CN115368255A - Anthraquinone-based diamine monomer, cyan intrinsic polyimide derived from anthraquinone-based diamine monomer and preparation method of cyan intrinsic polyimide - Google Patents
Anthraquinone-based diamine monomer, cyan intrinsic polyimide derived from anthraquinone-based diamine monomer and preparation method of cyan intrinsic polyimide Download PDFInfo
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- CN115368255A CN115368255A CN202210612142.8A CN202210612142A CN115368255A CN 115368255 A CN115368255 A CN 115368255A CN 202210612142 A CN202210612142 A CN 202210612142A CN 115368255 A CN115368255 A CN 115368255A
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- anthraquinone
- diamine monomer
- cyan
- based diamine
- intrinsic
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- 239000000178 monomer Substances 0.000 title claims abstract description 105
- 150000004985 diamines Chemical class 0.000 title claims abstract description 64
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 47
- 229920001721 polyimide Polymers 0.000 title claims description 68
- 239000004642 Polyimide Substances 0.000 title claims description 55
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims abstract description 30
- -1 anthraquinone diamine Chemical class 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229920005575 poly(amic acid) Polymers 0.000 claims description 20
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- 150000008064 anhydrides Chemical class 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000012456 homogeneous solution Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 3
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- CAHGWVAXFJXDNI-UHFFFAOYSA-N 1,4-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(Cl)=CC=C2Cl CAHGWVAXFJXDNI-UHFFFAOYSA-N 0.000 description 1
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
- C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
- C07C225/32—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by at least three rings
- C07C225/34—Amino anthraquinones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- 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
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- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
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- 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
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Abstract
The present application relates to an anthraquinone-based diamine monomer having a structure represented by the following general formula I:
the method adopts a chemical synthesis mode to introduce a cyan anthraquinone diamine monomer into a PI main chain to prepare the intrinsic cyan PI. Because of chemical direct bonding, the problems of uneven dispersion and poor thermal stability are effectively solved, and simultaneously, the problems of uneven dispersion and poor thermal stability are ensuredThe color of the introduced color body is remained, and the influence on other performances of the PI film is small.
Description
Technical Field
The present invention relates to the field of organic synthesis technologies, and in particular, to an anthraquinone-based diamine monomer, a cyan intrinsic polyimide derived from the anthraquinone-based diamine monomer, and a preparation method thereof, and in particular, to an anthraquinone-based diamine monomer, a preparation method of the anthraquinone-based diamine monomer, a cyan intrinsic polyimide derived from the anthraquinone-based diamine monomer, and a preparation method of the cyan intrinsic polyimide.
Background
Polyimide (PI) films have excellent heat resistance, chemical resistance, and mechanical strength, as well as good electrical strength and insulating properties, and are widely used in the fields of microelectronics, liquid crystal display, medical treatment, and other industries. With the development of the electronic industry, the requirement for polyimide properties is increasing, and in some special fields, PI films of special colors, such as cyan-green adhesive tapes, cyan-green labels, and cyan-green PCB protective films, are required, and they can also be used as blue light agents.
At present, the preparation of the color PI film mainly adopts inorganic filler or organic pigment as a preparation means. For example, patent document CN110724287A of Ningbo Jinshan company describes that an inorganic green pigment is added to a polyamic acid substrate after surface modification, and cast into a film, which can be stably used at 250 ℃. Patent document CN111647156A of guangzhou starry materials ltd describes that introduction of anthracene-pyrene-structured diamine into polyimide reduces the stacking and electron cloud density of its molecular chains to show a light blue appearance.
However, the existing preparation methods of colored polyimide have the following defects:
1. the preparation process is complex, and the filler needs to be modified in advance so as to be dispersed in the PI matrix more uniformly.
2. Although the mechanical property and the thermal property of the PI film can be improved to a certain extent by introducing the inorganic filler, the insulativity and the breakdown strength of the PI film can be damaged, and the application of the PI film in the field of electronic industry is adversely affected. Meanwhile, the inorganic pigment is not environment-friendly enough, is easy to agglomerate, fall off, settle and the like, and has poorer tinting strength in a polyimide system.
3. Although the introduction of the organic pigment avoids influencing the electrical property of the PI film, the application of the PI film in the high-temperature field is hindered by the lower thermal decomposition temperature of the organic pigment, and the PI film is easy to decompose under the influence of environmental factors and has poor weather resistance.
For this reason, there is a continuing need in the art to develop a cyan intrinsic polyimide and a method for preparing the same.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present application to provide an anthraquinone-based diamine monomer, a cyan intrinsic polyimide derived therefrom, and a method of preparing the same.
In order to solve the above technical problem, the present application provides the following technical solutions:
in a first aspect, the present application provides an anthraquinone-based diamine monomer having a compound name of 1, 4-bis ((4-aminophenyl) amino) -9, 10-anthrone, exhibiting a cyan color, and having a structure represented by the following general formula I:
in a second aspect, the present application provides a method for preparing an anthraquinone-based diamine monomer, the method comprising the steps of: in the presence of sodium bisulfite, anhydrous sodium sulfate and ethanol and in a nitrogen atmosphere, 1, 4-dihydroxy anthraquinone leuco body is used as an initiator to react 1, 4-dihydroxy anthraquinone with p-phenylenediamine to obtain the anthraquinone-based diamine monomer with the structure shown in the general formula I. In the preparation method, 1, 4-dihydroxy anthraquinone leuco is used as an initiator, so that the method not only has the effect of initiating reaction, but also plays a catalytic role in the reaction; sodium bisulfite is used as an antioxidant, and anhydrous sodium sulfate is used for absorbing water produced in the reaction process.
Preferably, the molar ratio of the 1, 4-dihydroxyanthraquinone leuco body, the 1, 4-dihydroxyanthraquinone, the p-phenylenediamine, the sodium bisulfite and the anhydrous sodium sulfate is (0.2-0.35): 1, (2-4): 0.05-0.2): 0.8-5. More preferably, the molar ratio is 0.3.
Preferably, the reaction temperature is 80-100 ℃, and the reaction time is 10-14h. More preferably, the reaction temperature is 85 ℃ and the reaction time is 12 hours.
In a third aspect, the present application provides a process for preparing another anthraquinone-based diamine monomer, the process comprising the steps of: in the presence of DMF and in a nitrogen atmosphere, 1, 4-dihydroxy anthraquinone reacts with p-phenylenediamine to obtain the anthraquinone diamine monomer with the structure shown in the general formula I.
Preferably, the molar ratio of the 1, 4-dihydroxyanthraquinone to the p-phenylenediamine is 1. More preferably, the molar ratio is 1.
Preferably, the reaction temperature is 150-180 ℃, and the reaction time is 10-14h. More preferably, the reaction temperature is 160 ℃ and the reaction time is 12 hours.
In a fourth aspect, the present application also provides a cyan intrinsic polyimide comprising structural units derived from the foregoing anthraquinone-based diamine monomer, structural units derived from a diamine monomer, and structural units derived from an acid anhydride monomer, wherein the structural units derived from the foregoing anthraquinone-based diamine monomer account for 1% to 100% of the total number of moles of the structural units derived from the foregoing anthraquinone-based diamine monomer and the structural units derived from the diamine monomer.
Preferably, the ratio of the total number of moles of the structural unit derived from an anthraquinone-based diamine monomer to the total number of moles of the structural unit derived from a diamine monomer to the number of moles of the structural unit derived from an acid anhydride monomer is 1.
Preferably, the acid anhydride monomer is one or more of the following: hexafluoro dianhydride, 4'- (acetylene-1, 2-diyl) diphthalic anhydride, pyromellitic dianhydride, 3',4 '-biphenyltetracarboxylic dianhydride, 3',4,4 '-benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 3',4' -diphenylsulfone tetracarboxylic dianhydride, naphthalene-1, 4,5, 8-tetracarboxylic dianhydride, and diphenyl sulfide dianhydride; more preferably, the anhydride monomer is hexafluorodianhydride.
Preferably, the diamine monomer is one or more of the following: : <xnotran> 2,2'- ( ) -4,4' - ,4,4'- , , ,4,4' - ,3,4 '- ,4,4' - ,4,4'- ,1,3- (4- ) ,1,4- (4- ) ,4,4' - -2,2'- ,2- (4- ) -5- ,2- (4- ) -5- ,1,4- (3- ) ,1,3- (3- -4- - ) ,2- (4- ) -6- ,2,2- - (5- ) 2,2' - - (6- ); </xnotran> More preferably, the diamine monomer is 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl or 4,4' -diaminodiphenyl ether.
In a fifth aspect, the present application provides a process for preparing a cyan intrinsic polyimide, the process comprising the steps of:
A. mixing the anthraquinone-based diamine monomer and the diamine monomer according to the claim 1 in a preset molar ratio under the conditions of no water, no oxygen and nitrogen protection, stirring until the mixture is dissolved to form a homogeneous solution, then adding an anhydride monomer, and stirring and reacting for a preset time period in a cold water bath to obtain a cyan polyamic acid solution;
B. coating the cyan polyamic acid solution on a substrate after vacuum defoaming, and performing thermal imidization to obtain cyan intrinsic polyimide; or
C. And adding acetic anhydride/pyridine solution into the cyan polyamic acid solution, stirring overnight, precipitating in ethanol solution, drying in vacuum, preparing a solution with the solid content of 8-12% from the dried product, coating the solution on a substrate, and removing the solvent to obtain cyan intrinsic polyimide.
Preferably, in step B, the coating is performed by using an automatic film coating machine, the substrate is a glass plate, and the temperature-rising curing procedure for performing thermal imidization is as follows: 80 ℃/3h,100 ℃/1h,200 ℃/2h,300 ℃/2h or 80 ℃/3h,100 ℃/1h,200 ℃/2h.
Preferably, in step C, the coating is performed by using an automatic coating machine, the substrate is a glass plate, and the desolvation adopts a temperature-rising curing procedure as follows: 80 ℃/3h,100 ℃/1h,200 ℃/2h.
Preferably, in the step A, the molar ratio of the anthraquinone-based diamine monomer to the diamine monomer is 1-100;
the ratio of the total mole number of the anthraquinone-based diamine monomer and the diamine monomer to the mole number of the anhydride monomer is 1.
Compared with the prior art, the beneficial effect of this application lies in:
1. the application synthesizes cyan anthraquinone diamine monomer with the chemical name of 1, 4-bis ((4-aminophenyl) amino) -9, 10-anthrone for the first time.
2. The method adopts a chemical synthesis mode to introduce a cyan anthraquinone diamine monomer into a PI main chain to prepare the intrinsic cyan PI. Because the chemical direct bonding is adopted, the problems of uneven dispersion and poor thermal stability are effectively solved, the color of the introduced color body is kept, and the influence on other performances of the PI film is small.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows a nuclear magnetic hydrogen spectrum of an anthraquinone-based diamine monomer prepared according to the method of example 1;
FIG. 2 shows a nuclear magnetic carbon spectrum of an anthraquinone-based diamine monomer prepared according to the method of example 1;
FIG. 3 shows an infrared spectrum of an anthraquinone-based diamine monomer prepared according to the method of example 1;
FIG. 4 shows a UV spectrum of an anthraquinone-based diamine monomer prepared according to the method of example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the invention.
In one embodiment, the present application provides an anthraquinone-based diamine monomer having the compound name 1, 4-bis ((4-aminophenyl) amino) -9, 10-anthrone, having the structure shown in the following formula I:
in one embodiment, the present application provides a method of making the anthraquinone-based diamine monomer described above, the method comprising the steps of: in the presence of sodium bisulfite, anhydrous sodium sulfate and ethanol and in a nitrogen atmosphere, 1, 4-dihydroxy anthraquinone leuco body is used as an initiator to react 1, 4-dihydroxy anthraquinone and p-phenylenediamine to obtain the anthraquinone-based diamine monomer with the structure shown in the general formula I.
In another embodiment, the present application provides another method of preparing the anthraquinone-based diamine monomer as described above, the method comprising the steps of: in the presence of DMF and in a nitrogen atmosphere, 1, 4-dihydroxy anthraquinone reacts with p-phenylenediamine to obtain the anthraquinone diamine monomer with the structure shown in the general formula I.
The principle of preparing the cyan anthraquinone diamine monomer with the structure shown in the general formula I is as follows: the substitution of the substituent group shown in the general formula I at the 1 and 4 sites can change the electron cloud distribution density of the anthraquinone structure, so that the absorption peak of the anthraquinone structure appears red shift, and the red waveband color light at 650nm is absorbed, thereby showing cyan.
In one embodiment, the present application provides a cyan intrinsic polyimide comprising structural units derived from the foregoing anthraquinone-based diamine monomer, structural units derived from a diamine monomer, and structural units derived from an anhydride monomer, wherein the structural units derived from the foregoing anthraquinone-based diamine monomer account for 1% to 100% of the total number of moles of the structural units derived from the foregoing anthraquinone-based diamine monomer and the structural units derived from the diamine monomer.
The present application also relates to a process for preparing a cyan intrinsic polyimide as described above, comprising first reacting an anthraquinone-based diamine monomer, a diamine monomer, and an anhydride monomer to provide a cyan polyamic acid solution, and then imidizing the polyamic acid solution to provide the cyan intrinsic polyimide.
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. 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.
1. The thermal performance evaluation method comprises the following steps:
1.1 thermomechanical analysis (TMA). The prepared intrinsic cyan polyimide film was tested on a thermal analyzer (TA corporation, Q400 series, usa), and the temperature increase rate: 10 ℃/min.
1.2 dynamic thermomechanical analysis (DMA). The prepared intrinsic cyan polyimide film was tested in a dynamic thermo-mechanical analyzer (TA corporation, Q800 series, usa), and the temperature increase rate: 5 ℃/min, frequency: 1Hz.
Thermogravimetric analysis (TGA). The prepared intrinsic cyan polyimide film was tested in a dynamic thermo-mechanical analyzer (TA corporation, Q800 series, usa), and the temperature increase rate: 5 ℃/min, frequency: 1Hz.
2. Optical performance evaluation method:
the ultraviolet-visible spectrum (UV-Vis) is used. The prepared intrinsic cyan polyimide film was tested in an ultraviolet spectrophotometer (Shimadzu, japan, UV-2600) for a wavelength range of 200 to 800nm.
3. The chroma parameter evaluation method comprises the following steps:
CIE1976 color space parameters (LAB) were used. The prepared intrinsic cyan polyimide film is tested by a spectrocolorimeter (Shenzhen Sanhen, YS 6060), the light source is a D65 standard light source, and the field of view is 10 degrees.
4. Mechanical property evaluation method:
a universal tensile machine is adopted. The prepared intrinsic cyan polyimide film was subjected to characterization of tensile strength, young's modulus and elongation at break by means of a Universal tensile machine (CMT-1104, sanstejie Electrical Equipment Co., ltd., zhuhai) in accordance with Standard test method for tensile Properties of plastics (ASTM-D638). Stretching speed: 5mm/min.
5. Structure correctness evaluation method:
5.1 nuclear magnetic resonance spectroscopy. The prepared monomer 1,4-BDDA was characterized by a 600MHz nuclear magnetic resonance spectrometer (Bruker BioSpin, germany, AVANCE III HD) to determine the correctness of the product. Considering solubility, deuterated dimethyl sulfoxide (DMSO-d 6: delta H =2.50ppm, delta C =39.52 ppm) was used as a deuterated reagent, and Tetramethylsilane (TMS) was used as an internal standard, and chemical shift was 0ppm.
5.2 Infrared Spectroscopy characterization (FTIR-ATR). The prepared anthraquinone diamine monomer and the intrinsic cyan polyimide film are characterized by a Fourier infrared spectrometer (Nicolet iS5, thermoFisher science and technology Co., ltd.) in an attenuated total reflection mode, so that the monomer and the prepared film are characterized by characteristic peaks and the imidization degree of the film iS verified. The test range covers 4000-600cm -1 And the test times are set to be 32 times, the sample is directly placed on the ATR assembly during the test, and the sample is carefully cleaned after the test is finished.
Examples of monomer Synthesis
Example 1
Adding 1, 4-dihydroxyanthraquinone leuco body (0.3 mmol), 1, 4-dihydroxyanthraquinone (1 mmol), p-phenylenediamine (2.2 mmol), sodium bisulfite (0.1 mmol), anhydrous sodium sulfate (1 mmol) and 25ml of ethanol into a three-neck flask, heating the atmosphere to 85 ℃ under nitrogen, stopping the reaction after 12 hours, filtering the reaction liquid, washing the solid substance with water, and placing the solid substance in a vacuum oven for vacuum drying to obtain a cyan crude product. The crude product was purified by silica gel chromatography, eluting with an eluent (ethyl acetate) to give a cyan product, 1, 4-bis ((4-aminophenyl) amino) -9, 10-anthrone (hereinafter referred to as 1, 4-BDDA), in a yield of 90.7%.
The nuclear magnetic hydrogen spectrum and nuclear magnetic carbon spectrum of the monomer 1,4-BDDA are measured, the obtained spectrogram results are shown in figures 1 and 2, the correctness of the monomer 1,4-BDDA is determined, and the structure is shown in the following general formula I:
the result of measuring the infrared spectrogram of the monomer 1,4-BDDA is shown in figure 3, and the characterization result is as follows: v =3415,3315cm -1 The vibration peak is attributed to amino group, v =3031cm -1 The vibration peak at (A) belongs to the imino group and appears at 3031cm -1 Nearby vibrational peaks belong to carbon-hydrogen bonds on the aromatic ring. Vibration peak at 1612 was ascribed to carbonyl group, 1563cm -1 The vibration peak belongs to a nitrogen hydrogen bond, 1512, 1484cm -1 Is a characteristic vibration peak of a benzene ring,1281cm -1 the peak at (a) belongs to the vibrational peak of the carbon-nitrogen bond.
ν＝3415,3315(-NH2),3211(-NH),3031(Ar-H),1612(ketone C＝O),1563(N-H),1512,1484(benzene ring),1281(C-N)
The ultraviolet-visible spectrum of the monomer 1,4-BDDA is measured, and the spectrogram result is shown in figure 4. As can be seen from FIG. 4, the monomer has strong absorption in the visible light band of 400-700 nm.
Example 2
1, 4-dichloroanthraquinone (1 mmol), p-phenylenediamine (15 mmol) and 25ml of DMF were added to a three-neck flask, and the mixture was stirred at 160 ℃ for 12 hours under a nitrogen atmosphere and quenched by addition of water. After standing for 1h, the solid material was filtered with hot water, washed with dichloromethane/petroleum ether solution and placed in a vacuum oven for vacuum drying overnight to give a crude cyan product. The crude product was purified by silica gel chromatography eluting with eluent (ethyl acetate) to give the cyan product 1, 4-bis ((4-aminophenyl) amino) -9, 10-anthrone (1, 4-BDDA) in 89.2% yield.
The results of measuring the NMR spectrum, UV absorption spectrum and IR spectrum of monomer 1,4-BDDA prepared in this example were substantially the same as those of example 1, indicating that the structures of the monomers prepared in both examples are completely the same.
Cyan intrinsic polyimide preparation example
Example 3
This example relates to the synthesis of cyan intrinsic polyimide PI-1.
An intrinsic cyan polyimide film was prepared from 1,4-BDDA monomer and TFMB (2, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl) and 6FDA (hexafluoro dianhydride) in a molar ratio of 1, 99, by the following specific steps:
adding 0.09mmol of 1,4-BDDA monomer, 8.91mmol of TFMB and 20mL of DMAc into a 100mL three-neck round-bottom flask with a nitrogen inlet, a mechanical stirrer and a cold water bath under the conditions of fully removing water and oxygen and protecting nitrogen, and stirring until the monomers are dissolved to form a homogeneous solution; adding total 9mmol 6FDA into the solution for three times, and stirring and reacting for 14h under a cold water bath to obtain a cyan polyamic acid solution with certain viscosity.
And (3) placing the polyamic acid solution in a vacuum oven for vacuum defoamation, then uniformly coating the polyamic acid solution on a dry and clean glass plate through an automatic coating machine, and performing thermal imidization to prepare a 20-micron cyan film. The temperature-rising curing procedure is as follows: 80 ℃/3h,100 ℃/1h,200 ℃/2h and 300 ℃/2h.
Example 4
This example relates to the synthesis of cyan intrinsic polyimide PI-2.
Preparing an intrinsic cyan polyimide film by using 1,4-BDDA monomer and ODA (4, 4' -diaminodiphenyl ether) and 6FDA (hexafluoro dianhydride) with the molar ratio of 1 to 99, wherein the method comprises the following specific steps:
adding 0.09mmol of 1,4-BDDA monomer, 8.91mmol of ODA and 20mL of DMAc into a 100mL three-neck round-bottom flask provided with a nitrogen inlet, a mechanical stirrer and a cold water bath under the conditions of sufficient water removal, oxygen removal and nitrogen protection, and stirring until the monomers are dissolved to form a homogeneous solution; adding total 9mmol 6FDA into the solution for three times, and stirring and reacting for 14h in a cold water bath to obtain a cyan polyamide acid solution with certain viscosity.
And (3) placing the polyamic acid solution in a vacuum oven for vacuum defoamation, then uniformly coating the polyamic acid solution on a dry and clean glass plate through an automatic coating machine, and performing thermal imidization to prepare a 20-micron cyan film. The temperature-rising curing procedure is as follows: 80 ℃/3h,100 ℃/1h,200 ℃/2h,300 ℃/2h.
Example 5
This example relates to the synthesis of cyan intrinsic polyimide PI-3.
An intrinsic cyan polyimide film was prepared from 1,4-BDDA monomer and TFMB (2, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl) and 6FDA (hexafluoro dianhydride) in a molar ratio of 1, 99, by the following specific steps:
adding 0.09mmol of 1,4-BDDA monomer, 8.91mmol of TFMB and 20mL of DMAc into a 100mL three-neck round-bottom flask provided with a nitrogen inlet, a mechanical stirrer and a cold water bath under the conditions of sufficient water removal, oxygen removal and nitrogen protection, and stirring until the monomers are dissolved to form a homogeneous solution; adding total 9mmol 6FDA into the solution for three times, and stirring and reacting for 14h in a cold water bath to obtain a cyan polyamide acid solution with certain viscosity.
3ml of acetic anhydride/pyridine solution was added to the polyamic acid solution and stirred overnight, precipitated from the ethanol solution, and placed in a vacuum oven for vacuum drying.
And (3) preparing the dried polyimide precipitate into a solution with the solid content of 10%, uniformly coating the solution on a dry and clean glass plate by an automatic coating machine, and removing the solvent to obtain a 20-micron film. The temperature-rising curing procedure is as follows: 80 ℃/3h,100 ℃/1h,200 ℃/2h.
Example 6
This example relates to the synthesis of cyan intrinsic polyimide PI-4.
Preparing an intrinsic cyan polyimide film by using 1,4-BDDA monomer and 6FDA (hexafluoro dianhydride), and specifically comprising the following steps:
under the conditions of sufficient water removal, oxygen removal and nitrogen protection, adding 9mmol 1,4-BDDA monomer and 20mL DMAc into a 100mL three-neck round-bottom flask provided with a nitrogen inlet, a mechanical stirrer and a cold water bath, and stirring until the monomers are dissolved to form a homogeneous solution; adding total 9mmol 6FDA into the solution for three times, and stirring and reacting for 14h in a cold water bath to obtain a dark cyan polyamide acid solution with certain viscosity.
And (3) placing the polyamic acid solution in a vacuum oven for vacuum defoamation, then uniformly coating the polyamic acid solution on a dry and clean glass plate through an automatic coating machine, and performing thermal imidization to prepare the black-cyan film with the thickness of 20 mu m. The temperature-rising curing procedure is as follows: 80 ℃/3h,100 ℃/1h,200 ℃/2h and 300 ℃/2h.
Comparative example 1
This example relates to a colorless transparent polyimide film prepared by synthesizing TFMB with 6 FDA.
Mixing a mixture of 1:1 TFMB (2, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl) with 6FDA (hexafluorodianhydride) produced a colorless transparent polyimide film.
Adding 9mmol of TFMB and 20mL of DMAc into a 100mL three-neck round-bottom flask provided with a nitrogen inlet, a mechanical stirrer and a cold water bath under the conditions of sufficient water removal, oxygen removal and nitrogen protection, and stirring until the TFMB and the DMAc are dissolved to form a homogeneous solution; adding total 9mmol 6FDA into the solution for three times, and stirring and reacting for 14h in a cold water bath to obtain a colorless polyamic acid solution with certain viscosity.
And (3) placing the polyamic acid solution in a vacuum oven for vacuum defoamation, then uniformly coating the polyamic acid solution on a dry and clean glass plate through an automatic coating machine, and performing thermal imidization to prepare a colorless film with the thickness of 20 microns. The temperature-rising curing procedure is as follows: 80 ℃/3h,100 ℃/1h,200 ℃/2h and 300 ℃/2h.
Performance characterization
The LAB values, thermal properties and other properties (modulus of elasticity, tensile strength, elongation at break, coefficient of thermal expansion) of the polyimides according to examples 3 to 6 and comparative example 1 were measured, and the test results are shown in tables 1 to 3 below.
TABLE 1 LAB value results for polyimides of examples 3-6 and comparative example 1
TABLE 2 comparison of thermal Properties of polyimides of examples 3 to 6 and comparative example 1
Table 3 comparison results of other properties of polyimides of examples 3 and 5 and comparative example 1
From the above data, it can be seen that when the molar amount of the anthraquinone-based diamine monomer in the amine monomers is greater than or equal to 1%, the cyan intrinsic polyimide can be prepared without substantially affecting the thermal and mechanical properties of the cyan intrinsic polyimide. It can be further seen from the results of table 3 that the polyimides prepared in examples 3 and 5 according to the present invention have significantly improved elongation at break compared to the polyimide prepared in comparative example 1, and the polyimide prepared in example 3 has improved tensile strength compared to the polyimide prepared in comparative example 1, that is, the thermal and mechanical properties of the polyimide are moderately enhanced by the introduction of the anthraquinone and diamine monomers.
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, in light of the present disclosure, will recognize that changes may be made in the form and detail of the embodiments without departing from the scope or spirit of the application.
Claims (10)
1. An anthraquinone-based diamine monomer, characterized by having a structure represented by the following general formula I:
2. a process for the preparation of the anthraquinone-based diamine monomer according to claim 1, comprising the steps of: in the presence of sodium bisulfite, anhydrous sodium sulfate and ethanol and in a nitrogen atmosphere, 1, 4-dihydroxy anthraquinone leuco body is used as an initiator to react 1, 4-dihydroxy anthraquinone with p-phenylenediamine to obtain the anthraquinone-based diamine monomer with the structure shown in the general formula I.
3. The method for preparing anthraquinone-based diamine monomer according to claim 2, wherein the molar ratio of 1, 4-dihydroxy anthraquinone leuco body, 1, 4-dihydroxy anthraquinone, p-phenylenediamine, sodium bisulfite and anhydrous sodium sulfate is (0.2-0.35) to 1 (2-4) to (0.05-0.2) to (0.8-5).
4. The method for producing the anthraquinone-based diamine monomer according to claim 2, wherein the reaction temperature is 80 to 100 ℃ and the reaction time is 10 to 14 hours.
5. A method for preparing the anthraquinone-based diamine monomer according to claim 1, comprising the steps of: in the presence of DMF and in a nitrogen atmosphere, 1, 4-dihydroxy anthraquinone reacts with p-phenylenediamine to obtain the anthraquinone diamine monomer with the structure shown in the general formula I.
6. The method of claim 5, wherein the molar ratio of 1, 4-dihydroxyanthraquinone to p-phenylenediamine is from 1.
7. The method for preparing an anthraquinone-based diamine monomer according to claim 5, wherein the reaction temperature is 150-180 ℃ and the reaction time is 10-14h.
8. An intrinsic cyan polyimide comprising a structural unit derived from the anthraquinone-based diamine monomer according to claim 1, a structural unit derived from a diamine monomer, and a structural unit derived from an acid anhydride monomer, wherein the structural unit derived from the anthraquinone-based diamine monomer according to claim 1 accounts for 1% to 100% of the total molar number of the structural unit derived from the anthraquinone-based diamine monomer according to claim 1 and the structural unit derived from the diamine monomer.
9. The cyan intrinsic polyimide of claim 8, wherein the anhydride monomer is one or more of: hexafluoro dianhydride, 4'- (acetylene-1, 2-diyl) diphthalic anhydride, pyromellitic dianhydride, 3',4 '-biphenyltetracarboxylic dianhydride, 3',4,4 '-benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 3',4' -diphenylsulfone tetracarboxylic dianhydride, naphthalene-1, 4,5, 8-tetracarboxylic dianhydride, and diphenyl sulfide dianhydride;
the diamine monomer is one or more of the following: <xnotran> 2,2'- ( ) -4,4' - ,4,4'- , , ,4,4' - ,3,4 '- ,4,4' - ,4,4'- ,1,3- (4- ) ,1,4- (4- ) ,4,4' - -2,2'- ,2- (4- ) -5- ,2- (4- ) -5- ,1,4- (3- ) ,1,3- (3- -4- - ) ,2- (4- ) -6- ,2,2- - (5- ) 2,2' - - (6- ). </xnotran>
10. A process for preparing a cyan intrinsic polyimide, as defined in claim 8 or 9, comprising the steps of:
A. under the conditions of no water, no oxygen and nitrogen protection, mixing the anthraquinone-based diamine monomer and the diamine monomer according to the claim 1 in a preset molar ratio, stirring until the anthraquinone-based diamine monomer and the diamine monomer are dissolved to form a homogeneous solution, then adding an anhydride monomer, and stirring and reacting for a preset time period in a cold water bath to obtain a cyan polyamic acid solution;
B. coating the cyan polyamic acid solution on a substrate after vacuum defoaming, and performing thermal imidization to obtain cyan intrinsic polyimide; or
C. And adding acetic anhydride/pyridine solution into the cyan polyamic acid solution, stirring overnight, precipitating in ethanol solution, drying in vacuum, preparing a solution with the solid content of 8-12% from the dried product, coating the solution on a substrate, and removing the solvent to obtain cyan intrinsic polyimide.
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