preparation steps:
[0066] In a 250 mL reaction flask, concentrated sulfuric acid (10 mL) was slowly added dropwise to 9-fluorenone (10.00 g, 55.49 mmol), with constant stirring to ensure dissolution. A mixture of HNO3 (65%, 11.45 mL, 166.48 mmol) and H2SO4 (98%, 9.24 mL, 166.48 mmol) was then slowly added dropwise to the flask. After the mixture was completely added, the temperature was gradually increased, and the reaction was carried out at 110 °C until the reaction solution became viscous. After 4 hours of reaction, TLC analysis was performed (using ethyl acetate as the developing solvent). If the reactants had not reacted completely, the mixture was added again. If the reaction was confirmed to be complete, the reaction mixture was slowly poured into 200 mL of water, resulting in a yellow precipitate. The precipitate was filtered to obtain the crude product, washed with water (3 × 100 mL), and dried in a vacuum drying oven. Recrystallization of the crude product from tetrahydrofuran yielded a yellow solid compound 2 (13.50 g, yield: 90.04%).
[0067] The compound was synthesized using a one-pot method. In a 250 mL three-necked flask, compound 2 (10.00 g, 37.01 mmol), m-aminophenol (12.12 g, 111.03 mmol), and p-toluenesulfonic acid (19.12 g, 111.03 mmol) were mixed thoroughly and heated until the reactants melted. The reaction was carried out in the molten state for 3 hours, and TLC analysis confirmed the completion of the reaction. The mixture was then cooled to room temperature, and 50 mL of ethyl acetate and 50 mL of saturated sodium bicarbonate aqueous solution were added to the flask. Stirring was continued. The filtrate was extracted with ethyl acetate, and the product dissolved in the ethyl acetate layer. The solvent was removed by vacuum distillation, and the product (compound 3) was purified by silica gel column chromatography. Compound 3 was a yellow powder (2.30 g, yield: 68.68%). Eluent: dichloromethane: methanol = 100:1.
[0068] Compound 3 (1 g, 2.21 mmol), Zn powder (1.73 g, 26.52 mmol), and ammonium chloride (118.23 mg, 2.21 mmol) were placed in a 100 mL reaction flask. The flask was evacuated and purged with argon gas three times to ensure the absence of oxygen. Under an argon atmosphere, THF / H2O solvent (3 / 1, 40 mL) was added, and the mixture was stirred thoroughly. Glacial acetic acid (0.6 mL) was added dropwise, and the reaction was carried out at 75 °C for 3 hours. TLC analysis indicated the reaction was complete. The mixture was extracted with ethyl acetate, the solvent was removed by vacuum distillation, and the solution was purified by dry column chromatography (DCM:MeOH = 30:1) to give a grayish-white compound 4 (489 mg, yield: 56.37%).
[0069] Example 1
[0070]
[0071] Specific steps: Bubbling 10 mL of N-methylpyrrolidone (NMP) under an argon atmosphere for 30 min. Dry the reaction flask and magnetic stirrer in an oven beforehand to ensure no moisture is removed. Vacuum the entire reaction system three times with argon to ensure the absence of oxygen and maintain an argon atmosphere. Place 10 mL of NMP in a two-necked flask and add diaminodiphenyl ether (ODA) (0.816 g, 4.08 mmol), ensuring complete dissolution in the NMP. Then add 6 FDA (1.64 g, 5.10 mmol) and stir to dissolve. Dissolve the tetraamine monomer (0.2 g, 0.509 mmol) in the NMP and add it to a constant-pressure dropping funnel. Add the solution dropwise to the reaction system. As the solution viscosity increases during the dropwise addition, add NMP as needed to prevent gel formation. The final solid content of the reaction system should be maintained at approximately 5%. Stir the reaction at 25°C for 12 h. Pyridine, acetic anhydride, and a trace amount of isoquinoline, an imide ring-closing catalyst, were added to the reaction solution, and then the temperature was raised to 180°C. Dehydration imidization was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was added dropwise to anhydrous ethanol. The reaction product precipitated, was centrifuged, and washed with anhydrous ethanol until the centrifuged liquid was clear and transparent. The centrifuged substance was repeatedly dissolved and eluted three times, and then dried under vacuum to obtain polymer HBPI1.
[0072] Example 2
[0073]
[0074] For specific synthesis steps, refer to Example 1. Replace diaminodiphenyl ether with 4,4'-methylenediphenylamine to obtain polymer HBPI2.
[0075] Example 3
[0076]
[0077] For specific synthesis steps, refer to Example 1. Replace diaminodiphenyl ether with 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine to obtain polymer HBPI3.
[0078] Example 4
[0079]
[0080] 10 mL of N-methylpyrrolidone (NMP) was bubbled under an argon atmosphere for 30 min. The reaction flask and magnetic stirrer were dried in an oven beforehand to ensure the removal of moisture. The entire reaction system was evacuated and subjected to argon three times to ensure the absence of oxygen. 10 mL of NMP was placed in a two-necked flask, and p-phenylenediamine (4.08 mmol) was added, ensuring complete dissolution. 6 FDA (5.10 mmol) was then added and stirred to dissolve the NMP. The tetraamine monomer (0.509 mmol) was dissolved in the NMP and added to a constant-pressure dropping funnel. The solution was added dropwise to the reaction system. As the solution viscosity increased during the dropwise addition, NMP was added as needed to prevent gel formation. The solid content of the reaction system was ultimately maintained at approximately 5%. The reaction was stirred at 25 °C for 12 h. Pyridine, acetic anhydride, and a trace amount of the imide ring-closing catalyst isoquinoline were added to the reaction solution, and the temperature was raised to 180 °C. Dehydration imidization was carried out for 6 h. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was added dropwise to anhydrous ethanol. The reaction product precipitated, centrifuged, and washed with anhydrous ethanol until the centrifuged liquid was clear and transparent. The centrifuged substance was repeatedly dissolved and eluted three times, and then dried under vacuum to obtain polymer HBPI4.
[0081] Example 5
[0082]
[0083] 10 mL of N-methylpyrrolidone (NMP) was bubbled under an argon atmosphere for 30 min. The reaction flask and magnetic stirrer were dried in an oven beforehand to ensure the removal of moisture. The entire reaction system was evacuated and purged with argon three times to ensure the absence of oxygen. 10 mL of NMP was placed in a two-necked flask, and 4,4'-diaminodiphenyl sulfone (4.08 mmol) was added, ensuring complete dissolution. Then, 6 FDA (5.10 mmol) was added and stirred until dissolved. The tetraamine monomer (0.509 mmol) was dissolved in NMP and added to a constant-pressure dropping funnel. The solution was added dropwise to the reaction system. As the solution viscosity increased during the dropwise addition, NMP was added as needed to prevent gel formation. The solid content of the reaction system was ultimately maintained at approximately 5%. The reaction was stirred at 25 °C for 12 h. Pyridine, acetic anhydride, and a trace amount of the imide ring-closing catalyst isoquinoline were added to the reaction solution, and the temperature was then raised to 180 °C. Dehydration imidization was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was added dropwise to anhydrous ethanol. The reaction product precipitated, and the product was centrifuged and washed with anhydrous ethanol until the centrifuged liquid was clear and transparent. The centrifuged substance was repeatedly dissolved and eluted 3 times, and then dried under vacuum to obtain polymer HBPI5.
[0084] Example 6
[0085]
[0086] For specific synthesis steps, refer to Example 1. Replace diaminodiphenyl ether with 4,4'-(1,4-phenylbis(oxy))diphenylamine to obtain polymer HBPI6.
[0087] Example 7
[0088]
[0089] The synthesis method is the same as in Example 1, using 2,2′-dimethyl-[1,1′-biphenyl]-4,4′-diamine instead of diaminodiphenyl ether to obtain polymer HBPI7.
[0090] Example 8
[0091]
[0092] The synthesis method is the same as in Example 1, using 5,5'-carbonylbis(isobenzofuran-1,3-dione) instead of hexafluorodianhydride to obtain polymer HBPI8.
[0093] Example 9
[0094]
[0095] 10 mL of N-methylpyrrolidone (NMP) was bubbled under an argon atmosphere for 30 min. The reaction flask and magnetic stirrer were dried in an oven beforehand to ensure that no moisture was removed. The entire reaction system was evacuated and purged with argon three times to ensure that no oxygen was present in the reaction system and to maintain an argon atmosphere. 10 mL of NMP was placed in a two-necked reaction flask and 4,4'-methylenediphenylamine (4.08 mmol) was added, ensuring that it was completely dissolved in the NMP. Then, 5,5'-carbonylbis(isobenzofuran-1,3-dione) (6.20 mmol) was added and stirred to dissolve. The tetraamine monomer (0.509 mmol) was dissolved in NMP and added to a constant pressure dropping funnel. The solution was added dropwise to the reaction system. During the dropwise addition, the viscosity of the solution will increase. To prevent gel formation, NMP can be added as needed. The solid content of the reaction system was finally maintained at about 5%. The reaction was stirred at 25°C for 12 h. Pyridine, acetic anhydride, and a trace amount of isoquinoline, an imide ring-closing catalyst, were added to the reaction solution, and then the temperature was raised to 180°C. Dehydration imidization was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was added dropwise to anhydrous ethanol. The reaction product precipitated, was centrifuged, and washed with anhydrous ethanol until the centrifuged liquid was clear and transparent. The centrifuged substance was repeatedly dissolved and eluted three times, and then dried under vacuum to obtain the polymer HBPI9.
[0096] Example 10
[0097]
[0098] The synthesis method is the same as in Example 3, using 5,5'-carbonylbis(isobenzofuran-1,3-dione) instead of hexafluorodianhydride to obtain polymer HBPI10.
[0099] Example 11
[0100]
[0101] The synthesis method is the same as in Example 4, using 5,5'-carbonylbis(isobenzofuran-1,3-dione) instead of hexafluorodianhydride to obtain polymer HBPI11.
[0102] Example 12
[0103]
[0104] 10 mL of N-methylpyrrolidone (NMP) was bubbled under an argon atmosphere for 30 min. The reaction flask and magnetic stirrer were dried in an oven beforehand to ensure that no moisture was removed. The entire reaction system was evacuated and purged with argon three times to ensure that no oxygen was present in the reaction system and to maintain an argon atmosphere. 10 mL of NMP was placed in a two-necked reaction flask and 4,4'-diaminodiphenyl sulfone (4.08 mmol) was added to ensure that it was completely dissolved in NMP. Then, 5,5'-carbonylbis(isobenzofuran-1,3-dione) (6.20 mmol) was added and stirred to dissolve. The tetraamine monomer (0.509 mmol) was dissolved in NMP and added to a constant pressure dropping funnel. The solution was added dropwise to the reaction system. During the dropwise addition, the viscosity of the solution will increase. To prevent gel formation, NMP can be added as needed. The solid content of the reaction system was finally maintained at about 5%. The reaction was stirred at 25°C for 12 h. Pyridine, acetic anhydride, and a trace amount of isoquinoline, an imide ring-closing catalyst, were added to the reaction solution, and then the temperature was raised to 180°C. Dehydration imidization was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was added dropwise to anhydrous ethanol. The reaction product precipitated, was centrifuged, and washed with anhydrous ethanol until the centrifuged liquid was clear and transparent. The centrifuged substance was repeatedly dissolved and eluted three times, and then dried under vacuum to obtain the polymer HBPI11.
[0105] Example 13
[0106]
[0107] The synthesis method is the same as in Example 6, using 5,5'-carbonylbis(isobenzofuran-1,3-dione) instead of hexafluorodianhydride to obtain polymer HBPI13.
[0108] Example 14
[0109]
[0110] The synthesis method is the same as in Example 7, using 5,5'-carbonylbis(isobenzofuran-1,3-dione) instead of hexafluorodianhydride to obtain polymer HBPI14.
[0111] Example 15
[0112]
[0113] 10 mL of N-methylpyrrolidone (NMP) was bubbled under an argon atmosphere for 30 min. The reaction flask and magnetic stirrer were dried in an oven beforehand to ensure that no moisture was removed. The entire reaction system was evacuated and purged with argon three times to ensure that no oxygen was present in the reaction system and to maintain an argon atmosphere. 10 mL of NMP was placed in a two-necked reaction flask and 4,4'-diaminodiphenyl ether (4.08 mmol) was added to ensure that it was completely dissolved in NMP. Then 6 FDA (5.10 mmol) was added and stirred to dissolve. The para-xanthrenetetramine monomer (0.509 mmol) was dissolved in NMP and added to a constant pressure dropping funnel. The solution was added dropwise to the reaction system. During the dropwise addition, the viscosity of the solution will increase. To prevent gel formation, NMP can be added as needed. The solid content of the reaction system was finally maintained at about 5%. The reaction was stirred at 25°C for 12 h. Pyridine, acetic anhydride, and a trace amount of isoquinoline, an imide ring-closing catalyst, were added to the reaction solution, and then the temperature was raised to 180°C. Dehydration imidization was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was added dropwise to anhydrous ethanol. The reaction product precipitated, was centrifuged, and washed with anhydrous ethanol until the centrifuged liquid was clear and transparent. The centrifuged substance was repeatedly dissolved and eluted three times, and then dried under vacuum to obtain the polymer HBPI15.
[0114] Example 16
[0115]
[0116] 10 mL of N-methylpyrrolidone (NMP) was bubbled under an argon atmosphere for 30 min. The reaction flask and magnetic stirrer were dried in an oven beforehand to ensure that no moisture was removed. The entire reaction system was evacuated and purged with argon three times to ensure that no oxygen was present in the reaction system and to maintain an argon atmosphere. 10 mL of NMP was placed in a two-necked reaction flask and 4,4'-methylenediphenylamine (4.08 mmol) was added to ensure that it was completely dissolved in the NMP. Then, 6 FDA (5.10 mmol) was added and stirred to dissolve. The para-xanthrenetetramine monomer (0.509 mmol) was dissolved in NMP and added to a constant pressure dropping funnel. The solution was added dropwise to the reaction system. During the dropwise addition, the viscosity of the solution will increase. To prevent gel formation, NMP can be added as needed. The solid content of the reaction system was finally maintained at about 5%. The reaction was stirred at 25°C for 12 h. Pyridine, acetic anhydride, and a trace amount of isoquinoline, an imide ring-closing catalyst, were added to the reaction solution, and then the temperature was raised to 180°C. Dehydration imidization was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was added dropwise to anhydrous ethanol. The reaction product precipitated, was centrifuged, and washed with anhydrous ethanol until the centrifuged liquid was clear and transparent. The centrifuged substance was repeatedly dissolved and eluted three times, and then dried under vacuum to obtain the polymer HBPI16.
[0117] Example 17
[0118]
[0119] The synthesis method is the same as in Example 6, with para-xanthine tetramine used instead of meta-xanthine tetramine to obtain polymer HBPI17.
[0120] Example 18
[0121]
[0122] The synthesis method is the same as in Example 8, with para-xanthine tetramine used instead of meta-xanthine tetramine to obtain polymer HBPI18.
[0123] Example 19
[0124]
[0125] 10 mL of N-methylpyrrolidone (NMP) was bubbled under an argon atmosphere for 30 min. The reaction flask and magnetic stirrer were dried in an oven beforehand to ensure that no moisture was removed. The entire reaction system was evacuated and purged with argon three times to ensure that no oxygen was present in the reaction system and to maintain an argon atmosphere. 10 mL of NMP was placed in a two-necked reaction flask and 4,4'-methylenediphenylamine (4.08 mmol) was added, ensuring that it was completely dissolved in the NMP. Then, 5,5'-carbonylbis(isobenzofuran-1,3-dione) (5.10 mmol) was added and stirred to dissolve. The para-xanthrenetetramine monomer (0.509 mmol) was dissolved in NMP and added to a constant pressure dropping funnel. The solution was added dropwise to the reaction system. During the dropwise addition, the viscosity of the solution will increase. To prevent gel formation, NMP can be added as needed. The solid content of the reaction system was finally maintained at about 5%. The reaction was stirred at 25°C for 12 h. Pyridine, acetic anhydride, and a trace amount of isoquinoline, an imide ring-closing catalyst, were added to the reaction solution, and then the temperature was raised to 180°C. Dehydration imidization was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was added dropwise to anhydrous ethanol. The reaction product precipitated, was centrifuged, and washed with anhydrous ethanol until the centrifuged liquid was clear and transparent. The centrifuged substance was repeatedly dissolved and eluted three times, and then dried under vacuum to obtain the polymer HBPI19.
[0126] Example 20
[0127]
[0128] 10 mL of N-methylpyrrolidone (NMP) was bubbled under an argon atmosphere for 30 min. The reaction flask and magnetic stirrer were dried in an oven beforehand to ensure that no moisture was removed. The entire reaction system was evacuated and purged with argon three times to ensure that no oxygen was present in the reaction system and to maintain an argon atmosphere. 10 mL of NMP was placed in a two-necked reaction flask and 4,4'-diaminodiphenyl sulfone (4.08 mmol) was added to ensure that it was completely dissolved in NMP. Then, 5,5'-carbonylbis(isobenzofuran-1,3-dione) (5.10 mmol) was added and stirred to dissolve. The para-xanthrenetetramine monomer (0.509 mmol) was dissolved in NMP and added to a constant pressure dropping funnel. The solution was added dropwise to the reaction system. During the dropwise addition, the viscosity of the solution will increase. To prevent gel formation, NMP can be added as needed. The solid content of the reaction system was finally maintained at about 5%. The reaction was stirred at 25°C for 12 h. Pyridine, acetic anhydride, and a trace amount of isoquinoline, an imide ring-closing catalyst, were added to the reaction solution, and then the temperature was raised to 180°C. Dehydration imidization was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was added dropwise to anhydrous ethanol. The reaction product precipitated, was centrifuged, and washed with anhydrous ethanol until the centrifuged liquid was clear and transparent. The centrifuged substance was repeatedly dissolved and eluted three times, and then dried under vacuum to obtain the polymer HBPI20.
[0129] Example 21
[0130]
[0131] The synthesis method is the same as in Example 14, using para-xanthine tetramine instead of meta-xanthine tetramine to obtain polymer HBPI21.
[0132] Test Example 1
[0133] Structural characterization of spirozanol-fluorenyltetramine molecule (compound 4) and HBPI1 prepared in Example 1.
[0134] Nuclear magnetic resonance hydrogen spectrum test ( 1 1H-NMR, Bruker Advance III 400MHz NMR spectrometer: Deuterated dimethyl sulfoxide (DMSO) was used as the solvent, and tetramethylsilane (TMS) was used as the internal standard. The sample was thoroughly dried to ensure no solvent was present. 3–5 mg of the sample was weighed and dissolved in DMSO (10–15 mg for polymer HBPI1), as shown in the figure. Figure 1 and Figure 4 As shown, by analyzing the position, type, and area of the proton peak in the spectrum, it was determined that the structure of compound 4 is correct compared to that of HBPI1 prepared in Example 1.
[0135] High-resolution mass spectrometry analysis was performed on spirozanthine-fluorenyltetramine molecules (compound 4) using an Agilent Technologies G6224A liquid chromatography / time-of-flight mass spectrometer. Figure 2 As shown, the tetraamine molecule has the correct structure.
[0136] Infrared spectra of spiroxane-fluorenyltetramine (compound 4) and HBPI1 were obtained using a Fourier transform infrared spectrometer (FT-IR) (Nicolet iN10). Approximately 3 mg of sample, after thorough drying, was uniformly mixed with potassium bromide and pressed into transparent sheets. The wavenumber range for testing was 4000 cm⁻¹. -1 ~500cm -1 .like Figure 3 and Figure 5 As shown, the structures of compound 4 and HBPI1 prepared in Example 1 are confirmed to be correct.
[0137] Solubility test of HBPI1 prepared in Example 1
[0138] The HBPI1 prepared in Example 1 was mixed with different solvents at a mass fraction of 20% for HBPI1. The mixtures were then treated under the following conditions: shaking the solvent, sonication, heating, room temperature sonication, and sonication heating. The solubility of HBPI1 in different solvents was tested, and the specific data are shown in Table 1.
[0139] Table 1. Solubility of HBPI1 in different solvents
[0140]
[0141] 1): ++: Soluble at room temperature (minimum solids content >20wt%); +-: Soluble by ultrasound or heating; -: Slightly soluble at room temperature, by ultrasound, and by heating; --: Insoluble at room temperature, by ultrasound, and by heating. 2): NMP, N-methyl-2-pyrrolidone; DMSO: Dimethylsulfoxide; DMF, N,N-dimethylformamide; DMAc, N,N-dimethylacetamide;
[0142] Test Example 2
[0143] The polymers prepared in Examples 1-5 were used to prepare thin films for transparency testing.
[0144] Thin film preparation steps: At room temperature, hyperbranched polyimide was completely dissolved in DMAC (dimethylacetamide) to prepare a polymer solution with a solid content of 5%. The obtained polyimide solution was placed in a vacuum drying oven at room temperature and -0.1 MPa for 2.5 hours to eliminate air bubbles. The film was then coated on a clean substrate and dried sequentially at 40°C for 2 hours, 60°C for 2 hours, 80°C for 2 hours, 120°C for 2 hours, 150°C for 2 hours, and 180°C for 2 hours. The film was then allowed to cool naturally to room temperature and demolded to obtain a polyimide film with a thickness of 30 μm.
[0145] The transparency of the polyimide film was tested: A UV-Vis-NIR spectrophotometer (PerkinElmer, China, Lambda 1050+) was used to scan the prepared polymer film. The scanning wavelength range was 200–800 nm with a spacing of 5 nm, obtaining the UV-Vis spectrum curve of the polyimide film, and the transmittance data were recorded. For example... Figure 6 As shown in Table 2, the various polyimide films prepared by this invention all have high light transmittance.
[0146] Table 2. Key data on UV-Vis transmittance of the thin film.
[0147]
[0148]
[0149] 1)λ cut-off T is the cutoff wavelength of the incident light. λ＝400nm λ is the transmittance at an incident wavelength of 400 nm. T＝85％ The incident wavelength with 85% transmittance; T avg The average transmittance of the thin film in the range of 400-800 nm; T max This represents the maximum transmittance of the thin film.
[0150] The above-described embodiments are preferred embodiments of the present invention, but not exhaustive examples of all possible implementations of the present invention. For those skilled in the art, any modifications, equivalent substitutions, improvements, etc., made without departing from the spirit and substance of the present invention should be considered to be included within the protection scope of the present invention.
Claims
1. A spirozanol-fluorenyltetramine, characterized in that, Selected from the following structure: 。 2. The application of the spirozanol-fluorenyltetramine according to claim 1 in the preparation of hyperbranched polyimides.
3. A hyperbranched polyimide, characterized in that, It is obtained by polymerization of the spiroxanthine-fluorenyltetramine, organic diamine, and organic tetracarboxylic dianhydride as described in claim 1; The organic diamine is selected from at least one of aromatic diamines containing 1-10 benzene rings with or without substituents, and alicyclic diamines having 3-10 carbon atoms; The organic tetracarboxylic dianhydride is selected from at least one of the following: aromatic tetracarboxylic dianhydrides containing 1-10 benzene rings with or without substituents, aliphatic tetracarboxylic dianhydrides with 4-20 carbon atoms, and heterocyclic tetracarboxylic dianhydrides with 3-12 carbon atoms. Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect; The substituents are each independently selected from C1-C15 alkyl groups and C1-C15 fluoroalkyl groups.
4. A hyperbranched polyimide, characterized in that, It is obtained by polymerization of the spiroxanthine-fluorenyltetramine, organic diamine, and organic tetracarboxylic dianhydride as described in claim 1; The organic diamine is selected from at least one of aromatic diamines containing 1-10 benzene rings with or without substituents, and alicyclic diamines having 3-10 carbon atoms; The organic tetracarboxylic dianhydride is selected from at least one of aromatic tetracarboxylic dianhydrides containing 1-10 benzene rings with or without substituents, and alicyclic tetracarboxylic dianhydrides having 3-12 carbon atoms. Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect; The substituents are each independently selected from C1-C15 alkyl groups and C1-C15 fluoroalkyl groups.
5. The hyperbranched polyimide according to claim 3, characterized in that, It has the following structure: ； R1 is independently selected from arylene groups containing 1-10 benzene rings with or without substituents, and alicyclic groups with 3-10 carbon atoms. R2 is independently selected from the parent structures of aromatic tetracarboxylic dianhydrides containing 1-10 benzene rings with or without substituents, aliphatic tetracarboxylic dianhydrides with 5-20 carbon atoms, and heterocyclic tetracarboxylic dianhydrides with 3-12 carbon atoms. Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect; Each of the substituents is independently selected from C1-C15 alkyl groups and C1-C15 fluoroalkyl groups; n is an integer greater than 1.
6. A hyperbranched polyimide, characterized in that, The hyperbranched polyimide is obtained by polymerization of the spiroxanthine-fluorenyltetramine, organic diamine, and organic tetracarboxylic dianhydride as described in claim 1; the hyperbranched polyimide has the following structure: ； R1 is independently selected from arylene groups containing 1-10 benzene rings with or without substituents, and alicyclic groups with 3-10 carbon atoms. R2 is independently selected from the parent structure of aromatic tetracarboxylic dianhydrides containing 1-10 benzene rings with or without substituents, or alicyclic tetracarboxylic dianhydrides with 3-16 carbon atoms; Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect; Each of the substituents is independently selected from C1-C15 alkyl groups and C1-C15 fluoroalkyl groups; n is an integer greater than 1.
7. The hyperbranched polyimide according to claim 5, characterized in that, R1 is independently selected from arylene groups containing 1-6 benzene rings with or without substituents, or alicyclic groups with 3-10 carbon atoms; R2 is independently selected from the parent structures of aromatic tetracarboxylic dianhydrides containing 1-6 benzene rings with or without substituents, aliphatic tetracarboxylic dianhydrides with 5-15 carbon atoms, and heterocyclic tetracarboxylic dianhydrides with 3-10 carbon atoms. Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect; The substituents are each independently selected from C1-C10 alkyl groups and C1-C10 fluoroalkyl groups.
8. The hyperbranched polyimide according to claim 6, characterized in that, R1 is independently selected from arylene groups containing 1-6 benzene rings with or without substituents, or alicyclic groups with 3-10 carbon atoms; R2 is independently selected from the parent structure of alicyclic tetracarboxylic dianhydrides with 3-12 carbon atoms; Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect; The substituents are each independently selected from C1-C10 alkyl groups and C1-C10 fluoroalkyl groups.
9. The hyperbranched polyimide according to claim 6, characterized in that, R1 is independently selected from arylene groups containing 1-6 benzene rings with or without substituents, or alicyclic groups with 3-10 carbon atoms; R2 is independently selected from the parent structure of aromatic tetracarboxylic dianhydrides containing 1-6 benzene rings with or without substituents, or alicyclic tetracarboxylic dianhydrides with 3-12 carbon atoms; Adjacent benzene rings are connected by single bonds, methylene groups (with or without substituents), oxygen groups, carbonyl groups, etc. connect; The substituents are each independently selected from C1-C5 alkyl groups and C1-C5 fluoroalkyl groups.
10. The hyperbranched polyimide according to claim 6, characterized in that, R1 is selected independently from each of the following: , , , , , , , , , , ; R2 is selected independently from each of the following: , , , , , , , , , , , .
11. The hyperbranched polyimide according to any one of claims 5-10, characterized in that, n is an integer between 1 and 100.
12. The hyperbranched polyimide according to any one of claims 5-10, characterized in that, n is an integer between 1 and 50.
13. The hyperbranched polyimide according to any one of claims 5-10, characterized in that, n is an integer between 1 and 20.
14. The hyperbranched polyimide according to any one of claims 5-10, characterized in that, n is an integer between 1 and 5.
15. The method for preparing hyperbranched polyimide according to claim 5, characterized in that, The reaction steps and reaction formula are as follows: ； Spiroxane-fluorenyltetramine, and The hyperbranched polyimide was obtained by copolymerization in an organic solvent at 0-30°C. The definitions of R1 and R2 are the same as those in claim 5.
16. The method for preparing hyperbranched polyimide according to claim 6, characterized in that, The reaction steps and reaction formula are as follows: ； Spiroxane-fluorenyltetramine, and The hyperbranched polyimide was obtained by copolymerization in an organic solvent at 0-30°C. The definitions of R1 and R2 are the same as those in claim 6.