CN114805332A - Bismaleimide containing oxazine side group and Cardo structure and preparation method thereof - Google Patents
Bismaleimide containing oxazine side group and Cardo structure and preparation method thereof Download PDFInfo
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- CN114805332A CN114805332A CN202210496519.8A CN202210496519A CN114805332A CN 114805332 A CN114805332 A CN 114805332A CN 202210496519 A CN202210496519 A CN 202210496519A CN 114805332 A CN114805332 A CN 114805332A
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- bismaleimide
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- oxazine
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- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 67
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- -1 bisphenol fluorene compound Chemical class 0.000 claims description 96
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 27
- 229930185605 Bisphenol Natural products 0.000 claims description 26
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 12
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006683 Mannich reaction Methods 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 13
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 70
- 239000000203 mixture Substances 0.000 description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- 239000008367 deionised water Substances 0.000 description 44
- 229910021641 deionized water Inorganic materials 0.000 description 44
- 239000000047 product Substances 0.000 description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- 238000001914 filtration Methods 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 23
- 239000012043 crude product Substances 0.000 description 21
- 239000002244 precipitate Substances 0.000 description 19
- 238000005406 washing Methods 0.000 description 18
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 16
- 239000003208 petroleum Substances 0.000 description 15
- 238000010992 reflux Methods 0.000 description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 230000001376 precipitating effect Effects 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- CYEZXDVLBGFROE-UHFFFAOYSA-N 2,4-Dihydroxy-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C(O)=C1 CYEZXDVLBGFROE-UHFFFAOYSA-N 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- QQURWFRNETXFTN-UHFFFAOYSA-N 5-fluoro-2-nitrophenol Chemical compound OC1=CC(F)=CC=C1[N+]([O-])=O QQURWFRNETXFTN-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ODJPWXGMNLXNCU-UHFFFAOYSA-N 2-(1-adamantyl)phenol Chemical compound OC1=CC=CC=C1C1(C2)CC(C3)CC2CC3C1 ODJPWXGMNLXNCU-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical class OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 229940061334 2-phenylphenol Drugs 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- GJIZHYHGIAPLJN-UHFFFAOYSA-N 3-hydroxy-4-nitrobenzoyl chloride Chemical compound OC1=CC(C(Cl)=O)=CC=C1[N+]([O-])=O GJIZHYHGIAPLJN-UHFFFAOYSA-N 0.000 description 1
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- ODGIMMLDVSWADK-UHFFFAOYSA-N 4-trifluoromethylaniline Chemical compound NC1=CC=C(C(F)(F)F)C=C1 ODGIMMLDVSWADK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A bismaleimide containing an oxazine side group and a Cardo structure and a preparation method thereof are disclosed, and the molecular formula is as follows:
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures:
r3 is any one of the following structures:
a non-coplanar Cardo structure is introduced into a main chain, so that molecular chains can be prevented from being densely packed, and intermolecular force is reduced to improve the solubility of the molecules. The side chain is introduced with large functional groups to effectively reduce the acting force between molecular chains and destroy the regular structure so as to increase the solubility, and the oxazine functional groups can be subjected to ring-opening polymerization under the heating condition without discharging small molecules, so that the crosslinking density of a cured substance is increased, and the heat resistance is improved. The introduced benzoxazine also has excellent flame retardance, dielectric property and corrosion resistance. The bismaleimide can be used alone or mixed with other resins, and the obtained cured product has higher heat resistance, flame retardance, dielectricity and anticorrosion performance.
Description
Technical Field
The invention belongs to the field of high-performance thermosetting resin, and relates to bismaleimide containing an oxazine side group and a Cardo structure 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 have been no other reports to date of the incorporation of oxazine rings into bismaleimide molecules, and no more so far has the oxazine ring been incorporated into the bismaleimide pendant group. The inventor designs a maleimide 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 containing an oxazine side group and a Cardo structure and a preparation method thereof through repeated design and experiments. The invention is found to be a practical invention through various performance characterizations.
Disclosure of Invention
The invention mainly aims to solve the defects of the existing bismaleimide monomer, and provides a novel bismaleimide monomer containing an oxazine side group and a Cardo structure 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 invention adopts the technical scheme that:
a bismaleimide containing an oxazine side group and a Cardo structure is prepared by taking o-hydroxy bismaleimide as an intermediate and performing Mannich reaction with paraformaldehyde and primary amine, wherein the structural formula of the bismaleimide is as follows:
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures:
R 3 is any one of the following structures:
the molecular structural formula of the o-hydroxy bismaleimide is as follows:
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures:
the bismaleimide containing the oxazine side group and the Cardo structure has the carbon residue rate of 50-82% at 800 ℃, and the carbon residue rate of 60-82% at 800 ℃.
The glass transition temperature of the bismaleimide containing the oxazine side group and the Cardo structure is 300-500 ℃.
The bismaleimide containing the oxazine side group and the Cardo structure has the solubility of more than or equal to 50mg mL in ethanol, methanol, dichloromethane, dichloroethane, chloroform, toluene, xylene, ethyl acetate, tetrahydrofuran, dioxane, acetonitrile, acetone, acetic anhydride, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and the like -1 。
A method for preparing bismaleimide monomer containing oxazine side group and Cardo structure comprises the following steps,
step one, 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 4 is any one of the following structures:
specifically, the method comprises the following steps: mixing 9-fluorenone, a phenolic compound, 3-mercaptopropionic acid and toluene, stirring for 0.5-1.5 h at 30-60 ℃, then dropwise adding concentrated sulfuric acid, and heating to 45-70 ℃ for reacting for 8-15 h. 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 molar ratio of the 9-fluorenone to the phenolic compound is 1: 2-1: 3, and the molar ratio of the 3-mercaptopropionic acid to the 9-fluorenone is 1: 20-1: 40.
Step two, reacting bisphenol fluorene compounds with nitrophenol compounds to synthesize bis (nitrophenol) fluorene compounds, wherein the reaction is as follows:
wherein R is 1 Is any one of the following structures:
R 2 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: -F, -Cl, -Br, -I,
R 6 is any one of the following structures:
specifically, the method comprises the following steps: in the first route (above), a bisphenol fluorene compound is added into DMF to be dissolved, potassium carbonate is added, and after stirring for 1-5 h at 100-120 ℃, a nitrophenol compound is added. And after reacting for 12-24 hours, cooling, adding water to separate out, filtering, washing with 20% ethanol water solution for several times, filtering, and drying to obtain the bis (nitrophenol) fluorene compound. The bisphenol fluorene compound and the nitrophenol compound react according to the molar ratio of 1: 2-1: 2.5. And in the second route (below), a bisphenol fluorene compound is added into DMF for dissolving, potassium carbonate is added, and a dichloro compound is added after stirring for 1-5 hours at 100-120 ℃. After reacting for 12-24 h, cooling, adding water to separate out, filtering, washing with 20% ethanol water solution for several times, filtering, and drying to obtain the dichlorofluorene compound. Adding a dichlorofluorene compound into DMF (dimethyl formamide) for dissolving, adding potassium carbonate, stirring at 100-120 ℃ for 1-5 h, and adding a nitrophenol compound. And after reacting for 12-24 hours, cooling, adding water to separate out, filtering, washing with 20% ethanol water solution for several times, filtering, and drying to obtain the bis (nitrophenol) fluorene compound. The dichlorofluorene compound and the nitrophenol compound react according to a molar ratio of 1: 2-1: 2.5.
Step three, reducing the nitro group in the bis (nitrophenol) fluorene compound into amino to prepare the bis (aminophenol) fluorene compound, wherein the reaction is as follows:
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures:
specifically, the method comprises the following steps: adding a bis (nitrophenol) fluorene compound into absolute ethyl alcohol, then adding palladium carbon, stirring, and heating to 60-80 ℃. And then adding hydrazine hydrate dropwise for reacting for 6-16 h, wherein the molar ratio of the bis (nitrophenol) fluorene compound to the hydrazine hydrate is 1: 20-1: 40. And (3) filtering after the reaction is finished, adding water into the filtrate, and filtering, washing and drying to obtain the bis (aminophenol) fluorene compound.
And step four, synthesizing the o-hydroxy bismaleimide by using a bis (aminophenol) fluorene compound and maleic anhydride.
Wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures:
specifically, the method comprises the following steps: adding a bis (aminophenol) fluorene compound and maleic anhydride into glacial acetic acid in sequence, and reacting the bis (aminophenol) fluorene compound and maleic anhydride according to a molar ratio of 1: 2-1: 2.5. And (3) reacting for 8-24 h at 110-130 ℃, pouring into water, filtering, washing with water, drying, and finally recrystallizing to obtain the o-hydroxy bismaleimide.
And step five, synthesizing a bismaleimide monomer containing an oxazine side group and a Cardo structure by using o-hydroxy bismaleimide, a primary amine compound and paraformaldehyde.
Wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures:
specifically, o-hydroxy bismaleimide, a primary amine compound and paraformaldehyde are added into a reaction solvent according to the molar ratio of 1:2: 4-1: 2:4.4, and react for 12-32 hours at 75-125 ℃. And after the reaction is finished, adding petroleum ether, filtering and recrystallizing to obtain the bismaleimide monomer containing the oxazine side group and the Cardo structure.
Further, in the fifth step, the reaction solvent is any one or more of toluene, xylene, dioxane, tetrahydrofuran and chloroform.
Compared with the prior art, the invention has the following beneficial effects:
(1) the bismaleimide monomer containing the oxazine side group and the Cardo structure synthesized by the method has a high glass transition temperature after being cured. The resin has excellent comprehensive performance and is suitable for matrix resin of high-performance composite materials.
(2) Aiming at the existing defects of bismaleimide, the invention introduces large side groups, aromatic ether bonds and a non-coplanar structure to effectively reduce the symmetry and internal rotation energy of a molecular chain and prevent the molecular chain from being tightly piled, thereby reducing intermolecular force to reduce the melting point and improve the solubility and the processability, thereby having more practical significance.
(3) Besides the solidification and crosslinking of imide groups at two ends of bismaleimide, oxazine ring groups at two sides of molecules 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 will be in part understood by those skilled in the art upon examination of the invention and by study of the time.
Drawings
FIG. 1 shows an infrared spectrum of 9, 9-bis [4- (3-hydroxy-4-maleimidophenoxy) phenyl ] fluorene, aniline type bismaleimide of example 1.
FIG. 2 shows 9, 9-bis [4- (3-hydroxy-4-maleimidophenoxy) phenyl ] in example 1]Method for preparing fluorene and aniline bismaleimide 1 H-NMR。
FIG. 3 is a DSC chart of 9, 9-bis [4- (3-hydroxy-4-maleimidophenoxy) phenyl ] fluorene, aniline type bismaleimide of example 1.
FIG. 4 is a TGA graph of 9, 9-bis [4- (3-hydroxy-4-maleimidophenoxy) phenyl ] fluorene, aniline type bismaleimide of example 1.
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 (23.5g,0.25mol), 9-fluorenone (18g,0.1mol), and 3-addition mercaptopropionic acid (0.44mL) were mixed. The mixture was heated to 60 ℃ 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 45 ℃ 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 yield was 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 5h under nitrogen protection. Then, 10.79g (68.7mmol) of 5-fluoro-2-nitrophenol was slowly added to the system. Finally, the reaction was controlled at reflux temperature for 18 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 83%.
In a 250mL round bottom flask, a dinitrofluorene compound (10g,16mmol) and Pd/C (0.48g) were added to anhydrous ethanol (60mL) and warmed to 60 ℃ under nitrogen. Hydrazine hydrate (31mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 12 hours. After the reaction is finished, Pd/C is removed, and a proper amount of deionized water is added into the solution to precipitate a white product. The white product was filtered, washed with water and dried under vacuum at 80 ℃ to give the bisaminofluorene compound in 75% yield.
A dinitrofluorene compound (10g, 17.71mmol), maleic anhydride (3.65g, 37.22mmol) and 150mL of acetic acid were placed in a 250mL round flask under nitrogen. The mixture was stirred and at 110 ℃ for 24 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 10 min. The precipitate was filtered and washed several times with deionized water. Recrystallizing the crude product in isopropanol to obtain bismaleimide compound with yield of 41%
An o-hydroxybismaleimide compound (4.3g,5.9mmol), aniline (1.11g,11.8mmol), paraformaldehyde (0.7g,23.6mmol), and 35mL xylene were charged into a 50mL three-necked flask. The mixture was reacted at 110 ℃ for 32 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 pendant oxazine groups and Cardo structures of 72%.
Example 2
Toluene (50mL), phenol (18.8g,0.2mol), 9-fluorenone (18g,0.1mol), and 3-addition mercaptopropionic acid (0.23mL) were mixed. The mixture was heated to 45 ℃ and stirred for 60 minutes. Concentrated sulfuric acid (3.45mL) was then added gradually to the well stirred solution. After the addition was complete, the mixture was heated to 55 ℃ 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 88%.
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 110 ℃ for 3 hours under a nitrogen blanket. Then 12.14g (77.29mmol) of 5-fluoro-2-nitrophenol was slowly added to the system. Finally, the reaction was controlled at reflux temperature for 12 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 72%.
In a 250mL round-bottom flask, a dinitrofluorene compound (10g,16mmol) and Pd/C (0.40g) were added to anhydrous ethanol (60mL) and warmed to 70 ℃ under nitrogen. Hydrazine hydrate (45mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 16 hours. After the reaction is finished, Pd/C is removed, and a proper amount of deionized water is added into the solution to precipitate a white product. The white product was filtered, washed with water, and dried under vacuum at 80 ℃ to give the bisaminofluorene compound in 75% yield.
Bisaminofluorene compound (10g, 17.71mmol), maleic anhydride (3.47g, 35.42mmol) and 130mL of acetic acid were put into a 250mL round bottle under nitrogen. The mixture was stirred and refluxed for 15 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 10 min. The precipitate was filtered and washed several times with deionized water. The crude product was recrystallized from isopropanol to give the o-hydroxybismaleimide compound in a yield of 38%.
An o-hydroxybismaleimide compound (4.3g,5.9mmol), aniline (1.1g,11.81mmol), paraformaldehyde (0.74g,24.78mmol), and 35mL of toluene were charged into a 50mL three-necked flask. The mixture was heated under reflux for 24 hours, after the reaction was complete 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 80% yield of bismaleimides containing pendant oxazine groups and Cardo structures.
Example 3
Toluene (50mL), phenol (28.2g,0.3mol), 9-fluorenone (18g,0.1mol), and 3-addition mercaptopropionic acid (0.28mL) were mixed. The mixture was heated to 30 ℃ and stirred for 30 minutes. Concentrated sulfuric acid (3.45mL) was then added gradually to the well stirred solution. After the addition was complete, the mixture was heated to 70 ℃ and stirred for 10 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 yield was 81%.
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 120 ℃ for 1 hour under a nitrogen blanket. Then 17.31g (85.88mmol) of 3-hydroxy-4-nitrobenzoyl chloride was slowly added to the system. Finally, the reaction was controlled at reflux temperature for 24 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 86%.
In a 250mL round bottom flask, a dinitrofluorene compound (10.88g,16mmol) and Pd/C (0.45g) were added to absolute ethanol (60mL) and warmed to 80 ℃ under nitrogen. Hydrazine hydrate (45mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 6 hours. After the reaction is finished, Pd/C is removed, and a proper amount of deionized water is added into the solution to precipitate a white product. The product was filtered, washed with water and dried under vacuum at 80 ℃ to give the bisaminofluorene compound in 80% yield.
Bisaminofluorene compound (10.99g, 17.71mmol), maleic anhydride (4.34g, 44.28mmol) and 130mL of acetic acid were placed in a 250mL round flask under nitrogen. The mixture was stirred and refluxed for 8 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 10 min. The precipitate was filtered and washed several times with deionized water. The crude product was recrystallized from isopropanol to give the o-hydroxybismaleimide compound in a yield of 46%.
An o-hydroxybismaleimide compound (4.27g,5.9mmol), aniline (1.1g,11.81mmol), paraformaldehyde (0.78g,25.96mmol), and 35mL xylene were charged into a 50mL three-necked flask. The mixture was heated under reflux for 8 hours, after the reaction was complete 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 product with a yield of bismaleimides containing pendant oxazine groups and Cardo structures of 69%.
Example 4
Toluene (50mL), 2-allylphenol (24.4g,0.2mol), 9-fluorenone (18g,0.1mol), and 3-addition mercaptopropionic acid (0.66mL) were mixed. The mixture was heated to 45 ℃ and stirred for 60 minutes. Concentrated sulfuric acid (3.45mL) was then added gradually to the well stirred solution. After the addition was complete, the mixture was heated to 55 ℃ 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 yield was 56%.
To 120mL of DMF were added 14.72g (34.2mmol) of a bisphenol fluorene compound and 12.96g (93.8mmol) of anhydrous potassium carbonate, and the mixture was stirred at 110 ℃ for 3 hours under a nitrogen blanket. Then 9.98g (77.29mmol) of dimethyldichlorosilane were slowly added to the system. Finally, the reaction was controlled at reflux temperature for 12 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering, precipitating, washing with 20% ethanol water solution for several times, and vacuum drying at 100 deg.C to obtain dichlorofluorene compound with yield of 43%.
To 120mL of DMF were added 11.99g (77.29mmol) of 4-nitroresorcinol and 12.96g (93.8mmol) of anhydrous potassium carbonate, and the mixture was stirred at 110 ℃ for 3 hours under nitrogen. Then, 21.3g (34.2mmol) of a dichlorofluorene compound was added to the system. Finally, the reaction was controlled at reflux temperature for 12 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering and precipitating, washing with 20% ethanol water solution for several times, and vacuum drying at 100 ℃ to obtain the dinitrofluorene compound with the yield of 71%.
In a 250mL round bottom flask, a dinitrofluorene compound (13.65g,16mmol) and Pd/C (0.40g) were added to absolute ethanol (60mL) and warmed to 70 ℃ under nitrogen. Hydrazine hydrate (15mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 16 hours. After the reaction is finished, Pd/C is removed, and a proper amount of deionized water is added into the solution to precipitate a white product. The white product was filtered, washed with water and dried under vacuum at 80 ℃ to give bisaminofluorene in 71% yield.
Bisaminofluorene (14.05g, 17.71mmol), maleic anhydride (3.47g, 35.42mmol), and 130mL of acetic acid were placed in a 250mL round vial under nitrogen. The mixture was stirred and reacted at 130 ℃ for 15 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 10 min. The precipitate was filtered and washed several times with deionized water. The crude product was recrystallized from toluene to give the o-hydroxybismaleimide compound in a yield of 56%.
An o-hydroxybismaleimide compound (5.62g,5.9mmol), p-aminobenzonitrile (1.4g,11.81mmol), paraformaldehyde (0.74g,24.78mmol), and 35mL of toluene were charged into a 50mL three-necked flask. The mixture was reacted at 125 ℃ for 24 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 product with 80% yield of bismaleimides containing pendant oxazine groups and Cardo structures.
Example 5
Toluene (50mL), 2, 6-dimethylphenol (36.65g,0.3mol), 9-fluorenone (18g,0.1mol), and 3-mercaptopropionic acid (0.88mL) were mixed. The mixture was heated to 30 ℃ and stirred for 30 minutes. Concentrated sulfuric acid (3.45mL) was then added gradually to the well stirred solution. After the addition was complete, the mixture was heated to 70 ℃ and stirred for 10 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 yield was 88%.
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 120 ℃ for 1 hour under nitrogen protection. Then 20.53g (85.88mmol) of 4.4-dichlorodiphenyl ether was slowly added to the system. Finally, the reaction was controlled at reflux temperature for 24 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering, precipitating, washing with 20% ethanol water solution for several times, and vacuum drying at 100 deg.C to obtain dichlorofluorene compound with yield of 77%.
13.3g (85.5mmol) of 4-nitroresorcinol and 12.96g (93.8mmol) of anhydrous potassium carbonate are added to 120mL of DMF and the mixture is stirred at 120 ℃ for 1 hour under nitrogen protection. Then, 27.8g (34.2mmol) of a dichlorofluorene compound was added to the system. Finally, the reaction was controlled at reflux temperature for 24 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering and precipitating, 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 (16.79g,16mmol) and Pd/C (0.45g) were added to absolute ethanol (60mL) and warmed to 80 ℃ under nitrogen. Hydrazine hydrate (23.3mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 6 hours. After the reaction is finished, Pd/C is removed, and a proper amount of deionized water is added into the solution to precipitate 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.
Bisaminofluorene compound (17.52g, 17.71mmol), maleic anhydride (4.34g, 44.28mmol) and 130mL of acetic acid were placed in a 250mL round flask under nitrogen. The mixture was reacted at 120 ℃ for 8 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 10 min. The precipitate was filtered and washed several times with deionized water. The crude product was recrystallized from toluene to give the o-hydroxybismaleimide compound in a yield of 44%.
An o-hydroxybismaleimide compound (6.8g,5.9mmol), allylamine (0.67g,11.81mmol), paraformaldehyde (0.78g,25.96mmol), and 35mL of chloroform were charged into a 50mL three-necked flask. The mixture was reacted at 75 ℃ for 8 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 pendant oxazine groups and Cardo structures of 75%.
Example 6
Toluene (50mL), 2-phenylphenol (42.6g,0.25mol), 9-fluorenone (18g,0.1mol), and 3-mercaptopropionic acid (0.44mL) were mixed. The mixture was heated to 60 ℃ 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 45 ℃ 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 95%.
To 120mL of DMF were added 17.19g (34.2mmol) of a bisphenol fluorene compound and 12.96g (93.8mmol) of anhydrous potassium carbonate, and the mixture was stirred at 100 ℃ for 5h under nitrogen protection. Then, 25.63g (68.7mmol) of 2,2- (4-chlorophenyl) hexafluoropropane was added to the system. Finally, the reaction was controlled at reflux temperature for 18 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering, precipitating, washing with 20% ethanol water solution for several times, and vacuum drying at 100 deg.C to obtain dichlorofluorene compound with yield of 65%.
13.3g (85.5mmol) of 4-nitroresorcinol and 12.96g (93.8mmol) of anhydrous potassium carbonate are added to 120mL of DMF and the mixture is stirred at 100 ℃ for 5h under nitrogen protection. Then, 40.22g (34.2mmol) of a dichlorofluorene compound was added to the system. Finally, the reaction was controlled at reflux temperature for 18 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering and precipitating, washing with 20% ethanol water solution for several times, and vacuum drying at 100 ℃ to obtain the dinitrofluorene compound with the yield of 71%.
In a 250mL round bottom flask, a dinitrofluorene compound (22.61g,16mmol) and Pd/C (0.48g) were added to absolute ethanol (60mL) and warmed to 60 ℃ under nitrogen. Hydrazine hydrate (31mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 12 hours. After the reaction is finished, Pd/C is removed, and a proper amount of deionized water is added into the solution to precipitate a white product. The white product was filtered, washed with water and dried under vacuum at 80 ℃ to give the bisaminofluorene compound in a yield of 72%.
Bisaminofluorene compound (23.97g, 17.71mmol), maleic anhydride (3.65g, 37.22mmol) and 150mL of acetic acid were placed in a 250mL round flask under nitrogen. The mixture was stirred and at 110 ℃ for 24 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 10 min. The precipitate was filtered and washed several times with deionized water. The crude product is recrystallized in toluene to obtain the o-hydroxy bismaleimide compound with the yield of 50 percent
An o-hydroxybismaleimide compound (8.9g,5.9mmol), 3-aminopropylmethyldiethoxysilane (2.26g,11.8mmol), paraformaldehyde (0.7g,23.6mmol) and 35mL of chloroform were charged into a 50mL three-necked flask. The mixture was reacted at 85 ℃ for 32 hours, after the reaction was completed, petroleum ether was added, and the precipitate was filtered. Recrystallization was further purified to obtain a white product with 81% yield of bismaleimide containing pendant oxazine groups and Cardo structures.
Example 7
Toluene (50mL), 2-fluorophenol (22.42g,0.2mol), 9-fluorenone (18g,0.1mol), and 3-mercaptopropionic acid (0.66mL) were mixed. The mixture was heated to 45 ℃ and stirred for 60 minutes. Concentrated sulfuric acid (3.45mL) was then added gradually to the well stirred solution. After the addition was complete, the mixture was heated to 55 ℃ 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 yield of the bisphenol fluorene compound was 68%.
13.2g (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 3 hours under nitrogen protection. Then 19.64g (68.4mmol) of 4.4-dichlorodiphenyl sulfone was slowly added to the system. Finally, the reaction was controlled at reflux temperature for 12 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 dichlorofluorene compound with yield of 66%.
To 120mL of DMF were added 10.6g (68.4mmol) of 4-nitroresorcinol and 12.96g (93.8mmol) of anhydrous potassium carbonate, and the mixture was stirred at 110 ℃ for 3 hours under nitrogen protection. Then, 30.4g (34.2mmol) of a dichlorofluorene compound was added to the system. Finally, the reaction was controlled at reflux temperature for 12 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering, precipitating, washing with 20% ethanol water solution for several times, and vacuum drying at 100 ℃ to obtain the dinitrofluorene compound with the yield of 76%.
In a 250mL round bottom flask, a dinitrofluorene compound (18g,16mmol) and Pd/C (0.40g) were added to anhydrous ethanol (80mL) and warmed to 75 ℃ under nitrogen. Hydrazine hydrate (15mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 16 hours. After the reaction is finished, Pd/C is removed, and a proper amount of deionized water is added into the solution to precipitate a white product. The product was filtered, washed with water and dried under vacuum at 80 ℃ to give the bisaminofluorene compound in 79% yield.
Bisaminofluorene compound (18.86g, 17.71mmol), maleic anhydride (3.99g, 40.73mmol) and 130mL of acetic acid were placed in a 250mL round flask under nitrogen. The mixture was stirred and reacted at 130 ℃ for 15 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 10 min. The precipitate was filtered and washed several times with deionized water. Recrystallizing the crude product to obtain the o-hydroxy bismaleimide compound, wherein the yield is 42%.
An o-hydroxybismaleimide compound (7.2g,5.9mmol), 4-aminotrifluorotoluene (1.9g,11.81mmol), paraformaldehyde (0.74g,24.78mmol), and 35mL dioxane were charged into a 50mL three-necked flask. And (3) reacting the mixture at 105 ℃ for 24 hours, adding petroleum ether after the reaction is finished, filtering, precipitating, recrystallizing and further purifying to obtain a product, wherein the yield of the bismaleimide containing the oxazine side groups and the Cardo structure is 71%.
Example 8
Toluene (50mL), 2- (1-adamantyl) -phenol (68.5g,0.3mol), 9-fluorenone (18g,0.1mol), and 3-mercaptopropionic acid (0.88mL) were mixed. The mixture was heated to 30 ℃ and stirred for 30 minutes. Concentrated sulfuric acid (3.45mL) was then added gradually to the well stirred solution. After the addition was complete, the mixture was heated to 70 ℃ and stirred for 10 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 yield was 65%.
To 120mL of DMF were added 21.14g (34.2mmol) of a bisphenol fluorene compound and 12.96g (93.8mmol) of anhydrous potassium carbonate, and the mixture was stirred at 120 ℃ for 1 hour under a nitrogen blanket. Then 13.49g (85.88mmol) of 5-fluoro-2-nitrophenol was slowly added to the system. Finally, the reaction was controlled at reflux temperature for 24 hours. After completion of the reaction, the system was cooled to room temperature. Adding a proper amount of deionized water, filtering and precipitating, washing with 20% ethanol water solution for several times, and vacuum drying at 100 ℃ to obtain the dinitrofluorene compound with the yield of 83%.
In a 250mL round bottom flask, the dinitrofluorene compound (14.26g,16mmol) and Pd/C (0.45g) were added to absolute ethanol (60mL) and warmed to 80 ℃ under nitrogen. Hydrazine hydrate (23.3mL) was then slowly added dropwise through a constant pressure funnel. The reaction was carried out at this temperature for 6 hours. After the reaction is finished, Pd/C is removed, and a proper amount of deionized water is added into the solution to precipitate a product. The product was filtered, washed with water and dried under vacuum at 80 ℃ to give bisaminofluorene in 87% yield.
Bisaminofluorene (14.75g, 17.71mmol), maleic anhydride (4.34g, 44.28mmol), and 130mL of acetic acid were placed in a 250mL round flask under nitrogen. The mixture was reacted at 120 ℃ for 8 hours. After the reaction is finished, pouring the solution into a certain amount of deionized water, and stirring for 10 min. The precipitate was filtered and washed several times with deionized water. Recrystallization to obtain the o-hydroxy bismaleimide compound with the yield of 38 percent.
An o-hydroxybismaleimide compound (6.2g,5.9mmol), allylamine (0.67g,11.81mmol), paraformaldehyde (0.78g,25.96mmol), and 35mL of chloroform were charged into a 50mL three-necked flask. The mixture was reacted at 75 ℃ for 8 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 yield a white product with 82% yield of bismaleimides containing pendant oxazine groups and Cardo structures.
FIG. 1 is an infrared spectrum of a bismaleimide monomer containing oxazine side groups and a Cardo structure: 1774 (carbonyl, asymmetric stretch), 1717 (carbonyl, symmetric stretch), 1261(C-O-C, asymmetric stretch), 911 (oxazine ring-related mode), 825 (C-H on imide, wobble).
FIG. 2 is a nuclear magnetic hydrogen spectrum of bismaleimide monomer containing oxazine side groups and Cardo structure: 6.87-7.97(30H, Ar-H),6.44(4H, HC ═ CH),5.43(4H, O-CH2-N),4.62(4H, Ar-CH 2-N).
FIG. 3 is a DSC of bismaleimide monomer containing oxazine side group and Cardo structure: melting point, 153 ℃; curing initiation temperature, 193 ℃; peak temperature, 249 ℃.
Fig. 4 is a TGA spectrum of bismaleimide monomers containing oxazine side groups and Cardo structure: the char yield at 800 ℃ was 65%.
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 containing an oxazine side group and a Cardo structure is characterized in that the bismaleimide is prepared by taking o-hydroxy bismaleimide as an intermediate and performing Mannich reaction with paraformaldehyde and primary amine, wherein the molecular structural formula of the bismaleimide is as follows:
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures: -O-,
R 3 is any one of the following structures:
2. the bismaleimide containing oxazine side groups and Cardo structures according to claim 1, wherein the molecular structure of the o-hydroxybismaleimide is as follows:
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures: -O-,
3. the bismaleimide containing oxazine side groups and Cardo structures according to claim 1, wherein the bismaleimide containing oxazine side groups and Cardo structures has a char yield of 50% to 82% at 800 ℃.
4. The bismaleimide containing oxazine side groups and Cardo structures according to claim 1, wherein the bismaleimide containing oxazine side groups and Cardo structures has a glass transition temperature of 300 ℃ to 500 ℃.
5. The bismaleimide containing oxazine side groups and Cardo structures according to claim 1, wherein the bismaleimide containing oxazine side groups and Cardo structures has a solubility greater than or equal to 50mg mL/mL in ethanol, methanol, dichloromethane, dichloroethane, chloroform, toluene, xylene, ethyl acetate, tetrahydrofuran, dioxane, acetonitrile, acetone, acetic anhydride, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and the like -1 。
6. A method for preparing bismaleimide containing oxazine side groups and Cardo structures according to claim 1 or 3 or 4 or 5, comprising the steps of,
mixing 9-fluorenone, a phenolic compound, 3-mercaptopropionic acid and toluene at 30-60 ℃, stirring for 0.5-1.5 h, then dropwise adding concentrated sulfuric acid, and raising to 45-70 ℃ for reacting for 8-15 h to obtain a bisphenol fluorene compound; the molar ratio of the 9-fluorenone to the phenolic compound is 1: 2-1: 3, and 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 4 is any one of the following structures:
step two, preparing the bis (nitrophenol) fluorene compound
Adding the bisphenol fluorene compound obtained in the first step into DMF (dimethyl formamide) for dissolving, adding potassium carbonate, stirring at 100-120 ℃ for 1-5 hours, and adding a nitrophenol compound; reacting for 12-24 h to obtain a bis (nitrophenol) fluorene compound; the bisphenol fluorene compound and the nitrophenol compound react according to a molar ratio of 1: 2-1: 2.5;
or adding the bisphenol fluorene compound obtained in the first step into DMF (dimethyl formamide) for dissolving, adding potassium carbonate, stirring at 100-120 ℃ for 1-5 hours, and adding a dichloro compound; reacting for 12-24 h to obtain a dichlorofluorene compound; adding a dichlorofluorene compound into DMF (dimethyl formamide) for dissolving, adding potassium carbonate, stirring at 100-120 ℃ for 1-5 hours, and adding a nitrophenol compound; reacting for 12-24 h to obtain a bis (nitrophenol) fluorene compound; the dichlorofluorene compound and the nitrophenol compound react according to a molar ratio of 1: 2-1: 2.5;
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures: -O-,
R 4 is any one of the following structures:
R 5 is as followsAny one of the column structures: -F, -Cl, -Br, -I,
R 6 is any one of the following structures:
step three, adding the bis (nitrophenol) fluorene compound obtained in the step two into absolute ethyl alcohol, then adding palladium carbon, stirring, and heating to 60-80 ℃; then, dropwise adding hydrazine hydrate to react for 6-16 h to obtain a bis (aminophenol) fluorene compound; the molar ratio of the bis (nitrophenol) fluorene compound to the hydrazine hydrate is 1: 20-1: 40;
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures: -O-,
adding a bis (aminophenol) fluorene compound and maleic anhydride into glacial acetic acid in sequence, and reacting the bis (aminophenol) fluorene compound and maleic anhydride according to a molar ratio of 1: 2-1: 2.5; reacting for 8-24 h at the temperature of 110-130 ℃ to obtain o-hydroxy bismaleimide;
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures: -O-,
adding o-hydroxy bismaleimide, a primary amine compound and paraformaldehyde into a reaction solvent according to a molar ratio of 1:2: 4-1: 2:4.4, and reacting at 75-125 ℃ for 12-32 hours to obtain a bismaleimide monomer containing an oxazine side group and a Cardo structure;
wherein R is 1 Is any one of the following structures:
R 2 is any one of the following structures: -O-,
R 3 is any one of the following structures:
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Cited By (4)
| 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 |
| CN117362285A (en) * | 2023-12-06 | 2024-01-09 | 成都科宜高分子科技有限公司 | Benzoxazine derivative and preparation method thereof |
| WO2024029352A1 (en) * | 2022-08-03 | 2024-02-08 | 信越化学工業株式会社 | Fluorene compound having halogen atom and allyl group, and method for producing same |
| WO2024029351A1 (en) * | 2022-08-03 | 2024-02-08 | 信越化学工業株式会社 | Fluorene compound having sulfonic acid ester structure and allyl group and method for producing same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN112094412A (en) * | 2020-08-21 | 2020-12-18 | 江苏大学 | Cross-linked polybenzoxazole and preparation method thereof |
-
2022
- 2022-05-09 CN CN202210496519.8A patent/CN114805332B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN112094412A (en) * | 2020-08-21 | 2020-12-18 | 江苏大学 | Cross-linked polybenzoxazole and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024029352A1 (en) * | 2022-08-03 | 2024-02-08 | 信越化学工業株式会社 | Fluorene compound having halogen atom and allyl group, and method for producing same |
| WO2024029351A1 (en) * | 2022-08-03 | 2024-02-08 | 信越化学工業株式会社 | Fluorene compound having sulfonic acid ester structure and allyl group and method for producing same |
| 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 |
| CN117362285A (en) * | 2023-12-06 | 2024-01-09 | 成都科宜高分子科技有限公司 | Benzoxazine derivative and preparation method thereof |
| CN117362285B (en) * | 2023-12-06 | 2024-02-09 | 成都科宜高分子科技有限公司 | Benzoxazine derivative and preparation method thereof |
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