CN114805333A - Bismaleimide with main chain containing oxazine and Cardo structures and preparation method thereof - Google Patents
Bismaleimide with main chain containing oxazine and Cardo structures and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of bismaleimide with a main chain containing oxazine and Cardo structures, belonging to the technical field of high-performance thermosetting resin. The molecular structural formula of the bismaleimide monomer is as follows:
wherein R is
Any one of them; r 1 Is any one of the following structures:
R 2 is as followsAny one of the structures:
the invention introduces a non-coplanar Cardo structure into the main chain to prevent molecular chains from being densely packed and reduce intermolecular force, thereby improving the solubility of the molecules. The introduced oxazine can undergo ring-opening polymerization under heating conditions without small molecule release, and the crosslinking density of a cured product is further increased, so that the heat resistance is improved. The introduced benzoxazine also has excellent performances of flame retardance, dielectric property, corrosion resistance and the like. The bismaleimide prepared by the method can be used alone or mixed with other resins, and the obtained cured product has higher heat resistance, flame retardance, dielectricity and corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of high-performance thermosetting resin, and relates to bismaleimide with a main chain containing oxazine and Cardo structures and a preparation method thereof.
Background
Bismaleimide (BMI) resin is an important thermosetting polyimide and has good thermal property, mechanical property, electrical insulation, wave permeability, flame retardance and dimensional stability. BMI has strong molecular design flexibility and can also react with other monomers to carry out modification. Therefore, the method has wide application in the fields of aerospace, mechano-electronics, transportation and the like. The bismaleimide resin integrates excellent properties of various resins, but the traditional bismaleimide also has the defects of high melting point, poor solubility, poor toughness and the like, and the defects seriously restrict the application of the bismaleimide resin in some fields. At present, the approaches for solving the defects are to design a new structure from the molecular design and introduce inorganic elements, aromatic ether bonds, twisted or non-coplanar structures and the like.
Benzoxazines are novel resins developed on the basis of conventional phenolic resins. The benzoxazine resin not only has the high temperature resistance, flame retardance and good dielectric property and mechanical property of the traditional phenolic resin, but also has the advantages of high carbon residue rate, high glass transition temperature, good dimensional stability, no need of a catalyst in the curing process, no release of small molecules, low water absorption, strong molecular design property and the like. Therefore, benzoxazine is often used in modification studies of other resins, for example, chinese patent application discloses a bis-benzoxazine monomer containing ortho-maleimide group and its preparation method (CN 106366079a), and an oxazine ring is introduced to a bis-maleimide backbone, which has excellent properties. There are no other reports to introduce an oxazine ring into a bismaleimide molecule to date, and no more reports are made of introducing an oxazine ring and a Cardo structure together onto a bismaleimide backbone. The inventor designs a bismaleimide group monomer with low melting point, excellent solubility and excellent thermal stability based on abundant experience of synthesizing thermosetting resin monomers, and finally creates a bismaleimide with a main chain containing oxazine and Cardo structures and a preparation method thereof through repeated design and experiments. The invention is found to be a practical invention through various performance characterizations.
The invention content is as follows:
the invention mainly aims to solve the defects of the existing bismaleimide monomer, and provides a novel bismaleimide monomer with a main chain containing oxazine and Cardo structures and a preparation method thereof, which can reduce the symmetry and internal rotation energy of a molecular chain and prevent the molecular chain from being tightly stacked, further reduce intermolecular force to reduce a melting point, and improve the solubility and the processability, thereby having more practical significance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a bismaleimide with a main chain containing oxazine and Cardo structures has a molecular formula as follows:
wherein R is
Any one of them; r 1 Is any one of the following structures:
R 2 is any one of the following structures:
the bismaleimide with the main chain containing oxazine and Cardo structures has a carbon residue rate of 50-80% at 800 ℃.
The glass transition temperature of the bismaleimide with the main chain containing oxazine and Cardo structures is 300-500 ℃.
The solubility of the bismaleimide with the main chain containing oxazine and Cardo structures in dichloromethane, chloroform, xylene, ethyl acetate, tetrahydrofuran, dioxane, acetonitrile, acetone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and the like is more than or equal to 50mg mL -1 。
A preparation method of bismaleimide with a main chain containing oxazine and Cardo structures adopts the following two methods for preparation, and the specific preparation process is as follows:
the first method comprises the following specific steps:
step one, maleic anhydride and o-aminophenol are reacted under the reflux of glacial acetic acid to prepare o-hydroxy maleimide, and the reaction is as follows.
Specifically, the method comprises the following steps: adding o-aminophenol and maleic anhydride into a solvent glacial acetic acid, stirring, adding a catalyst p-toluenesulfonic acid, refluxing at 115-130 ℃ for 10-16 h, pouring into ice water, filtering, washing with water, and drying to obtain the o-hydroxy maleimide compound. The o-aminophenol and the maleic anhydride are mixed according to a molar ratio of 1: 1.1-1: 1.3.
Step two, reacting 9-fluorenone with a phenol compound to synthesize a bisphenol fluorene compound, wherein the reaction is as follows:
wherein X is any one of the following structures:
R 3 is any one of the following structures:
specifically, 9-fluorenone, a phenolic compound, 3-mercaptopropionic acid and toluene are mixed and stirred for 0.5 to 1.5 hours at the temperature of 30 to 60 ℃, concentrated sulfuric acid is then dripped, and the mixture is heated to the temperature of 45 to 70 ℃ to react for 8 to 15 hours. After the reaction is finished, pouring the mixture into a 20% ethanol water solution, filtering, washing for several times, and drying to obtain the bisphenol fluorene compound. The 9-fluorenone and the phenolic compound are mixed according to a molar ratio of 1: 2-1: 3. The molar ratio of the 3-mercaptopropionic acid to the 9-fluorenone is 1: 20-1: 40.
Step three, reacting the bisphenol fluorene compound obtained in the step two with a nitrophenol compound to synthesize a bis-nitrofluorene compound, wherein the reaction is as follows:
wherein Y is any one of the following structures:
R 1 is any one of the following structures:
R 3 is any one of the following structures:
R 4 is any one of the following structures:
specifically, a bisphenol fluorene compound is added into DMF to be dissolved, potassium carbonate is added, and after stirring is carried out for 2-4 hours at 100-120 ℃, a nitrophenol compound is added. Reacting the bisphenol fluorene compound and the nitro compound according to a molar ratio of 1: 2-1: 2.2. And after reacting for 15-20 h, cooling, adding water to precipitate, filtering, washing with 20% ethanol water solution for several times, filtering, and drying to obtain the dinitrofluorene compound.
Step four, reducing the dinitrofluorene compound obtained in the step three to prepare a bisaminofluorene compound, wherein the reaction is as follows:
wherein R is 1 Is any one of the following structures:
R 4 is any one of the following structures:
R 5 is any one of the following structures:
specifically, adding a dinitrofluorene compound into a solvent, adding activated carbon, stirring, and heating to 60-75 ℃. Then, hydrazine hydrate is dripped to react for 10-18 h. And after the reaction is finished, filtering, adding water into the filtrate, and filtering, washing and drying to obtain the bisaminofluorene compound.
And step five, synthesizing bismaleimide with a main chain containing oxazine and Cardo structures by using the diamino fluorene compound obtained in the step four, paraformaldehyde and the o-hydroxy maleimide obtained in the step one.
Wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures:
R 5 is any one of the following structures:
specifically, the bisaminofluorene compound, paraformaldehyde and o-hydroxymaleimide are sequentially added into a reaction solvent in a molar ratio of 1:4: 2-1: 4.4: 2.1. And carrying out reflux reaction for 18-32 h at 75-130 ℃ in a nitrogen atmosphere, removing the solvent, dissolving tetrahydrofuran, and adding water to precipitate the bismaleimide with the main chain containing oxazine and Cardo structure.
The second method comprises the following specific steps:
step one, maleic anhydride and o-aminophenol are reacted under the reflux of glacial acetic acid to prepare o-hydroxy maleimide, and the reaction is as follows.
Specifically, the method comprises the following steps: adding o-aminophenol and maleic anhydride into a solvent glacial acetic acid, stirring, adding a catalyst p-toluenesulfonic acid, refluxing at 115-130 ℃ for 10-16 h, pouring into ice water, filtering, washing with water, and drying to obtain the o-hydroxy maleimide compound. The o-aminophenol and the maleic anhydride are mixed according to a molar ratio of 1: 1.1-1: 1.3.
And step two, reacting aniline compounds with fluorenone to synthesize the diamino fluorene compounds.
Wherein Z is any one of the following structures:
R 6 is any one of the following structures:
specifically, heating 9-fluorenone, aniline compounds and methanesulfonic acid at 140-160 ℃ for 10-18 h in a nitrogen atmosphere, cooling after the heating, pouring the cooled aniline compounds into a proper amount of ethanol, filtering, washing and drying in vacuum to obtain the diamino fluorene compounds. The molar ratio of the 9-fluorenone to the aniline compound to the methanesulfonic acid is 1: 8: 0.5-1: 8: 0.7.
and step three, synthesizing bismaleimide with a main chain containing oxazine and Cardo structures by using the diamino fluorene compound obtained in the step two, paraformaldehyde and the o-hydroxy maleimide obtained in the step one. The reaction formula is as follows:
wherein R is 1 Is any one of the following structures:
R 6 is any one of the following structures:
specifically, the bisaminofluorene compound, paraformaldehyde and o-hydroxymaleimide are sequentially added into a reaction solvent in a molar ratio of 1:4: 2-1: 4.4: 2.1. And carrying out reflux reaction for 18-32 h at 75-120 ℃ in a nitrogen atmosphere, removing the solvent, dissolving tetrahydrofuran, and adding water to precipitate the bismaleimide with the main chain containing oxazine and Cardo structure.
Compared with the prior art, the invention has the beneficial effects that:
(1) the bismaleimide monomer with the main chain containing oxazine and Cardo structures synthesized by the method has the advantages that the cured thermosetting material has higher glass transition temperature, the comprehensive performance of the resin is excellent, and the bismaleimide monomer is suitable for matrix resin of high-performance composite materials.
(2) Aiming at the existing defects of bismaleimide, the aromatic ether bond and the non-coplanar structure effectively increase the toughness of the main chain, reduce the symmetry and internal rotation energy of a molecular chain and prevent the molecular chain from being tightly piled, thereby reducing the intermolecular force to reduce the melting point and improving the solubility and the processability, thereby having more practical significance.
(3) Besides the solidification and crosslinking of imide groups at two ends of bismaleimide, an oxazine ring group on a main chain can be subjected to secondary double crosslinking, so that the thermal stability of the resin is further improved.
The foregoing is merely a summary of the technical solutions of the present invention, and other advantages, objects, and features of the present invention will be in part apparent from the following description and in part will become apparent to those skilled in the art upon examination of the following and by study of the time of the invention.
Drawings
FIG. 1 shows an infrared spectrum of 9, 9-bis (4-aminophenyl) fluorene, o-hydroxymaleimide-type bismaleimide of example 8.
FIG. 2 shows the preparation of 9, 9-bis (4-aminophenyl) fluorene, o-hydroxymaleimide-type bismaleimide of example 8 1 H-NMR。
Detailed Description
The following are preferred embodiments of the present invention, it being understood that the preferred embodiments described herein are for purposes of illustration and explanation only and are not intended to be limiting of the invention.
Example 1
Toluene (50mL), phenol (18.8g,250mmol), 9-fluorenone (18g,100mmol) and 3-mercaptopropionic acid (0.44mL) were combined. The mixture was heated to 45 ℃ and stirred for 90 minutes. Concentrated sulfuric acid (3.75mL) was then added gradually to the well stirred solution. After the addition was complete, the mixture was heated to 50 ℃ and stirred for 8 hours. After completion of the reaction, the mixture was cooled to room temperature. The mixture was poured into 20% ethanol solution and filtered. The solid crude product was redissolved in acetone, then deionized water was added and filtered. The product was dried under vacuum at 80 ℃ for 12 hours. The bisphenol fluorene compound was obtained in a yield of 91%.
To 120mL of DMF were added 12g (34.2mmol) of a bisphenol fluorene compound and 12.96g (93.8mmol) of anhydrous potassium carbonate, and the mixture was stirred at 100 ℃ for 3 hours under a nitrogen blanket. Then, 10.75g (68.4mmol) of p-nitrochlorobenzene was slowly added to the system. Finally, the reaction was controlled at reflux temperature for 18 hours. After the reaction was completed, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering yellow precipitate, washing with 20% ethanol water solution for several times, and vacuum drying at 100 ℃ to obtain the dinitrofluorene compound with the yield of 82%.
In a 250mL round bottom flask, bisphenol fluorene compound (10g,16mmol) and 9g of activated carbon were added to dioxane (60mL) and warmed to 60 ℃ under nitrogen blanket. Hydrazine hydrate (41.2mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 18 hours. After the reaction is finished, removing the active carbon, adding a proper amount of deionized water into the solution, and precipitating a white product. The white product was filtered, washed with water, and dried under vacuum at 80 ℃ to give the bisaminofluorene compound in 83% yield.
Ortho-aminophenol (10.92g, 100mmol), maleic anhydride (10.78g, 110mmol) and 120mL of acetic acid were placed in a 250mL round bottle under nitrogen, followed by the addition of 1.4g of p-toluenesulfonic acid. The mixture was stirred and refluxed at 130 ℃ for 10 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 30 min. The precipitate was filtered and washed several times with deionized water. The crude product was recrystallized from isopropanol to give the o-hydroxymaleimide in 45% yield.
An o-hydroxymaleimide (4.5g,24mmol), a bisaminofluorene compound (6.3g,12mmol), paraformaldehyde (1.44g,105.2mmol) and 35mL of toluene were charged into a 40mL three-necked flask. The mixture was refluxed at 130 ℃ for 18 hours, after the reaction was completed, petroleum ether was added, and the precipitate was filtered. The crude product was further purified by recrystallization from a petroleum ether/toluene mixture to obtain a white product with a yield of bismaleimides containing oxazine and Cardo structures in the main chain of 76%.
Example 2
Toluene (50mL), 2, 6-dimethylphenol (30.5g,250mmol), 9-fluorenone (18g,100mmol), and 3-mercaptopropionic acid (0.66mL) were combined. The mixture was heated to 30 ℃ and stirred for 60 minutes. Concentrated sulfuric acid (3.75mL) was then added gradually to the well stirred solution. After the addition was complete, the mixture was heated to 45 ℃ and stirred for 15 hours. After completion of the reaction, the mixture was cooled to room temperature. The mixture was poured into 20% ethanol solution and filtered. The solid crude product was redissolved in acetone, then deionized water was added and filtered. The product was dried under vacuum at 80 ℃ for 12 hours. The bisphenol fluorene compound was obtained in a yield of 87%.
13.9g (34.2mmol) of bisphenol fluorene compound and 12.96g (93.8mmol) of anhydrous potassium carbonate were added to 120mL of DMF, and the mixture was stirred at 110 ℃ for 4 hours under nitrogen protection. Then 16.2g (71.82mmol) of 2-chloro-5-nitrobenzotrifluoride was added to the system. Finally, the reaction was controlled at reflux temperature for 20 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering yellow precipitate, washing with 20% ethanol water solution for several times, and vacuum drying at 100 deg.C to obtain the dinitrofluorene compound with a yield of 85%.
In a 250mL round bottom flask, a dinitrofluorene compound (12.6g,16mmol) and 7g of activated carbon were added to dioxane (50mL) and the temperature was raised to 68 ℃ under nitrogen. Hydrazine hydrate (35mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 14 hours. After the reaction is finished, removing the active carbon, adding a proper amount of deionized water into the solution, and precipitating a white product. The white product was filtered, washed with water and dried under vacuum at 80 ℃ to give the bisaminofluorene compound in 71% yield.
Ortho-aminophenol (10.92g, 100mmol), maleic anhydride (11.76g, 120mmol) and 120mL of acetic acid were placed in a 250mL round flask under nitrogen, followed by the addition of 1.1g of p-toluenesulfonic acid. The mixture was stirred and refluxed at 120 ℃ for 13 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 30 min. The precipitate was filtered and washed several times with deionized water. Recrystallizing the crude product in isopropanol to obtain o-hydroxy maleimide with yield of 38%
An o-hydroxymaleimide (4.63g,24.6mmol), a bisaminofluorene compound (8.7g,12.0mmol), paraformaldehyde (1.51g,50.4mmol) and 35mL of toluene were charged into a 40mL three-necked flask. The mixture is refluxed for 24 hours at 115 ℃, and toluene is distilled off under reduced pressure after the reaction is finished, and the mixture is dried. The crude product was further purified by recrystallization from a toluene mixture to obtain a product, the yield of bismaleimide containing oxazine and Cardo structures in the main chain was 75%.
Example 3
Toluene (100mL), 2-hydroxytrifluorotoluene (48.6g,300mol), 9-fluorenone (18g,0.1mol), and 3-mercaptopropionic acid (0.88mL) were combined. The mixture was heated to 60 ℃ and stirred for 60 minutes. Concentrated sulfuric acid (3.75mL) was then added gradually to the well stirred solution. After the addition was complete, the mixture was heated to 60 ℃ and stirred for 12 hours. After completion of the reaction, the mixture was cooled to room temperature. The mixture was poured into 20% ethanol solution and filtered. The solid crude product was redissolved in acetone, then deionized water was added and filtered. The product was dried under vacuum at 80 ℃ for 12 hours. The bisphenol fluorene compound was obtained in a yield of 69%.
16.6g (34.2mmol) of bisphenol fluorene compound and 16.3g (93.8mmol) of anhydrous potassium carbonate were added to 120mL of DMF, and the mixture was stirred at 120 ℃ for 2 hours under nitrogen protection. Then, 11.85g (75.24mmol) of 5-chloro-2-nitrophenol was added to the system. Finally, the reaction was controlled at reflux temperature for 15 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering yellow precipitate, washing with 20% ethanol water solution for several times, and vacuum drying at 100 ℃ to obtain the dinitrofluorene compound with the yield of 89%.
In a 250mL round bottom flask, a dinitrofluorene compound (12.1g,16mmol) and 9g of activated carbon were added to dioxane (50mL) and the temperature was raised to 75 ℃ under nitrogen. Hydrazine hydrate (35mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 10 hours. After the reaction is finished, removing the active carbon, adding a proper amount of deionized water into the solution, and precipitating a white product. The white product was filtered, washed with water and dried in vacuo at 80 ℃ to give the bisaminofluorene compound in 63% yield.
Ortho-aminophenol (10.92g, 100mmol), maleic anhydride (12.74g, 130mmol) and 120mL of acetic acid were placed in a 250mL round bottle under nitrogen, followed by the addition of 1.1g of p-toluenesulfonic acid. The mixture was stirred and refluxed at 115 ℃ for 16 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 30 min. The precipitate was filtered and washed several times with deionized water. Recrystallizing the crude product in isopropanol to obtain o-hydroxy maleimide with a yield of 42%
An o-hydroxymaleimide (4.74g,25.2mmol), a bisaminofluorene compound (8.8g,12.0mmol), paraformaldehyde (1.58g,52.8mmol) and 35mL of chloroform were charged into a 50mL three-necked flask. The mixture is refluxed for 32 hours at 75 ℃, and toluene is distilled off under reduced pressure after the reaction is finished, and the mixture is dried. The crude product was further purified by recrystallization from a toluene mixture to obtain a product, the yield of bismaleimide containing oxazine and Cardo structures in the main chain was 78%.
Example 4
Toluene (100mL), 2-phenylphenol (51.1g,300mol), 9-fluorenone (18g,0.1mol), and 3-mercaptopropionic acid (0.88mL) were combined. The mixture was heated to 60 ℃ and stirred for 60 minutes. Concentrated sulfuric acid (3.75mL) was then added gradually to the well-stirred solution. After the addition was complete, the mixture was heated to 60 ℃ and stirred for 12 hours. After completion of the reaction, the mixture was cooled to room temperature. The mixture was poured into 20% ethanol solution and filtered. The solid crude product was redissolved in acetone, then deionized water was added and filtered. The product was dried under vacuum at 80 ℃ for 12 hours. The bisphenol fluorene compound was obtained in a yield of 84%.
To 120mL of DMF were added 15.1g (34.2mmol) of a bisphenol fluorene compound and 16.3g (93.8mmol) of anhydrous potassium carbonate, and the mixture was stirred at 120 ℃ for 2 hours under nitrogen protection. Then, 14.0g (75.24mmol) of 2-chloro-5-nitrobenzonitrile was added to the system. Finally, the reaction was controlled at reflux temperature for 15 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering yellow precipitate, washing with 20% ethanol water solution for several times, and vacuum drying at 100 ℃ to obtain the dinitrofluorene compound with the yield of 81%.
In a 250mL round bottom flask, a dinitrofluorene compound (12.7g,16mmol) and 9g of activated carbon were added to dioxane (50mL) and the temperature was raised to 75 ℃ under nitrogen. Hydrazine hydrate (35mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 10 hours. After the reaction is finished, removing the active carbon, adding a proper amount of deionized water into the solution, and precipitating a white product. The white product was filtered, washed with water and dried under vacuum at 80 ℃ to give the bisaminofluorene compound in 58% yield.
Ortho-aminophenol (10.92g, 100mmol), maleic anhydride (12.74g, 130mmol) and 120mL of acetic acid were placed in a 250mL round bottle under nitrogen, followed by the addition of 1.1g of p-toluenesulfonic acid. The mixture was stirred and refluxed at 115 ℃ for 16 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 30 min. The precipitate was filtered and washed several times with deionized water. Recrystallizing the crude product in isopropanol to obtain o-hydroxy maleimide with a yield of 42%
An o-hydroxymaleimide (4.74g,25.2mmol), a bisaminofluorene compound (8.8g,12.0mmol), paraformaldehyde (1.58g,52.8mmol) and 35mL of chloroform were charged into a 50mL three-necked flask. The mixture is refluxed for 32 hours at 75 ℃, and toluene is distilled off under reduced pressure after the reaction is finished, and the mixture is dried. The crude product was further purified by recrystallization from a toluene mixture to obtain a product, the yield of bismaleimide containing oxazine and Cardo structures in the main chain was 72%.
Example 5
Ortho-aminophenol (10.92g, 100mmol), maleic anhydride (10.78g, 110mmol) and 120mL of acetic acid were placed in a 250mL round bottle under nitrogen, followed by the addition of 1.4g of p-toluenesulfonic acid. The mixture was stirred and refluxed at 130 ℃ for 10 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 30 min. The precipitate was filtered and washed several times with deionized water. The crude product was recrystallized from isopropanol to give the o-hydroxymaleimide in 45% yield.
Heating 9-fluorenone (18.02g, 100mmol), 2, 6-dimethylaniline (96.9g, 800mmol) and methanesulfonic acid (4.80g, 50mmol) at 140 ℃ for 18h under nitrogen atmosphere, cooling after the end, pouring into an appropriate amount of ethanol, filtering, washing and drying under vacuum to obtain the bisaminofluorene compound with a yield of 72%.
Bisaminofluorene compound (20.2g, 50mmol), paraformaldehyde (6g, 200mmol) and o-hydroxymaleimide (18.9g, 100mmol) were added successively to 150mL of chloroform under a nitrogen atmosphere, reacted at 75 ℃ for 32 hours, after the reaction was completed, the solvent was removed, and the crude product was purified by column chromatography with a yield of bismaleimide of 72%.
Example 6
Ortho-aminophenol (10.92g, 100mmol), maleic anhydride (11.76g, 120mmol) and 120mL of acetic acid were placed in a 250mL round flask under nitrogen, followed by the addition of 1.1g of p-toluenesulfonic acid. The mixture was stirred and refluxed at 120 ℃ for 13 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 30 min. The precipitate was filtered and washed several times with deionized water. The crude product was recrystallized from isopropanol to give the o-hydroxymaleimide in 38% yield.
9-fluorenone (18.02g, 100mmol), o-anisidine (98.5g, 800mmol) and methanesulfonic acid (4.80g, 70mmol) were heated at 150 ℃ for 14h under nitrogen, cooled after completion and poured into an appropriate amount of ethanol, filtered, washed and dried under vacuum to give the bisaminofluorene compound in 82% yield.
Bisaminofluorene compound (20.4g, 50mmol), paraformaldehyde (6.3g, 210mmol) and o-hydroxymaleimide (19.37g, 102.5mmol) were added successively to 150mL dioxane under a nitrogen atmosphere, reacted at 100 ℃ for 24 hours, after the reaction was completed, the solvent was removed, and the crude product was purified by column chromatography with a yield of bismaleimide of 78%.
Example 7
Ortho-aminophenol (10.92g, 100mmol), maleic anhydride (12.74g, 130mmol) and 120mL of acetic acid were placed in a 250mL round bottle under nitrogen, followed by the addition of 1.1g of p-toluenesulfonic acid. The mixture was stirred and refluxed at 115 ℃ for 16 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 30 min. The precipitate was filtered and washed several times with deionized water. The crude product was recrystallized from isopropanol to give the o-hydroxymaleimide in 42% yield.
9-fluorenone (18.02g, 100mmol), 2-aminobiphenyl (135.4g, 800mmol), xylene (100mL) and methanesulfonic acid (4.80g, 60mmol) were heated at 160 ℃ for 10h under nitrogen atmosphere, after completion, cooled, the solvent was removed and washed with an appropriate amount of ethanol, filtered, washed and dried under vacuum to obtain the bisaminofluorene compound with a yield of 85%.
Bisaminofluorene compound (25.0g, 50mmol), paraformaldehyde (6.6g, 220mmol) and o-hydroxymaleimide (19.84g, 105mmol) were added successively to 150mL of xylene under a nitrogen atmosphere, reacted at 120 ℃ for 18 hours, after the reaction was completed, the solvent was removed, and the crude product was purified by column chromatography with a yield of bismaleimide of 68%.
Example 8
Ortho-aminophenol (10.92g, 100mmol), maleic anhydride (12.74g, 130mmol) and 120mL of acetic acid were placed in a 250mL round bottle under nitrogen, followed by the addition of 1.1g of p-toluenesulfonic acid. The mixture was stirred and refluxed at 115 ℃ for 16 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 30 min. The precipitate was filtered and washed several times with deionized water. The crude product was recrystallized from isopropanol to give the o-hydroxymaleimide in 42% yield.
Heating 9-fluorenone (18.02g, 100mmol), aniline (74.6g, 800mmol) and methanesulfonic acid (4.80g, 60mmol) at 160 ℃ for 10h under nitrogen atmosphere, cooling after the end, pouring into an appropriate amount of ethanol, filtering, washing and vacuum drying to obtain 9, 9-bis (4-aminophenyl) fluorene with a yield of 85%.
Adding 9, 9-bis (4-aminophenyl) fluorene (17.42, 50mmol), paraformaldehyde (6.6g, 220mmol) and o-hydroxymaleimide (19.84g, 105mmol) into 150mL dimethylbenzene in sequence under a nitrogen atmosphere, reacting at 120 ℃ for 18 hours, removing the solvent after the reaction is finished, and purifying a crude product by a column chromatography method to obtain the yield of the 9, 9-bis (4-aminophenyl) fluorene and o-hydroxymaleimide type bismaleimide of 69%.
Example 9
Ortho-aminophenol (10.92g, 100mmol), maleic anhydride (12.74g, 130mmol) and 120mL of acetic acid were placed in a 250mL round bottle under nitrogen, followed by the addition of 1.1g of p-toluenesulfonic acid. The mixture was stirred and refluxed at 115 ℃ for 16 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 30 min. The precipitate was filtered and washed several times with deionized water. The crude product was recrystallized from isopropanol to give the o-hydroxymaleimide in 42% yield.
9-fluorenone (18.02g, 100mmol), 2-aminotrifluorotone (128.9g, 800mmol) and methanesulfonic acid (4.80g, 60mmol) were heated at 160 ℃ for 10h under nitrogen, cooled after completion and poured into an appropriate amount of ethanol, filtered, washed and dried under vacuum to give the bisaminofluorene compound in 73% yield.
Bisaminofluorene compound (24.2, 50mmol), paraformaldehyde (6.6g, 220mmol) and o-hydroxymaleimide (19.84g, 105mmol) were sequentially added to 150mL of xylene under a nitrogen atmosphere, reacted at 120 ℃ for 18 hours, after the reaction was completed, the solvent was removed, and the crude product was purified by column chromatography with a yield of bismaleimide of 75%.
Specific results for example 8 are shown in FIGS. 1 and 2.
FIG. 1 is an infrared spectrum of a bismaleimide monomer with a main chain containing oxazine and Cardo structures: 1776 (carbonyl, asymmetric stretch), 1717 (carbonyl, symmetric stretch), 1237(C-O-C, asymmetric stretch), 927 (oxazine ring-related patterns), 826 (C-H on imide, wobble).
FIG. 2 is a bismaleimide having a main chain containing oxazine and Cardo structuresNuclear magnetic hydrogen spectrum of monomer: 6.95-7.91(22H, Ar-H),7.16(4H, HC ═ CH),5.35(4H, O-CH) 2 -N),4.64(4H,Ar-CH 2 -N)。
The foregoing embodiments are intended to illustrate that the invention may be implemented or used by those skilled in the art, and modifications to the above embodiments will be apparent to those skilled in the art, and therefore the invention includes, but is not limited to, the above embodiments, any methods, processes, products, etc., consistent with the principles and novel and inventive features disclosed herein, and fall within the scope of the invention.
Claims (6)
1. The bismaleimide with the main chain containing oxazine and Cardo structures is characterized in that the formula of the bismaleimide is as follows:
wherein R is
Any one of them; r 1 Is any one of the following structures:
R 2 is any one of the following structures:
2. the bismaleimide with the main chain containing oxazine and Cardo structures as claimed in claim 1, wherein the bismaleimide with the main chain containing oxazine and Cardo structures has a char yield of 50% to 80% at 800 ℃.
3. The bismaleimide with a main chain containing oxazine and Cardo structures as claimed in claim 1, wherein the bismaleimide with a main chain containing oxazine and Cardo structures has a glass transition temperature of 300 ℃ to 500 ℃.
4. The bismaleimide with an oxazine and Cardo structure in the main chain as claimed in claim 1, wherein the bismaleimide with an oxazine and Cardo structure in the main chain has a solubility in dichloromethane, chloroform, xylene, ethyl acetate, tetrahydrofuran, dioxane, acetonitrile, acetone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone of 50 mg/mL or more -1 。
5. A method for preparing bismaleimide with a main chain containing oxazine and Cardo structures as claimed in claim 1, 2, 3 or 4, comprising the steps of:
adding o-aminophenol and maleic anhydride into a solvent glacial acetic acid, stirring, adding a catalyst p-toluenesulfonic acid, and refluxing at the temperature of 115-130 ℃ for 10-16 hours to obtain an o-hydroxy maleimide compound; the mol ratio of the o-aminophenol to the maleic anhydride is 1: 1.1-1: 1.3;
mixing 9-fluorenone, a phenolic compound, 3-mercaptopropionic acid and toluene, stirring for 0.5-1.5 h at the temperature of 30-60 ℃, then dropwise adding concentrated sulfuric acid, and raising the temperature to 45-70 ℃ for reacting for 8-15 h to obtain a bisphenol fluorene compound; the 9-fluorenone and the phenolic compound are mixed according to a molar ratio of 1: 2-1: 3; the molar ratio of the 3-mercaptopropionic acid to the 9-fluorenone is 1: 20-1: 40;
wherein X is any one of the following structures:
R 3 is any one of the following structures:
step three, adding a bisphenol fluorene compound into DMF (dimethyl formamide) for dissolving, adding potassium carbonate, stirring at 100-120 ℃ for 2-4 h, and adding a nitrophenol compound; reacting the bisphenol fluorene compound and the nitro compound according to a molar ratio of 1: 2-1: 2.2; reacting for 15-20 h to obtain a dinitrofluorene compound;
wherein Y is any one of the following structures:
R 1 is any one of the following structures:
R 3 is any one of the following structures:
R 4 is any one of the following structures:
adding the dinitrofluorene compound into a solvent, adding activated carbon, stirring, and heating to 60-75 ℃; then, dropwise adding hydrazine hydrate to react for 10-18 h to obtain a bisaminofluorene compound;
wherein R is 1 Is any one of the following structures:
R 4 is any one of the following structures:
R 5 is any one of the following structures:
adding the bisaminofluorene compound, paraformaldehyde and o-hydroxymaleimide into a reaction solvent in sequence according to a molar ratio of 1:4: 2-1: 4.4: 2.1; carrying out reflux reaction for 18-32 h at 75-130 ℃ in a nitrogen atmosphere to obtain bismaleimide with a main chain containing oxazine and Cardo structure;
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures:
R 5 is any one of the following structures:
6. a method for preparing bismaleimide with a main chain containing oxazine and Cardo structures as claimed in claim 1, 2, 3 or 4, comprising the steps of:
adding o-aminophenol and maleic anhydride into a solvent glacial acetic acid, stirring, adding a catalyst p-toluenesulfonic acid, and refluxing at the temperature of 115-130 ℃ for 10-16 hours to obtain an o-hydroxy maleimide compound; the mol ratio of the o-aminophenol to the maleic anhydride is 1: 1.1-1: 1.3;
heating 9-fluorenone, aniline compounds and methanesulfonic acid at 140-160 ℃ for 10-18 h in a nitrogen atmosphere to obtain bisaminofluorene compounds; the molar ratio of the 9-fluorenone to the aniline compound to the methanesulfonic acid is 1: 8: 0.5-1: 8: 0.7;
wherein Z is any one of the following structures:
R 6 is any one of the following structures:
adding the bisaminofluorene compound, paraformaldehyde and o-hydroxymaleimide into a reaction solvent in sequence, wherein the molar ratio is 1:4: 2-1: 4.4: 2.1; carrying out reflux reaction for 18-32 h at 75-120 ℃ in a nitrogen atmosphere to obtain bismaleimide with a main chain containing oxazine and Cardo structure;
wherein R is 1 Is any one of the following structures:
R 6 is any one of the following structures:
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|---|---|---|---|---|
| CN117362644A (en) * | 2023-10-28 | 2024-01-09 | 韶关市北纺智造科技有限公司 | Polyimide resin for improving hydrophobicity of cotton fabric and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716632A (en) * | 1989-11-22 | 1998-02-10 | Margolin; Solomon B. | Compositions and methods for reparation and prevention of fibrotic lesions |
| CN103408442A (en) * | 2013-07-16 | 2013-11-27 | 常州大学 | Aromatic diamine monomer containing bis(trifluoromethyl), bisisopropyl and fluorenyl structures simultaneously, and preparation method and application thereof |
| CN106366079A (en) * | 2016-08-30 | 2017-02-01 | 常州市宏发纵横新材料科技股份有限公司 | Dibenzoxazine monomer containing ortho-position maleimide groups and preparation method thereof |
| CN106905529A (en) * | 2017-03-17 | 2017-06-30 | 大连理工大学 | Cyano-containing and fluorenyl bimaleimide resin and preparation method thereof |
| CN111117154A (en) * | 2019-12-31 | 2020-05-08 | 广东生益科技股份有限公司 | Flame-retardant thermosetting resin composition, and prepreg, laminated board and printed circuit board manufactured from same |
| CN111675621A (en) * | 2020-05-11 | 2020-09-18 | 南通新纳希新材料有限公司 | Synthesis method of 9, 9-bis (4-aminophenyl) fluorene derivative |
-
2022
- 2022-05-09 CN CN202210496543.1A patent/CN114805333A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716632A (en) * | 1989-11-22 | 1998-02-10 | Margolin; Solomon B. | Compositions and methods for reparation and prevention of fibrotic lesions |
| CN103408442A (en) * | 2013-07-16 | 2013-11-27 | 常州大学 | Aromatic diamine monomer containing bis(trifluoromethyl), bisisopropyl and fluorenyl structures simultaneously, and preparation method and application thereof |
| CN106366079A (en) * | 2016-08-30 | 2017-02-01 | 常州市宏发纵横新材料科技股份有限公司 | Dibenzoxazine monomer containing ortho-position maleimide groups and preparation method thereof |
| CN106905529A (en) * | 2017-03-17 | 2017-06-30 | 大连理工大学 | Cyano-containing and fluorenyl bimaleimide resin and preparation method thereof |
| CN111117154A (en) * | 2019-12-31 | 2020-05-08 | 广东生益科技股份有限公司 | Flame-retardant thermosetting resin composition, and prepreg, laminated board and printed circuit board manufactured from same |
| CN111675621A (en) * | 2020-05-11 | 2020-09-18 | 南通新纳希新材料有限公司 | Synthesis method of 9, 9-bis (4-aminophenyl) fluorene derivative |
Non-Patent Citations (1)
| Title |
|---|
| 张丽影;陈平;那立艳;夏连连;范圣第;: "含芴基Cardo环结构双马来酰亚胺的合成及与二烯丙基双酚A共聚物的热性能", 高分子材料科学与工程, vol. 30, no. 12, pages 20 - 22 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117362644A (en) * | 2023-10-28 | 2024-01-09 | 韶关市北纺智造科技有限公司 | Polyimide resin for improving hydrophobicity of cotton fabric and preparation method thereof |
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