Preparation method of 2, 2 '-bis [4-(4-maleimide phenoxy) phenyl] propane
By using triquinolyl ionic liquids and triethylamine to adjust the reaction conditions, the problems of harsh reaction conditions and low yield in existing methods have been solved, and efficient and low-cost preparation of 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane has been achieved, which is suitable for large-scale industrial applications.
Patent Information
- Application Number
- CN202511407857.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-29
- Publication Date
- 2025-11-21
AI Technical Summary
Existing methods for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane suffer from problems such as harsh reaction conditions, low yield, and low product purity, which limit its large-scale industrial production and application.
Using triquinolyl ionic liquid as a co-solvent and triethylamine as an acid-binding agent, the solubility and collision frequency of the reactants were improved by adjusting the reaction conditions and intermolecular interactions. Combined with the acylation reaction of acetic anhydride, high-purity 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane was prepared.
It significantly improves reaction rate and yield, reduces costs, is suitable for large-scale industrial production, and produces products with high purity and yield.
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic compound synthesis technology, and in particular to a method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane. Background Technology
[0002] Polyimide is a class of high-molecular polymers with imide groups (-CO-N-CO-) embedded in its main chain. High-performance polyimide films, along with carbon fiber and aramid fiber, are recognized as one of the three core polymer material bottlenecks currently restricting the development of my country's high-tech industries.
[0003] Polyimide is hailed as one of the "most promising engineering plastics of the 21st century" due to its outstanding properties, including excellent electrical insulation, mechanical strength, chemical inertness, aging resistance, radiation resistance, low dielectric constant, low coefficient of thermal expansion, and excellent flame retardant properties. Particularly noteworthy is its ability to withstand temperatures exceeding 400°C, with a long-term operating temperature range spanning -269°C to 260°C, and some varieties even lacking a distinct melting point. Its radiation resistance is also exceptional, making it suitable for applications in aerospace environments. Furthermore, polyimide possesses outstanding dielectric properties, with a stable dielectric constant of approximately 3.4 and a dielectric strength ranging from 100-300 kV / mm.
[0004] Bismaleimide resins, as an important branch of thermosetting polyimides, have a wide range of applications. 2,2'-bis[4-(4-maleimide phenoxy)phenyl]propane is an important bismaleimide with extensive applications in aerospace, electronics, and other fields. Its excellent heat resistance, mechanical properties, and chemical stability make it a key raw material for the preparation of high-performance polyimide resins. However, existing preparation methods suffer from harsh reaction conditions, low yields, and low product purity, limiting its large-scale industrial production and application. Therefore, developing an efficient, environmentally friendly, and low-cost method for preparing 2,2'-bis[4-(4-maleimide phenoxy)phenyl]propane is of significant practical importance. Summary of the Invention
[0005] To address the above problems, this invention provides a method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, the steps of which are as follows: S1: Add 10-20 parts of bismaleamic acid intermediate to the reactor, then add 150-200 parts of toluene and start stirring; simultaneously add 5-15 parts of triquinolyl ionic liquid as a co-solvent, then add 20-80 parts of triethylamine as an acid-binding agent, and stir at 60-80℃ for 5-10 minutes to ensure the system is homogeneous; triethylamine can neutralize the acid produced during the reaction and promote the reaction. S2: Continue to add 20-100 parts of acetic anhydride, and observe the temperature change of the reaction system during the addition process; heat the reaction system to carry out the reaction, and monitor the reaction progress through thin-layer chromatography (TLC); among them, ionic liquids are miscible with toluene, which can significantly improve the solubility of reactants and the frequency of molecular collisions, thereby accelerating the reaction rate; S3: After the reaction is complete, add hot water to the reaction system and stir and wash it 2-3 times. The amount of water used each time is 1-2 times the volume of the reaction liquid. Stir for 10-15 minutes to fully remove impurities and residual triethylamine hydrochloride from the reaction system. S4: After washing with water, perform liquid-liquid separation to collect the organic phase; cool the organic phase to room temperature, at which point a large amount of solid will precipitate; collect the solid by vacuum filtration to obtain the crude product; S5: Add 10-20 parts of crude product to 50-200 parts of chloroform, heat to dissolve the crude product at a temperature of 45-55℃, and keep stirring during heating; after the crude product is completely dissolved, stop heating and allow the solution to cool naturally to room temperature; add another 50-200 parts of chloroform to the solution for recrystallization; after recrystallization, perform vacuum filtration, collect the solid, and dry the solid in a vacuum drying oven to obtain 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane; The triquinolyl ionic liquid cosolvent is prepared by reacting 1-allyl-3-methylimidazolium tetrafluoroborate, guanidine aminosulfonate, 2-amino-1,3,5-triazine, and sodium tert-butoxide.
[0006] As a preferred embodiment of the present invention, the reaction temperature of S2 is 60-80℃, the heating time is 20-30min, and the reaction time is 120-180min.
[0007] As a preferred embodiment of the present invention, the recrystallization temperature of S5 is 0-5°C and the time is 6-8 hours.
[0008] As a preferred embodiment of the present invention, the drying temperature of S5 is 60-80℃ and the drying time is 12-24h.
[0009] As a preferred embodiment of the present invention, the method for preparing the bismaleamic acid intermediate is as follows: H1: Add 10-20 parts of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to the reactor, followed by 50-60 parts of acetone. Turn on the stirring device to fully dissolve 2,2'-bis[4-(4-aminophenoxyphenyl)]propane in the acetone, while controlling the temperature of the reaction system at 0-5℃. H2: Add 20-60 parts of maleic anhydride to 80-100 parts of acetone to dissolve and prepare an acetone solution of maleic anhydride; slowly add the acetone solution of maleic anhydride to the reaction vessel while stirring continuously during the addition process, and continue stirring for 20-30 minutes after the addition is completed. H3: After stirring, heat the reaction system and stir to react; after the reaction is complete, filter the reaction solution to separate the filtrate and filter cake. H4: Transfer the filtrate to a rotary evaporator for rotary evaporation to recover the acetone solvent; the recovered acetone can be reused in subsequent reactions to reduce production costs and solvent waste; H5: The filter cake is pulped with the recovered acetone to fully disperse it in the acetone; after pulping, it is filtered again and the filter cake is dried to obtain the bismaleamic acid intermediate.
[0010] As a preferred embodiment of the present invention, the reaction temperature of H3 is 25-35°C and the reaction time is 3-4 hours.
[0011] As a preferred embodiment of the present invention, the pulping time of H5 is 60-120 min.
[0012] As a preferred embodiment of the present invention, the method for preparing the triquinolyl ionic liquid co-solvent is as follows: A1: Add 21-42 parts of 1-allyl-3-methylimidazolium tetrafluoroborate, 10-20 parts of guanidine aminosulfonate, and 0.2-0.5 parts of 2-amino-1,3,5-triazine to 200-280 parts of DMF, and stir at 100-150 r / min to fully mix the raw materials and form a homogeneous solution. A2: Slowly add 2-5 parts of sodium tert-butoxide to the above homogeneous solution while stirring. Then, stir the mixture at a constant temperature of 60-80℃ for 4-6 hours. Remove DMF by vacuum distillation to obtain a triquinolyl ionic liquid cosolvent.
[0013] Reaction mechanism: During the reaction, the bismaleamic acid intermediate neutralizes the acid generated in the reaction under the action of triethylamine as an acid-binding agent, maintaining the acid-base balance of the reaction system and creating suitable conditions for the reaction. The mechanism of action of the triquinolyl ionic liquid as a co-solvent is more complex and crucial. From a molecular structure perspective, triquinolyl ionic liquids possess unique cation and anion structures. The triquinolyl structure of the cation moiety has a large conjugated system, which enables strong π-π interactions between it and reactant molecules; the anion moiety, on the other hand, attracts polar groups in the reactant molecules through electrostatic interactions. This multi-layered intermolecular interaction significantly enhances the solubility of reactants in toluene-triquinolyl ionic liquid mixtures. Once the reactant molecules are fully dissolved, the microenvironment formed by the triquinolyl ionic liquid effectively reduces the diffusion resistance between reactant molecules. The ionic atmosphere of the ionic liquid acts like a "molecular conveyor belt," guiding reactant molecules to move more orderly and increasing the effective collision frequency between molecules. Simultaneously, the presence of the triquinolyl ionic liquid stabilizes the transition states generated during the reaction, lowers the activation energy, and allows the reaction to proceed rapidly under relatively mild conditions. With the addition of acetic anhydride, the acetic anhydride acts as an acylation reagent, undergoing a more efficient acylation reaction with the bismaleamic acid intermediate in the optimized reaction environment, ultimately generating the target product 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane. Furthermore, the presence of the triquinolyl ionic liquid positively influences the selectivity of the reaction; its unique molecular environment suppresses side reactions, further improving the yield and purity of the target product.
[0014] Technical effects: The present invention provides a method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane. Compared with the prior art, the present invention has the following significant advantages: 1. This invention uses triquinolyl ionic liquid as a co-solvent. Through its unique molecular structure and mechanism of action, it significantly improves the solubility of reactants and the frequency of molecular collisions, accelerates the reaction rate, and shortens the reaction time. 2. The present invention uses triethylamine as an acid-binding agent, which can neutralize the acid generated during the reaction, promote the reaction, and improve the reaction yield. 3. The co-solvent preparation method of the present invention is simple, the raw materials are readily available, the cost is low, and it is suitable for large-scale production.
[0015] 4. The 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane prepared by this invention has high purity and yield, good economic benefits, and is suitable for large-scale industrial production. Detailed Implementation
[0016] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the following detailed description is provided in conjunction with embodiments and comparative examples: Purity test of 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane: Detection was performed by high performance liquid chromatography (HPLC).
[0017] Example 1 A method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, comprising the following steps: S1: Add 10g of bismaleamic acid intermediate to the reaction vessel, then add 150g of toluene and start stirring; at the same time, add 5g of triquinolyl ionic liquid as a co-solvent, then add 20g of acid-binding agent triethylamine, and stir at 60℃ for 5 minutes to make the system uniformly mixed; triethylamine can neutralize the acid produced during the reaction and promote the reaction. S2: Continue adding 20g of acetic anhydride, and observe the temperature change of the reaction system during the addition process; heat the reaction system to carry out the reaction, and monitor the reaction progress through thin-layer chromatography (TLC); among them, ionic liquids are miscible with toluene, which can significantly improve the solubility of reactants and the frequency of molecular collisions, thereby accelerating the reaction rate; S3: After the reaction is complete, add hot water to the reaction system and stir and wash it twice. The amount of water used each time is 1 times the volume of the reaction liquid. Stir for 10 minutes to fully remove impurities and residual triethylamine hydrochloride from the reaction system. S4: After washing with water, perform liquid-liquid separation to collect the organic phase; cool the organic phase to room temperature, at which point a large amount of solid will precipitate; collect the solid by vacuum filtration to obtain the crude product; S5: Add 10g of crude product to 50g of chloroform and heat to dissolve the crude product at 45℃, stirring continuously during heating; after the crude product is completely dissolved, stop heating and allow the solution to cool naturally to room temperature; add another 50g of chloroform to the solution and recrystallize; after recrystallization, perform vacuum filtration, collect the solid, and dry the solid in a vacuum drying oven to obtain 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane.
[0018] The reaction temperature of S2 is 60℃, the heating time is 20min, and the reaction time is 120min.
[0019] The recrystallization temperature of S5 is 0°C, and the time is 6 hours.
[0020] The drying temperature of S5 is 60°C, and the drying time is 12 hours.
[0021] The method for preparing the bismaleamic acid intermediate is as follows: H1: Add 10g of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to the reactor, followed by 50g of acetone. Turn on the stirring device to fully dissolve the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane in the acetone, while controlling the temperature of the reaction system at 0℃. H2: Add 20g of maleic anhydride to 80g of acetone to dissolve and prepare an acetone solution of maleic anhydride; slowly add the acetone solution of maleic anhydride to the reaction vessel while stirring continuously during the addition process, and continue stirring for 20 minutes after the addition is completed; H3: After stirring, heat the reaction system and stir to react; after the reaction is complete, filter the reaction solution to separate the filtrate and filter cake. H4: Transfer the filtrate to a rotary evaporator for rotary evaporation to recover the acetone solvent; the recovered acetone can be reused in subsequent reactions to reduce production costs and solvent waste; H5: The filter cake is pulped with the recovered acetone to fully disperse it in the acetone; after pulping, it is filtered again and the filter cake is dried to obtain the bismaleamic acid intermediate.
[0022] The reaction temperature of H3 is 25°C and the reaction time is 3 hours.
[0023] The pulping time for H5 is 60 minutes.
[0024] The preparation method of the triquinolyl ionic liquid co-solvent is as follows: A1: Add 21g of 1-allyl-3-methylimidazolium tetrafluoroborate, 10g of guanidine aminosulfonate, and 0.2g of 2-amino-1,3,5-triazine to 200g of DMF and stir at 100r / min to ensure the raw materials are fully mixed and form a homogeneous solution. A2: Slowly add 2g of sodium tert-butoxide to the above homogeneous solution while stirring. Then, stir and react at a constant temperature of 60°C for 4 hours. Remove DMF by vacuum distillation to obtain a triquinolyl ionic liquid cosolvent.
[0025] Example 2 A method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, comprising the following steps: S1: Add 13g of bismaleamic acid intermediate to the reactor, then add 160g of toluene and start stirring; at the same time, add 8g of triquinolyl ionic liquid as a co-solvent, then add 40g of triethylamine as an acid-binding agent, and stir at 65°C for 6 minutes to make the system uniformly mixed; triethylamine can neutralize the acid produced during the reaction and promote the reaction. S2: Continue adding 40g of acetic anhydride, and observe the temperature change of the reaction system during the addition process; heat the reaction system to carry out the reaction, and monitor the reaction progress through thin-layer chromatography (TLC); among them, ionic liquids are miscible with toluene, which can significantly improve the solubility of reactants and the frequency of molecular collisions, thereby accelerating the reaction rate; S3: After the reaction is complete, add hot water to the reaction system and stir and wash it twice. The amount of water used each time is 1 times the volume of the reaction liquid. The stirring time is 12 minutes to fully remove impurities and residual triethylamine hydrochloride from the reaction system. S4: After washing with water, perform liquid-liquid separation to collect the organic phase; cool the organic phase to room temperature, at which point a large amount of solid will precipitate; collect the solid by vacuum filtration to obtain the crude product; S5: Add 13g of crude product to 100g of chloroform and heat to dissolve the crude product at 50℃, stirring continuously during heating; after the crude product is completely dissolved, stop heating and allow the solution to cool naturally to room temperature; add another 100g of chloroform to the solution and recrystallize; after recrystallization, perform vacuum filtration, collect the solid, and dry the solid in a vacuum drying oven to obtain 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane.
[0026] The reaction temperature of S2 is 65℃, the heating time is 25min, and the reaction time is 140min.
[0027] The recrystallization temperature of S5 is 0℃, and the time is 7 hours.
[0028] The drying temperature of S5 is 65°C, and the drying time is 16 hours.
[0029] The method for preparing the bismaleamic acid intermediate is as follows: H1: Add 13g of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to the reactor, followed by 55g of acetone. Turn on the stirring device to fully dissolve the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane in the acetone, while controlling the temperature of the reaction system at 0℃. H2: Add 30g of maleic anhydride to 85g of acetone to dissolve and prepare an acetone solution of maleic anhydride; slowly add the acetone solution of maleic anhydride to the reaction vessel while stirring continuously during the addition process, and continue stirring for 25 minutes after the addition is completed; H3: After stirring, heat the reaction system and stir to react; after the reaction is complete, filter the reaction solution to separate the filtrate and filter cake. H4: Transfer the filtrate to a rotary evaporator for rotary evaporation to recover the acetone solvent; the recovered acetone can be reused in subsequent reactions to reduce production costs and solvent waste; H5: The filter cake is pulped with the recovered acetone to fully disperse it in the acetone; after pulping, it is filtered again and the filter cake is dried to obtain the bismaleamic acid intermediate.
[0030] The reaction temperature of H3 is 30°C and the reaction time is 3.5 hours.
[0031] The pulping time for H5 is 80 minutes.
[0032] The preparation method of the triquinolyl ionic liquid co-solvent is as follows: A1: Add 27g of 1-allyl-3-methylimidazolium tetrafluoroborate, 13g of guanidine aminosulfonate, and 0.3g of 2-amino-1,3,5-triazine to 220g of DMF and stir at 110r / min to ensure the raw materials are fully mixed and form a homogeneous solution. A2: Slowly add 3g of sodium tert-butoxide to the above homogeneous solution while stirring. Then, stir and react at a constant temperature of 65°C for 5 hours. Remove DMF by vacuum distillation to obtain a triquinolyl ionic liquid cosolvent.
[0033] Example 3 A method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, comprising the following steps: S1: Add 18g of bismaleamic acid intermediate to the reaction vessel, then add 180g of toluene and start stirring; at the same time, add 13g of triquinolyl ionic liquid as a co-solvent, then add 60g of triethylamine as an acid-binding agent, and stir at 75°C for 8 minutes to make the system uniformly mixed; triethylamine can neutralize the acid produced during the reaction and promote the reaction. S2: Continue adding 80g of acetic anhydride, and observe the temperature change of the reaction system during the addition process; heat the reaction system to carry out the reaction, and monitor the reaction progress through thin-layer chromatography (TLC); among them, ionic liquids are miscible with toluene, which can significantly improve the solubility of reactants and the frequency of molecular collisions, thereby accelerating the reaction rate; S3: After the reaction is complete, add hot water to the reaction system and stir and wash it. Wash it 3 times, and use twice the volume of water for each wash. Stir for 14 minutes to fully remove impurities and residual triethylamine hydrochloride from the reaction system. S4: After washing with water, perform liquid-liquid separation to collect the organic phase; cool the organic phase to room temperature, at which point a large amount of solid will precipitate; collect the solid by vacuum filtration to obtain the crude product; S5: Add 18g of crude product to 150g of chloroform and heat to dissolve the crude product at 50℃, stirring continuously during heating; after the crude product is completely dissolved, stop heating and allow the solution to cool naturally to room temperature; add another 150g of chloroform to the solution and recrystallize; after recrystallization, perform vacuum filtration, collect the solid, and dry the solid in a vacuum drying oven to obtain 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane.
[0034] The reaction temperature of S2 is 75℃, the heating time is 25min, and the reaction time is 160min.
[0035] The recrystallization temperature of S5 is 5°C, and the time is 7 hours.
[0036] The drying temperature of S5 is 75°C, and the drying time is 20 hours.
[0037] The method for preparing the bismaleamic acid intermediate is as follows: H1: Add 18g of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to the reactor, followed by 55g of acetone. Turn on the stirring device to fully dissolve the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane in the acetone, while controlling the temperature of the reaction system at 5℃. H2: Add 50g of maleic anhydride to 95g of acetone to dissolve and prepare an acetone solution of maleic anhydride; slowly add the acetone solution of maleic anhydride to the reaction vessel while stirring continuously during the addition process, and continue stirring for 25 minutes after the addition is completed; H3: After stirring, heat the reaction system and stir to react; after the reaction is complete, filter the reaction solution to separate the filtrate and filter cake. H4: Transfer the filtrate to a rotary evaporator for rotary evaporation to recover the acetone solvent; the recovered acetone can be reused in subsequent reactions to reduce production costs and solvent waste; H5: The filter cake is pulped with the recovered acetone to fully disperse it in the acetone; after pulping, it is filtered again and the filter cake is dried to obtain the bismaleamic acid intermediate.
[0038] The reaction temperature of H3 is 30°C and the reaction time is 3.5 hours.
[0039] The pulping time for H5 is 100 minutes.
[0040] The preparation method of the triquinolyl ionic liquid co-solvent is as follows: A1: Add 35g of 1-allyl-3-methylimidazolium tetrafluoroborate, 18g of guanidine aminosulfonate, and 0.4g of 2-amino-1,3,5-triazine to 260g of DMF and stir at 140r / min to fully mix the raw materials and form a homogeneous solution. A2: Slowly add 4g of sodium tert-butoxide to the above homogeneous solution while stirring. Then, stir and react at a constant temperature of 75°C for 5 hours. Remove DMF by vacuum distillation to obtain a triquinolyl ionic liquid cosolvent.
[0041] Example 4
[0042] A method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, comprising the following steps: S1: Add 20g of bismaleamic acid intermediate to the reaction vessel, then add 200g of toluene and start stirring; at the same time, add 15g of triquinolyl ionic liquid as a co-solvent, then add 80g of acid-binding agent triethylamine, and stir at 80℃ for 10 minutes to make the system uniformly mixed; triethylamine can neutralize the acid produced during the reaction and promote the reaction. S2: Continue adding 100g of acetic anhydride, and observe the temperature change of the reaction system during the addition process; heat the reaction system to carry out the reaction, and monitor the reaction progress through thin-layer chromatography (TLC); among them, ionic liquids are miscible with toluene, which can significantly improve the solubility of reactants and the frequency of molecular collisions, thereby accelerating the reaction rate; S3: After the reaction is complete, add hot water to the reaction system and stir and wash it. Wash it 3 times, and use twice the volume of water for each wash. Stir for 15 minutes to fully remove impurities and residual triethylamine hydrochloride from the reaction system. S4: After washing with water, perform liquid-liquid separation to collect the organic phase; cool the organic phase to room temperature, at which point a large amount of solid will precipitate; collect the solid by vacuum filtration to obtain the crude product; S5: Add 20g of crude product to 200g of chloroform and heat to dissolve the crude product at 55℃, stirring continuously during heating; after the crude product is completely dissolved, stop heating and allow the solution to cool naturally to room temperature; add another 200g of chloroform to the solution and recrystallize; after recrystallization, perform vacuum filtration, collect the solid, and dry the solid in a vacuum drying oven to obtain 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane.
[0043] The reaction temperature of S2 is 80℃, the heating time is 30min, and the reaction time is 180min.
[0044] The recrystallization temperature of S5 is 5°C, and the time is 8 hours.
[0045] The drying temperature of S5 is 80℃, and the drying time is 24 hours.
[0046] The method for preparing the bismaleamic acid intermediate is as follows: H1: Add 20g of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to the reactor, followed by 60g of acetone. Turn on the stirring device to fully dissolve the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane in the acetone, while controlling the temperature of the reaction system at 5℃. H2: Add 60g of maleic anhydride to 100g of acetone to dissolve and prepare an acetone solution of maleic anhydride; slowly add the acetone solution of maleic anhydride to the reaction vessel while stirring continuously during the addition process, and continue stirring for 30 minutes after the addition is completed; H3: After stirring, heat the reaction system and stir to react; after the reaction is complete, filter the reaction solution to separate the filtrate and filter cake. H4: Transfer the filtrate to a rotary evaporator for rotary evaporation to recover the acetone solvent; the recovered acetone can be reused in subsequent reactions to reduce production costs and solvent waste; H5: The filter cake is pulped with the recovered acetone to fully disperse it in the acetone; after pulping, it is filtered again and the filter cake is dried to obtain the bismaleamic acid intermediate.
[0047] The reaction temperature of H3 is 35°C and the reaction time is 4 hours.
[0048] The pulping time for H5 is 120 minutes.
[0049] The preparation method of the triquinolyl ionic liquid co-solvent is as follows: A1: Add 42g of 1-allyl-3-methylimidazolium tetrafluoroborate, 20g of guanidine aminosulfonate, and 0.5g of 2-amino-1,3,5-triazine to 280g of DMF and stir at 150r / min to fully mix the raw materials and form a homogeneous solution. A2: Slowly add 5g of sodium tert-butoxide to the above homogeneous solution while stirring. Then, stir and react at a constant temperature of 80°C for 6 hours. Remove DMF by vacuum distillation to obtain a triquinolyl ionic liquid cosolvent.
[0050] Comparative Example 1 A method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, comprising the following steps: S1: Add 10g of bismaleamic acid intermediate to the reaction vessel, then add 150g of toluene and start stirring; add 20g of triethylamine as an acid-binding agent and stir at 60℃ for 5 minutes to make the system uniformly mixed; triethylamine can neutralize the acid produced during the reaction and promote the reaction. S2: Continue adding 20g of acetic anhydride, and observe the temperature change of the reaction system during the addition process; heat the reaction system to carry out the reaction, and monitor the reaction progress through thin-layer chromatography (TLC); among them, ionic liquids are miscible with toluene, which can significantly improve the solubility of reactants and the frequency of molecular collisions, thereby accelerating the reaction rate; S3: After the reaction is complete, add hot water to the reaction system and stir and wash it twice. The amount of water used each time is 1 times the volume of the reaction liquid. Stir for 10 minutes to fully remove impurities and residual triethylamine hydrochloride from the reaction system. S4: After washing with water, perform liquid-liquid separation to collect the organic phase; cool the organic phase to room temperature, at which point a large amount of solid will precipitate; collect the solid by vacuum filtration to obtain the crude product; S5: Add 10g of crude product to 50g of chloroform and heat to dissolve the crude product at 45℃, stirring continuously during heating; after the crude product is completely dissolved, stop heating and allow the solution to cool naturally to room temperature; add another 50g of chloroform to the solution and recrystallize; after recrystallization, perform vacuum filtration, collect the solid, and dry the solid in a vacuum drying oven to obtain 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane.
[0051] The reaction temperature of S2 is 60℃, the heating time is 20min, and the reaction time is 120min.
[0052] The recrystallization temperature of S5 is 0°C, and the time is 6 hours.
[0053] The drying temperature of S5 is 60°C, and the drying time is 12 hours.
[0054] The method for preparing the bismaleamic acid intermediate is as follows: H1: Add 10g of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to the reactor, followed by 50g of acetone. Turn on the stirring device to fully dissolve the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane in the acetone, while controlling the temperature of the reaction system at 0℃. H2: Add 20g of maleic anhydride to 80g of acetone to dissolve and prepare an acetone solution of maleic anhydride; slowly add the acetone solution of maleic anhydride to the reaction vessel while stirring continuously during the addition process, and continue stirring for 20 minutes after the addition is completed; H3: After stirring, heat the reaction system and stir to react; after the reaction is complete, filter the reaction solution to separate the filtrate and filter cake. H4: Transfer the filtrate to a rotary evaporator for rotary evaporation to recover the acetone solvent; the recovered acetone can be reused in subsequent reactions to reduce production costs and solvent waste; H5: The filter cake is pulped with the recovered acetone to fully disperse it in the acetone; after pulping, it is filtered again and the filter cake is dried to obtain the bismaleamic acid intermediate.
[0055] The reaction temperature of H3 is 25°C and the reaction time is 3 hours.
[0056] The pulping time for H5 is 60 minutes.
[0057] Comparative Example 2 A method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, comprising the following steps: S1: Add 10g of bismaleamic acid intermediate to the reaction vessel, then add 150g of toluene and start stirring; at the same time, add 5g of triquinolyl ionic liquid as a co-solvent, then add 20g of acid-binding agent triethylamine, and stir at 60℃ for 5 minutes to make the system uniformly mixed; triethylamine can neutralize the acid produced during the reaction and promote the reaction. S2: Continue adding 20g of acetic anhydride, and observe the temperature change of the reaction system during the addition process; heat the reaction system to carry out the reaction, and monitor the reaction progress through thin-layer chromatography (TLC); among them, ionic liquids are miscible with toluene, which can significantly improve the solubility of reactants and the frequency of molecular collisions, thereby accelerating the reaction rate; S3: After the reaction is complete, add hot water to the reaction system and stir and wash it twice. The amount of water used each time is 1 times the volume of the reaction liquid. Stir for 10 minutes to fully remove impurities and residual triethylamine hydrochloride from the reaction system. S4: After washing with water, perform liquid-liquid separation to collect the organic phase; cool the organic phase to room temperature, at which point a large amount of solid will precipitate; collect the solid by vacuum filtration to obtain the crude product; S5: Add 10g of crude product to 50g of chloroform and heat to dissolve the crude product at 45℃, stirring continuously during heating; after the crude product is completely dissolved, stop heating and allow the solution to cool naturally to room temperature; add another 50g of chloroform to the solution and recrystallize; after recrystallization, perform vacuum filtration, collect the solid, and dry the solid in a vacuum drying oven to obtain 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane.
[0058] The reaction temperature of S2 is 60℃, the heating time is 20min, and the reaction time is 120min.
[0059] The recrystallization temperature of S5 is 0°C, and the time is 6 hours.
[0060] The drying temperature of S5 is 60°C, and the drying time is 12 hours.
[0061] The method for preparing the bismaleamic acid intermediate is as follows: H1: Add 10g of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to the reactor, followed by 50g of acetone. Turn on the stirring device to fully dissolve the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane in the acetone, while controlling the temperature of the reaction system at 0℃. H2: Add 20g of maleic anhydride to 80g of acetone to dissolve and prepare an acetone solution of maleic anhydride; slowly add the acetone solution of maleic anhydride to the reaction vessel while stirring continuously during the addition process, and continue stirring for 20 minutes after the addition is completed; H3: After stirring, heat the reaction system and stir to react; after the reaction is complete, filter the reaction solution to separate the filtrate and filter cake. H4: Transfer the filtrate to a rotary evaporator for rotary evaporation to recover the acetone solvent; the recovered acetone can be reused in subsequent reactions to reduce production costs and solvent waste; H5: The filter cake is pulped with the recovered acetone to fully disperse it in the acetone; after pulping, it is filtered again and the filter cake is dried to obtain the bismaleamic acid intermediate.
[0062] The reaction temperature of H3 is 25°C and the reaction time is 3 hours.
[0063] The pulping time for H5 is 60 minutes.
[0064] The preparation method of the triquinolyl ionic liquid co-solvent is as follows: A1: Add 21g of 1-allyl-3-methylimidazolium tetrafluoroborate and 0.2g of 2-amino-1,3,5-triazine to 200g of DMF and stir at 100r / min to fully mix the raw materials and form a homogeneous solution. A2: Slowly add 2g of sodium tert-butoxide to the above homogeneous solution while stirring. Then, stir and react at a constant temperature of 60°C for 4 hours. Remove DMF by vacuum distillation to obtain a triquinolyl ionic liquid cosolvent.
[0065] Comparative Example 3 A method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, comprising the following steps: S1: Add 10g of bismaleamic acid intermediate to the reaction vessel, then add 150g of toluene and start stirring; at the same time, add 5g of triquinolyl ionic liquid as a co-solvent, then add 20g of acid-binding agent triethylamine, and stir at 60℃ for 5 minutes to make the system uniformly mixed; triethylamine can neutralize the acid produced during the reaction and promote the reaction. S2: Continue adding 20g of acetic anhydride, and observe the temperature change of the reaction system during the addition process; heat the reaction system to carry out the reaction, and monitor the reaction progress through thin-layer chromatography (TLC); among them, ionic liquids are miscible with toluene, which can significantly improve the solubility of reactants and the frequency of molecular collisions, thereby accelerating the reaction rate; S3: After the reaction is complete, add hot water to the reaction system and stir and wash it twice. The amount of water used each time is 1 times the volume of the reaction liquid. Stir for 10 minutes to fully remove impurities and residual triethylamine hydrochloride from the reaction system. S4: After washing with water, perform liquid-liquid separation to collect the organic phase; cool the organic phase to room temperature, at which point a large amount of solid will precipitate; collect the solid by vacuum filtration to obtain the crude product; S5: Add 10g of crude product to 50g of chloroform and heat to dissolve the crude product at 45℃, stirring continuously during heating; after the crude product is completely dissolved, stop heating and allow the solution to cool naturally to room temperature; add another 50g of chloroform to the solution and recrystallize; after recrystallization, perform vacuum filtration, collect the solid, and dry the solid in a vacuum drying oven to obtain 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane.
[0066] The reaction temperature of S2 is 60℃, the heating time is 20min, and the reaction time is 120min.
[0067] The recrystallization temperature of S5 is 0°C, and the time is 6 hours.
[0068] The drying temperature of S5 is 60°C, and the drying time is 12 hours.
[0069] The method for preparing the bismaleamic acid intermediate is as follows: H1: Add 10g of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to the reactor, followed by 50g of acetone. Turn on the stirring device to fully dissolve the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane in the acetone, while controlling the temperature of the reaction system at 0℃. H2: Add 20g of maleic anhydride to 80g of acetone to dissolve and prepare an acetone solution of maleic anhydride; slowly add the acetone solution of maleic anhydride to the reaction vessel while stirring continuously during the addition process, and continue stirring for 20 minutes after the addition is completed; H3: After stirring, heat the reaction system and stir to react; after the reaction is complete, filter the reaction solution to separate the filtrate and filter cake. H4: Transfer the filtrate to a rotary evaporator for rotary evaporation to recover the acetone solvent; the recovered acetone can be reused in subsequent reactions to reduce production costs and solvent waste; H5: The filter cake is pulped with the recovered acetone to fully disperse it in the acetone; after pulping, it is filtered again and the filter cake is dried to obtain the bismaleamic acid intermediate.
[0070] The reaction temperature of H3 is 25°C and the reaction time is 3 hours.
[0071] The pulping time for H5 is 60 minutes.
[0072] The preparation method of the triquinolyl ionic liquid co-solvent is as follows: A1: Add 21g of 1-allyl-3-methylimidazolium tetrafluoroborate and 10g of guanidine aminosulfonate to 200g of DMF and stir at 100r / min to fully mix the raw materials and form a homogeneous solution. A2: Slowly add 2g of sodium tert-butoxide to the above homogeneous solution while stirring. Then, stir and react at a constant temperature of 60°C for 4 hours. Remove DMF by vacuum distillation to obtain a triquinolyl ionic liquid cosolvent.
[0073] Table 1: Detection data of the examples and comparative examples purity / % Yield / % Example 1 98.3 84.9 Example 2 98.5 85.3 Example 3 98.9 86.0 Example 4 99.1 86.3 Comparative Example 1 75.4 63.2 Comparative Example 2 91.5 78.3 Comparative Example 3 92.8 79.1 Based on the data analysis of the above examples and comparative examples, the 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane prepared by the present invention has high purity and yield, good economic benefits, and is suitable for large-scale industrial production.
[0074] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.
Claims
1. A method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, comprising the following steps: S1: Add 10-20 parts of bismaleamic acid intermediate to the reactor, then add 150-200 parts of toluene and start stirring; at the same time, add 5-15 parts of triquinolyl ionic liquid as a co-solvent, then add 20-80 parts of acid-binding agent triethylamine, and stir at 60-80℃ for 5-10 minutes to make the system uniformly mixed. S2: Continue to add 20-100 parts of acetic anhydride, and observe the temperature change of the reaction system during the addition process; heat the reaction system to carry out the reaction, and monitor the reaction progress through thin-layer chromatography (TLC); S3: After the reaction is complete, add hot water to the reaction system and stir and wash it. Wash it 2-3 times. The amount of water used each time is 1-2 times the volume of the reaction liquid. Stir for 10-15 minutes. S4: After washing with water, perform liquid-liquid separation to collect the organic phase; cool the organic phase to room temperature, at which point a large amount of solid will precipitate; collect the solid by vacuum filtration to obtain the crude product; S5: Add 10-20 parts of crude product to 50-200 parts of chloroform, heat to dissolve the crude product at a temperature of 45-55℃, and keep stirring during heating; after the crude product is completely dissolved, stop heating and allow the solution to cool naturally to room temperature; add another 50-200 parts of chloroform to the solution for recrystallization; after recrystallization, perform vacuum filtration, collect the solid, and dry the solid in a vacuum drying oven to obtain 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane; The triquinolyl ionic liquid cosolvent is prepared by reacting 1-allyl-3-methylimidazolium tetrafluoroborate, guanidine aminosulfonate, 2-amino-1,3,5-triazine, and sodium tert-butoxide.
2. The method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane according to claim 1, characterized in that: The reaction temperature of S2 is 60-80℃, the heating time is 20-30 min, and the reaction time is 120-180 min.
3. The method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane according to claim 1, characterized in that: The recrystallization temperature of S5 is 0-5℃, and the time is 6-8 hours.
4. The method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane according to claim 1, characterized in that: The drying temperature of S5 is 60-80℃, and the drying time is 12-24h.
5. The method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane according to claim 1, characterized in that: The preparation method of the bismaleamic acid intermediate is as follows: H1: Add 10-20 parts of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane to the reactor, followed by 50-60 parts of acetone. Turn on the stirring device to fully dissolve 2,2'-bis[4-(4-aminophenoxyphenyl)]propane in the acetone, while controlling the temperature of the reaction system at 0-5℃. H2: Add 20-60 parts of maleic anhydride to 80-100 parts of acetone to dissolve and prepare an acetone solution of maleic anhydride; slowly add the acetone solution of maleic anhydride to the reaction vessel while stirring continuously during the addition process, and continue stirring for 20-30 minutes after the addition is completed. H3: After stirring, heat the reaction system and stir to react; after the reaction is complete, filter the reaction solution to separate the filtrate and filter cake. H4: Transfer the filtrate to a rotary evaporator for rotary evaporation to recover the acetone solvent; the recovered acetone can be reused in subsequent reactions to reduce production costs and solvent waste; H5: The filter cake is pulped with the recovered acetone to fully disperse it in the acetone; after pulping, it is filtered again and the filter cake is dried to obtain the bismaleamic acid intermediate.
6. The method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane according to claim 5, characterized in that: The reaction temperature of H3 is 25-35℃, and the reaction time is 3-4 hours.
7. The method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane according to claim 5, characterized in that: The pulping time for H5 is 60-120 minutes.
8. The method for preparing 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane according to claim 1, characterized in that: The preparation method of the triquinolyl ionic liquid co-solvent is as follows: A1: Add 21-42 parts of 1-allyl-3-methylimidazolium tetrafluoroborate, 10-20 parts of guanidine aminosulfonate, and 0.2-0.5 parts of 2-amino-1,3,5-triazine to 200-280 parts of DMF, and stir at 100-150 r / min to fully mix the raw materials and form a homogeneous solution. A2: Slowly add 2-5 parts of sodium tert-butoxide to the above homogeneous solution while stirring. Then, stir the mixture at a constant temperature of 60-80℃ for 4-6 hours. Remove DMF by vacuum distillation to obtain a triquinolyl ionic liquid cosolvent.