CN111909102A - Synthetic method of dinitro-substituted quinoxaline, heat-resistant polyimide and preparation method thereof - Google Patents
Synthetic method of dinitro-substituted quinoxaline, heat-resistant polyimide and preparation method thereof Download PDFInfo
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- substituted quinoxaline
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 63
- -1 dinitro-substituted quinoxaline Chemical class 0.000 title claims abstract description 39
- 239000004642 Polyimide Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000010189 synthetic method Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 43
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 18
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical class CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229920005575 poly(amic acid) Polymers 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 11
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- 230000015572 biosynthetic process Effects 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- MBUPVGIGAMCMBT-UHFFFAOYSA-N 2-bromo-1-(4-nitrophenyl)ethanone Chemical group [O-][N+](=O)C1=CC=C(C(=O)CBr)C=C1 MBUPVGIGAMCMBT-UHFFFAOYSA-N 0.000 claims description 4
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
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- 239000011780 sodium chloride Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- RAUWPNXIALNKQM-UHFFFAOYSA-N 4-nitro-1,2-phenylenediamine Chemical compound NC1=CC=C([N+]([O-])=O)C=C1N RAUWPNXIALNKQM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- 230000008569 process Effects 0.000 description 8
- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
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- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 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 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical group NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- ZYYNLLHFNBENFK-UHFFFAOYSA-N 2-nitroquinoxaline Chemical compound C1=CC=CC2=NC([N+](=O)[O-])=CN=C21 ZYYNLLHFNBENFK-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical group C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000006664 bond formation reaction Methods 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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- 239000003480 eluent Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- LUDZVVVPVCUUBP-UHFFFAOYSA-N quinoxaline-2,3-diamine Chemical class C1=CC=C2N=C(N)C(N)=NC2=C1 LUDZVVVPVCUUBP-UHFFFAOYSA-N 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Substances O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The application relates to a method for synthesizing dinitro-substituted quinoxaline, which is characterized by comprising the steps of reacting 4-nitro-o-phenylenediamine and halogen-substituted p-nitroacetophenone in dimethyl sulfoxide for a preset time period at room temperature to obtain a dinitro-substituted quinoxaline crude product; wherein the dinitro-substituted quinoxaline is 3/2- (4-nitrophenyl) -6-nitroquinoxaline. The application also relates to a polyimide synthesized from 3/2- (4-aminophenyl) -6-aminoquinoxaline derived from 3/2- (4-nitrophenyl) -6-nitroquinoxaline and a preparation method thereof. The synthesis method of the dinitro-substituted quinoxaline is low in cost and environment-friendly. The polyimide prepared by the method has high heat resistance and excellent mechanical property and electrical property.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a method for synthesizing dinitro-substituted quinoxaline, heat-resistant polyimide prepared from diamino-substituted quinoxaline derived from the dinitro-substituted quinoxaline and a preparation method thereof.
Background
Quinoxaline is a benzopyrazine compound having excellent biological activity and thermal stability, and has been widely studied because it exists in various compounds and is expected to be used in the fields of dyes, organic semiconductors, electroluminescent materials, anion receptors, and the like. Similarly, quinoxaline derivatives are potentially applicable in many fields. Therefore, many methods have been developed in the art for synthesizing quinoxaline derivatives, for example, reacting a monomer containing an o-phenylenediamine structure with an α -hydroxyketone or an epoxide, etc.
Aminoquinoxaline has a higher chemical bond energy, a larger molar volume and a weaker polarity, which endows a polymer prepared from the aminoquinoxaline with excellent heat resistance and oxidation resistance, higher environmental stability, a low dielectric constant, dielectric loss and higher plasticity. The aminoquinoxaline can be dissolved in an organic solvent and has good processing performance.
The synthesis steps of aminoquinoxaline are generally divided into two parts: firstly, nitro-substituted quinoxaline is synthesized, and then nitro is reduced into amino to obtain corresponding amino quinoxaline. The reduction of the nitro group has been reported in a number of well-established routes, and the key to the preparation of quinoxalinediamines is the synthesis of the corresponding nitro substituent.
3/2- (4-aminophenyl) -6-aminoquinoxaline (QHDA) is an important diamine monomer and can be used for preparing polyimide with good heat resistance. The difficulty in synthesizing 3/2- (4-aminophenyl) -6-aminoquinoxaline is the synthesis of 3/2- (4-nitrophenyl) -6-nitroquinoxaline (QHDN).
The existing method for synthesizing 3/2- (4-nitrophenyl) -6-nitroquinoxaline (QHDN) needs to use a selenium dioxide compound or a dangerous compound such as concentrated hydrochloric acid or use a high-temperature condition of more than 120 ℃.
For this reason, there is a continuing need in the art to develop a cost-effective, mild reaction condition method for the synthesis of 3/2- (4-nitrophenyl) -6-nitroquinoxaline.
Disclosure of Invention
The purpose of the application is to provide a method for synthesizing dinitro-substituted quinoxaline, particularly 3/2- (4-nitrophenyl) -6-nitroquinoxaline, which has low cost, mild reaction conditions and environmental protection. The process described herein is a one-step process, can be carried out at room temperature, and does not require the use of hazardous reagents.
It is also an object of the present application to provide a method for synthesizing heat-resistant polyimides using 3/2- (4-aminophenyl) -6-aminoquinoxaline derived from 3/2- (4-nitrophenyl) -6-nitroquinoxaline.
It is also an object of the present invention to provide a heat-resistant polyimide synthesized by the method as described above.
In order to solve the above technical problem, the present application provides the following technical solutions:
in a first aspect, the present application provides a method for synthesizing a dinitro-substituted quinoxaline, characterized in that the method comprises reacting 4-nitrophthalenediamine with a halogen-substituted p-nitroacetophenone in dimethyl sulfoxide at room temperature for a predetermined period of time to obtain a dinitro-substituted quinoxaline crude product;
wherein, the dinitro-substituted quinoxaline is 3/2- (4-nitrophenyl) -6-nitroquinoxaline, and the structure of the dinitro-substituted quinoxaline is shown in the following general formula (1):
in one embodiment of the first aspect, the halogen-substituted p-nitroacetophenone is 2-bromo-4' -nitroacetophenone.
In one embodiment of the first aspect, the dimethylsulfoxide is ultra-dry dimethylsulfoxide.
In one embodiment of the first aspect, the predetermined period of time is 5-17 hours.
In one embodiment of the first aspect, the molar ratio of the 4-nitrophthalenediamine to the halogen-substituted p-nitroacetophenone is 1: 1.
In one embodiment of the first aspect, the process further comprises a quenching step comprising adding water to the reaction system after a predetermined period of time has elapsed, and precipitating and separating the crude dinitrosubstituted quinoxaline.
In one embodiment of the first aspect, the process further comprises a purification step comprising washing the crude dinitro-substituted quinoxaline with water, then dissolving in methylene chloride, washing with aqueous sodium chloride, drying, removing the solvent and then purifying with a silica gel column to obtain the dinitro-substituted quinoxaline.
In a second aspect, the present application provides a method of synthesizing a heat resistant polyimide, characterized in that the method comprises the steps of:
s1: reacting a diamino-substituted quinoxaline with an acid anhydride to obtain a polyamic acid; and
s2: performing thermal imidization on the polyamide acid to obtain heat-resistant polyimide;
wherein the diamino-substituted quinoxaline is 3/2- (4-aminophenyl) -6-aminoquinoxaline.
In one embodiment of the second aspect, the acid anhydride is one or more of 1,2,4, 5-pyromellitic anhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, and 3,3 ', 4, 4' -diphenylmethylether tetracarboxylic dianhydride.
In a third aspect, the present application provides a heat resistant polyimide prepared by the method as described in the second aspect.
In one embodiment of the third aspect, the 5% thermal decomposition temperature of the heat resistant polyimide is 528-560 ℃.
In one embodiment of the third aspect, the glass transition temperature of the heat resistant polyimide is 413-444 ℃.
Compared with the prior art, the synthesis process has the beneficial effects of low cost, mild reaction conditions and environmental protection, and is suitable for mass production.
Drawings
FIG. 1 shows the NMR spectrum of QHDN according to example 1.
FIG. 2 shows the NMR carbon spectrum of QHDN according to example 1.
FIG. 3 shows the NMR spectrum of QHDA according to example 1.
FIG. 4 shows the NMR carbon spectrum of QHDA according to example 1.
FIG. 5 shows total reflection infrared spectra of polyimide films according to examples 13 to 16. In FIG. 5, the abscissa is the wave number (cm)-1) And the ordinate represents the transmittance (%).
FIG. 6 shows ultraviolet absorption spectra of polyimide films according to examples 13 to 16. In fig. 6, the abscissa represents the wavelength (nm) and the ordinate represents the transmittance (%).
FIG. 7 shows thermogravimetric analysis (TGA) profiles of polyimide films according to examples 13-16. In FIG. 7, the abscissa represents temperature (. degree. C.) and the ordinate represents weight (%).
FIG. 8 shows dynamic thermo-mechanical analysis (DMA) patterns of polyimide films according to examples 13-16. In FIG. 8, the abscissa is temperature (. degree. C.) and the ordinate is tan.
FIG. 9 shows thermomechanical analysis (TMA) patterns of polyimide films according to examples 13-16. In fig. 9, the abscissa is temperature (deg.c) and the ordinate is the change in size (micrometers).
FIG. 10 shows dielectric constant patterns of polyimide films according to examples 13 to 16. In fig. 10, the abscissa is frequency (Hz) and the ordinate is dielectric constant.
FIG. 11 shows dielectric loss spectra of polyimide films according to examples 13-16. In fig. 11, the abscissa is frequency (Hz) and the ordinate is dielectric loss.
Detailed Description
Aminoquinoxaline or a derivative thereof is a novel diamine monomer, and polymers such as polyimide and the like synthesized by utilizing the aminoquinoxaline or the derivative thereof have excellent thermal stability and chemical stability. Nitroquinoxaline or a derivative thereof is a precursor compound for synthesizing aminoquinoxaline or a derivative thereof, and a process for converting nitro group into amino group, such as catalytic hydrogenation reduction, hydrazine hydrate reduction and the like, is well established in the industry. However, the prior art methods for the synthesis of dinitro-substituted quinoxalines, particularly 3/2- (4-nitrophenyl) -6-nitroquinoxaline, are either expensive or not environmentally friendly. Accordingly, there is a continuing need in the art to develop a low cost and environmentally friendly method for the synthesis of 3/2- (4-nitrophenyl) -6-nitroquinoxaline.
In a first aspect, the present application provides a method for synthesizing 3/2- (4-nitrophenyl) -6-nitroquinoxaline, the method comprising reacting 4-nitrophthalenediamine with a halogen-substituted p-nitroacetophenone in dimethyl sulfoxide for a predetermined period of time at room temperature to obtain 3/2- (4-nitrophenyl) -6-nitroquinoxaline (QHDN) crude product.
In a preferred embodiment, the synthetic route of the method is as follows:
in the above synthetic schemes, X represents halogen, preferably bromine.
3/2- (4-aminophenyl) -6-aminoquinoxaline (QHDA) was obtained by reducing 3/2- (4-nitrophenyl) -6-nitroquinoxaline's nitro group to an amino group. The heat-resistant polyimide can be prepared by using QHDA as a diamine monomer and reacting with an anhydride monomer.
In a second aspect, the present application provides a method of synthesizing a heat resistant polyimide, the method comprising the steps of:
s1: reacting a diamino-substituted quinoxaline with an acid anhydride to obtain a polyamic acid; and
s2: performing thermal imidization on the polyamide acid to obtain heat-resistant polyimide;
wherein the diamino-substituted quinoxaline is 3/2- (4-aminophenyl) -6-aminoquinoxaline.
In a preferred embodiment, the synthetic route of the method is as follows:
in the above-mentioned route, Ar represents an aromatic ring structure of an acid anhydride. In a preferred embodiment, the acid anhydride may be one or more of 1,2,4, 5-pyromellitic anhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, and 3,3 ', 4, 4' -diphenylmethylether tetracarboxylic dianhydride.
In a third aspect, the present application provides a polyimide prepared by the method as described in the second aspect. The polyimides described herein have good heat resistance.
Examples
The present application will now be described and illustrated in further detail with reference to the following examples. All chemical raw materials can be purchased from the market unless otherwise specified. 4-Nitro-o-phenylenediamine and 2-bromo-4' -nitroacetophenone were purchased from Annaiji chemical with a purity of 98%. Dimethyl sulfoxide was purchased from Annaiji chemical with ultra-dry purity. Those skilled in the art will appreciate that the following embodiments are exemplary only.
In the examples described below, the characterization methods used are as follows.
Nuclear magnetic resonance hydrogen/carbon spectrum (1H NMR、13C NMR)：
Nuclear magnetic resonance spectrum of reaction product and intermediate (1H NMR and13c NMR) spectra were obtained on brueck AVANCE III HD 400/500, germany. The sample preparation method comprises the following steps: in a clean and dry glass magnetic tube, about 10mg of the sample was completely dissolved in about 0.5mL of deuterated reagent. The better soluble product was deuterated chloroform as solvent (CDCl)3) The product is dissolved at room temperature, the product with poor solubility takes deuterated dimethyl sulfoxide (DMSO-d 6) as a solvent, DMSO-d6 is easy to solidify at low room temperature, and blowing is needed before loading. Tetramethylsilane (TMS) was used as an internal standard for the test at room temperature, and the chemical shift was 0 ppm.
Fourier Infrared transform Spectroscopy (FT-IR):
mixing proper amount of sample with potassium bromide powder in dry environment, grinding thoroughly, and homogenizingAnd preparing transparent thin slices on a tablet press. The model of the infrared spectrometer is Nicolet 6700, and the scanning range is set to 4000--1Resolution was set to 2cm-1The number of scans was set to 32, and the average value was automatically obtained.
Gel Permeation Chromatography (GPC):
the Hitachi gel permeation chromatograph (GPC LC-20AD) was adjusted with polystyrene standards and used to measure the molecular weight (M) of the polyamic acid solutionnAnd Mw) And molecular weight distribution (PDI). Samples were taken and diluted to 1mg/mL by calculating the solids content of the polyamic acid, supplemented with chromatographically pure DMAc, and filtered repeatedly until needed. After the sample injector is rinsed for many times, 100 mul of sample solution is loaded, and is rinsed by chromatographic pure DMAc, the flow rate is set to be 0.6 mL/min, the testing time is 15min, and the column temperature is set to be 40 ℃.
Total reflectance Infrared Spectroscopy (ATR-FTIR):
the structural characteristics of the polyimide film are tested by adopting a total reflection accessory on a Nicolet 6700 infrared spectrometer, and the resolution ratio is 4cm-1The scanning range is set to 4000-650cm-1The number of scans was set to 32.
Ultraviolet visible spectrum (UV-Vis):
the optical transmittance of the polyimide film was analyzed by Shimadzu UV-1800 Spectrophotometer, Japan, and the scanning range was set to 200--1And 32 scans at room temperature.
Thermal performance analysis (TGA & DMA & TMA):
the thermal weight loss behavior of the polyimide film is performed on a TA Discovery 550 thermogravimetric analyzer (TGA) under the protection of nitrogen, the gas flow is 50mL/min, the temperature is increased from room temperature to 120 ℃ at 20 ℃/min and stays for 15min, and then the temperature is increased from 50 ℃ to 800 ℃ at 10 ℃/min.
Glass transition temperature (T)g) The process was carried out on a TA Q800 dynamic thermomechanical analyzer (DMA), cutting the polyimide film into rectangular strips of uniform width, setting the loading frequency at 1Hz, increasing from 30 ℃ to 500 ℃ at a rate of 5 ℃/min, and protecting with nitrogen.
The thermal dimensional stability of the polyimide film was analyzed by a TA Q400 thermomechanical analyzer (TMA) in tensile mode to determine the change in the dimensions of the bars with increasing temperature. The polyimide film is prepared into a long and thin strip shape with uniform width, the static load is 0.05N, the heating rate is 5 ℃/min, the heating range is from room temperature to 400 ℃, and the nitrogen flow is 50 mL/min. The temperature programming step is divided into two parts, the temperature is raised at the same speed in the first step and then reduced to eliminate the residual internal stress of the film in the thermal imidization, and curve data of the second step of heating to 400 ℃ is recorded.
Mechanical property analysis:
the mechanical property of the polyimide film is measured by a Sagitaijie SUST CMT1104 universal tensile testing machine, a sample is cut into a rectangular strip, the traction rate is 10mm/min, and the average value of the multiple effective test results is taken.
And (3) dielectric property analysis:
the dielectric property of the polyimide film is measured by a German Novocontrol Concept 40 broadband dielectric resistance spectrometer, a square sample piece with the side length larger than 2cm is prepared, after the square sample piece is dried for two hours at the temperature of 80 ℃, copper is covered on the front side and the back side of the sample in a drying chamber by a vacuum electrodeposition method, the thickness of the film is measured by a thickness gauge, the electrical property of the sample is measured by a parallel plate capacitance method, and the measurement frequency range is 102～106Hz。
3/2- (4-Nitrophenyl) -6-nitroquinoxaline Synthesis example
Example 1
In a 250mL glass bottle in the form of a single-neck eggplant, 4-nitrophthalenediamine (7.66g, 50mmol) and 2-bromo-4' -nitroacetophenone (12.20g, 50mmol) were dissolved in 100mL of ultra-dry dimethyl sulfoxide, and the neck of the bottle was vented with a rubber hose connected with a glass joint. The mixture was stirred rapidly at room temperature for 12 hours, and the color of the system gradually changed from red to brown during the reaction. After the reaction was completed, the reaction was quenched by pouring 100mL of distilled water into the system, and then the mixture was poured into a large amount of distilled water (1L), and the product was precipitated from the mixed solution. The precipitate was filtered under vacuum and washed repeatedly with large amounts of water to remove residual dimethyl sulfoxide. The solid was redissolved in methylene chloride, washed with aqueous sodium chloride (200 mL. times.3), and dried over anhydrous magnesium sulfate at rest. The organic solvent was then removed by slow depressurization at 40 ℃ by a rotary evaporator to give the crude solid product. The crude product was purified by a 100-mesh 200-mesh silica gel column using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 2:1 as eluent to obtain the nitro compound QHDN (8.50g, 57%).
QHDN (7.00g, 22mmol) was dissolved in 200mL of an anhydrous methanol solution, and after stirring until the system became homogeneous, 5% by mass of palladium-carbon powder (0.70g) was added. The gas atmosphere in the reaction system was replaced with hydrogen gas using a hydrogen gas bag, the reaction mixture was stirred at room temperature for 12 hours by applying a load to the hydrogen gas bag, and the progress of the reaction was monitored by thin layer chromatography. After completion of the reaction, the palladium/carbon catalyst was filtered off with celite, and the filtrate was concentrated under reduced pressure and then recrystallized from methanol to give a yellow powder (5.14g, 75%).
The hydrogen nuclear magnetic resonance spectrum and the carbon nuclear magnetic resonance spectrum of 3/2- (4-nitrophenyl) -6-nitroquinoxaline QHDN according to example 1 were measured, respectively, and the obtained spectra are shown in FIG. 1 and FIG. 2, respectively. Of QHDN1H NMR (FIGS. 2-5) and13c NMR (FIGS. 2-6) data are as follows:
1H NMR(DMSO-d 6500 MHz): 9.92-9.91 (number 2, 1H), 9.00-8.98 (number 1, 1H), 8.70-8.67 (number 3, 2H), 8.65-8.61 (number 6, 1H), 8.50-8.48 (number 5, 2H), 8.45-8.42 (number 4, 1H).
13C NMR(DMSO-d6125 MHz): 151.50 (position 8), 149.33 (position 12), 148.59 (position 1), 147.68 (position 7), 146.90 (position 2), 144.26 (position 4), 141.47-141.46 (position 9), 140.72-140.67 (position 6), 131.87-131.42 (position 3), 129.80-129.62 (position 10), 125.84-125.47 (position 5), 124.67-124.40 (position 11).
In addition, the hydrogen nuclear magnetic resonance spectrum and the carbon nuclear magnetic resonance spectrum of 3/2- (4-aminophenyl) -6-aminoquinoxaline QHDA according to example 1 were measured, respectively, and the obtained spectra are shown in FIG. 3 and FIG. 4, respectively. Of QHDA1H NMR (FIGS. 2 to 7),13C NMR (FIGS. 2-8), FTIR and HRMS (FIGS. 2-9) data are as follows:
1H NMR(DMSO-d 6500 MHz): 9.14-8.97 (number 1H), 8.02-7.94 (number 6 2H), 7.73-7.68 (number 5 1H), 7.24-7.11 (number 2 1H), 6.96-6.91(position 4, 1H), 6.73-6.71 (position 7, 2H), 5.97-5.93 (position 3, 2H), 5.67-5.56 (position 8, 2H).
13C NMR(DMSO-d6125 MHz): 151.35-151.27 (position 12), 151.00-150.56 (position 1), 149.79-147.06 (position 2), 144.48-143.03 (position 8), 142.74-137.51 (position 3), 135.86-134.86 (position 7), 129.68-127.92 (position 10), 128.68 (position 5), 124.57-124.25 (position 9), 122.64-120.91 (position 6), 114.37-114.26 (position 11), 106.03-105.72 (position 4).
Examples 2 to 12
Examples 2-12 were obtained by varying the amount of starting materials and reaction time in the same synthetic procedure as in example 1. The specific reaction conditions and 3/2- (4-nitrophenyl) -6-nitroquinoxaline QHDN yields of examples 2-12 are given in Table 1 below.
Table 1: examples 2-12 raw material usage, reaction conditions and product yields.
Polyimide preparation examples
Example 13
Under the protection of nitrogen and an ice-water bath, 11.81g (50mmol) of QHDA powder is uniformly dissolved in DMAc, 10.91g (50mmol) of 1,2,4, 5-pyromellitic dianhydride (PMDA) is added in 2-3 batches and stirred for about 12 hours at room temperature to obtain a uniform polyamic acid glue solution. Removing bubbles involved in the glue solution in the reaction by a centrifugal defoaming machine. Uniformly scraping PAA glue solution on the surface of a dried glass plate by using a scraper with the gap width of 250 mu m, removing bubbles in the polyamide acid film again by a vacuumizing mode, and performing hot imidization in a muffle furnace by using a fixed temperature-rising program (115 ℃/15min, 140 ℃/15min, 200 ℃/30min, 250 ℃/5min and 380 ℃/90min) to obtain the polyimide film. After cooling to room temperature, the polyimide film was immersed in hot water, peeled from the glass substrate, and dried at 80 ℃ for 2 hours.
Example 14
Under the protection of nitrogen and an ice-water bath, 11.81g (50mmol) of QHDA powder is uniformly dissolved in DMAc, 14.71g (50mmol) of 4, 4' -biphenyl tetracarboxylic dianhydride (BPDA) is added in 2-3 batches, and the mixture is stirred for about 12 hours at room temperature to obtain a uniform polyamic acid glue solution. Removing bubbles involved in the glue solution in the reaction by a centrifugal defoaming machine. Uniformly scraping PAA glue solution on the surface of a dried glass plate by using a scraper with the gap width of 250 mu m, removing bubbles in the polyamide acid film again by a vacuumizing mode, and performing hot imidization in a muffle furnace by using a fixed temperature-rising program (115 ℃/15min, 140 ℃/15min, 200 ℃/30min, 250 ℃/5min and 380 ℃/90min) to obtain the polyimide film. After cooling to room temperature, the polyimide film was immersed in hot water, peeled from the glass substrate, and dried at 80 ℃ for 2 hours. A polyimide film according to example 14 was obtained.
Example 15
Under the protection of nitrogen and an ice water bath, 11.81g (50mmol) of QHDA powder is uniformly dissolved in DMAc, 16.11g (50mmol) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride (BTDA) is added in 2-3 batches and stirred for about 12 hours at room temperature to obtain a uniform polyamic acid glue solution. Removing bubbles involved in the glue solution in the reaction by a centrifugal defoaming machine. Uniformly scraping PAA glue solution on the surface of a dried glass plate by using a scraper with the gap width of 250 mu m, removing bubbles in the polyamide acid film again by a vacuumizing mode, and performing hot imidization in a muffle furnace by using a fixed temperature-rising program (115 ℃/15min, 140 ℃/15min, 200 ℃/30min, 250 ℃/5min and 380 ℃/90min) to obtain the polyimide film. After cooling to room temperature, the polyimide film was immersed in hot water, peeled from the glass substrate, and dried at 80 ℃ for 2 hours. A polyimide film according to example 15 was obtained.
Example 16
Under the protection of nitrogen and an ice-water bath, 11.81g (50mmol) of QHDA powder is uniformly dissolved in DMAc, 15.5g (50mmol) of 3,3 ', 4, 4' -diphenylmethylether tetracarboxylic dianhydride (OTDA) is added in 2-3 batches, and the mixture is stirred at room temperature for about 12 hours to obtain a uniform polyamic acid glue solution. Removing bubbles involved in the glue solution in the reaction by a centrifugal defoaming machine. Uniformly scraping PAA glue solution on the surface of a dried glass plate by using a scraper with the gap width of 250 mu m, removing bubbles in the polyamide acid film again by a vacuumizing mode, and performing hot imidization in a muffle furnace by using a fixed temperature-rising program (115 ℃/15min, 140 ℃/15min, 200 ℃/30min, 250 ℃/5min and 380 ℃/90min) to obtain the polyimide film. After cooling to room temperature, the polyimide film was immersed in hot water, peeled from the glass substrate, and dried at 80 ℃ for 2 hours. A polyimide film according to example 16 was obtained.
The molecular structure of the polyimide film is characterized by a characteristic peak of total reflection infrared detection, and the characterization result is shown in figure 5. 1604/1601cm-1Infrared absorption peak (C ═ N stretching vibration) at (b) confirmed that the quinoxaline ring structure was successfully introduced into the PI backbone. Amide groups at 1550 and 1660cm-1The absorption peak at (A) disappeared and the imide ring was observed at 1776/1778cm-1(asymmetric stretching vibration of C ═ O), 1708/1713cm-1(C-O symmetric stretching vibration) 1357/1356cm-1(stretching vibration of C-N-C) and 725cm-1Characteristic absorption peaks at positions (C ═ O bending vibration) and the like indicate that the polyamic acid has been successfully cyclized to polyimide.
The polyamic acids of examples 13 to 16 were tested for the number average molecular weight and the weight average molecular weight, and the polyimide films of examples 13 to 16 were tested for the optical properties, thermal properties, mechanical properties, and dielectric properties, respectively. The test results are shown in FIGS. 6-11. Some key performance parameters of the polyimide films of examples 13 to 16 are shown in tables 2 to 4 below.
Table 2 molecular weights of polyamic acids according to examples 13 to 16 and optical properties of polyimide films.
| Example numbering | Mn(×103) | Mw(×103) | PDI | Maximum cutoff wavelength of ultraviolet |
| Example 13 | 20 | 53 | 2.7 | 516nm |
| Example 14 | 15 | 38 | 2.5 | 490nm |
| Example 15 | 22 | 60 | 2.7 | 505nm |
| Example 16 | 11 | 28 | 2.5 | 477nm |
Table 3 thermal properties of the polyimide films according to examples 13 to 16.
Table 4 mechanical and electrical properties of the polyimide films according to examples 13 to 16.
| Example numbering | σmax(MPa) | εb(％) | E(GPa) | εr | tanδ(×10-3) |
| Example 13 | 57±3 | 1.1±0.2 | 6.2±0.4 | 3.8 | 7.8 |
| Example 14 | 195±7 | 8.2±0.7 | 3.9±0.4 | 3.7 | 6.8 |
| Examples15 | 209±4 | 8.3±0.5 | 4.1±0.4 | 3.8 | 6.5 |
| Example 16 | 172±4 | 7.4±0.3 | 3.4±0.2 | 3.9 | 4.7 |
In Table 3, Td 5％Denotes the thermal decomposition temperature at 5% weight loss, Td 10％Thermal decomposition temperature, R, representing 10% weight losswRepresents the char yield after firing to 800 ℃. In Table 4,. sigma.maxDenotes tensile strength, E denotes initial modulus,bthe elongation at break is shown byrRepresents the dielectric constant. From the data, the QHDA structure without side groups is better in linearity, hydrogen bonds are more easily generated to enhance intermolecular interaction force, so that corresponding polyimide chain segments are tightly stacked, and the polyimide prepared from the QHDA has the best comprehensive performance including the thermal weight loss temperature (T) of 528-560 DEG Cd 5％) High T at 413-444 ℃gCTE as low as 1ppm/K, and excellent tensile strength (209MPa) and initial modulus (6.2 GPa). QHDA-PIs have the strongest intermolecular interactions due to hydrogen bond formation, and exhibit the highest Tg(413 ℃ C.). about.444 ℃. Generally speaking, the introduction of flexible structure will lead to the reduction of glass transition temperature of the polymer, but ether bond and carbonyl group in ODPA and BTDA form free radical to generate crosslinking in the high-temperature thermal imidization process, and free rotation of chain segment is limited, thereby increasing T of polyimideg. The QHDA without side group brings the best linearity and the best linearity for QHDA-PIsLow in-plane CTE values.
Further, it can be seen that the quinoxaline type polyimide film has a higher dielectric constant and a lower dielectric loss in a lower frequency range (data corresponding to 1kHz is shown in table 4).
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (10)
1. A method for synthesizing dinitro-substituted quinoxaline is characterized by comprising the steps of reacting 4-nitrophthalenediamine and halogen-substituted p-nitroacetophenone in dimethyl sulfoxide for a preset time period at room temperature to obtain a dinitro-substituted quinoxaline crude product;
wherein, the dinitro-substituted quinoxaline is 3/2- (4-nitrophenyl) -6-nitroquinoxaline, and the structure of the dinitro-substituted quinoxaline is shown in the following general formula (1):
2. the method for the synthesis of dinitro-substituted quinoxalines according to claim 1, wherein said halogen-substituted p-nitroacetophenone is 2-bromo-4' -nitroacetophenone;
the dimethyl sulfoxide is ultra-dry dimethyl sulfoxide.
3. The method for synthesizing dinitro-substituted quinoxaline according to claim 1, wherein the predetermined period of time is 5 to 17 hours.
4. The method for the synthesis of dinitro-substituted quinoxalines according to claim 1, wherein the molar ratio of said 4-nitrophthalenediamine to said halogen-substituted p-nitroacetophenone is 1: 1.
5. The method for synthesizing a dinitro-substituted quinoxaline according to claim 1, further comprising a quenching step, wherein the quenching step comprises adding water to the reaction system after a predetermined period of time has been reached, and precipitating and separating the crude dinitro-substituted quinoxaline.
6. The method for synthesizing a dinitro-substituted quinoxaline according to claim 5, further comprising a purification step comprising washing the crude dinitro-substituted quinoxaline with water, dissolving in methylene chloride, washing with an aqueous solution of sodium chloride, drying, removing the solvent, and purifying with a silica gel column to obtain the dinitro-substituted quinoxaline.
7. A method of synthesizing a heat resistant polyimide, comprising the steps of:
s1: reacting a diamino-substituted quinoxaline with an acid anhydride to obtain a polyamic acid; and
s2: performing thermal imidization on the polyamide acid to obtain heat-resistant polyimide;
wherein the diamino-substituted quinoxaline is 3/2- (4-aminophenyl) -6-aminoquinoxaline.
8. The method of synthesizing heat resistant polyimide according to claim 7, wherein the acid anhydride is one or more of 1,2,4, 5-pyromellitic anhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, and 3,3 ', 4, 4' -diphenylmethylether tetracarboxylic dianhydride.
9. A heat resistant polyimide prepared by the method of claim 7 or 8.
10. The heat-resistant polyimide as described in claim 9, wherein the heat-resistant polyimide has a 5% thermal decomposition temperature of 528-560 ℃;
the glass transition temperature of the heat-resistant polyimide is 413-444 ℃.
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