CN116769161A - Polyimide with low CTE and high light transmittance, diamine monomer thereof and preparation method thereof - Google Patents
Polyimide with low CTE and high light transmittance, diamine monomer thereof and preparation method thereof Download PDFInfo
- Publication number
- CN116769161A CN116769161A CN202310750719.6A CN202310750719A CN116769161A CN 116769161 A CN116769161 A CN 116769161A CN 202310750719 A CN202310750719 A CN 202310750719A CN 116769161 A CN116769161 A CN 116769161A
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- Prior art keywords
- reaction
- polyimide
- diamine monomer
- binding agent
- acid
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- 239000000178 monomer Substances 0.000 title claims abstract description 147
- 229920001721 polyimide Polymers 0.000 title claims abstract description 145
- 150000004985 diamines Chemical class 0.000 title claims abstract description 134
- 239000004642 Polyimide Substances 0.000 title claims abstract description 101
- 238000002834 transmittance Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 79
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 185
- 239000003054 catalyst Substances 0.000 claims description 107
- 239000005457 ice water Substances 0.000 claims description 84
- 239000002253 acid Substances 0.000 claims description 79
- 239000011230 binding agent Substances 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 68
- 239000002904 solvent Substances 0.000 claims description 63
- 238000005984 hydrogenation reaction Methods 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- 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 31
- 238000003756 stirring Methods 0.000 claims description 28
- LETNCFZQCNCACQ-UHFFFAOYSA-N 2-fluoro-4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1F LETNCFZQCNCACQ-UHFFFAOYSA-N 0.000 claims description 23
- 239000012024 dehydrating agents Substances 0.000 claims description 20
- HXTYZWJVMWWWDK-UHFFFAOYSA-N cyclohexane-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1CCC(C(Cl)=O)CC1 HXTYZWJVMWWWDK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- HOTZLWVITTVZGY-UHFFFAOYSA-N 4-nitro-2-(trifluoromethyl)aniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1C(F)(F)F HOTZLWVITTVZGY-UHFFFAOYSA-N 0.000 claims description 14
- UTKUVRNVYFTEHF-UHFFFAOYSA-N 4-nitro-3-(trifluoromethyl)aniline Chemical compound NC1=CC=C([N+]([O-])=O)C(C(F)(F)F)=C1 UTKUVRNVYFTEHF-UHFFFAOYSA-N 0.000 claims description 13
- -1 diformyl chloride Chemical compound 0.000 claims description 12
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 11
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 claims description 9
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920005575 poly(amic acid) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 abstract description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002723 alicyclic group Chemical group 0.000 abstract description 4
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 77
- 239000000243 solution Substances 0.000 description 74
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 48
- 238000001914 filtration Methods 0.000 description 46
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 38
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- 239000007787 solid Substances 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 239000011521 glass Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000012065 filter cake Substances 0.000 description 26
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 19
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 18
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 239000007868 Raney catalyst Substances 0.000 description 15
- 229910000564 Raney nickel Inorganic materials 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 14
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 12
- 238000004537 pulping Methods 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 150000007529 inorganic bases Chemical class 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 10
- 150000007530 organic bases Chemical class 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- 235000011181 potassium carbonates Nutrition 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 8
- 235000015497 potassium bicarbonate Nutrition 0.000 description 8
- 239000011736 potassium bicarbonate Substances 0.000 description 8
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- LKRUZYNPJUZODM-UHFFFAOYSA-N adamantane-1,3-dicarbonyl chloride Chemical compound C1C(C2)CC3CC1(C(=O)Cl)CC2(C(Cl)=O)C3 LKRUZYNPJUZODM-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- ISUNZYFGWCNJLT-UHFFFAOYSA-N 4-nitrophenol;hydrochloride Chemical compound Cl.OC1=CC=C([N+]([O-])=O)C=C1 ISUNZYFGWCNJLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- 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
-
- 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
- C08G73/1067—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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a polyimide with low CTE and high light transmittance, diamine monomer and preparation method thereof, wherein the polyimide takes adamantane or cyclohexane as alicyclic structure, and simultaneously introduces a rigid aromatic structure and a strong electronegative group on the basis, thereby meeting the colorless and transparent characteristics and having good thermal performance. The diamine monomer is introduced with strong electronegative groups, and the preparation of colorless transparent polyimide is facilitated by an alicyclic structure, a large substituent group, an asymmetric structure and a rigid non-coplanar structure. The diamine monomer can be used for preparing colorless transparent polyimide, the monomer takes adamantane or cyclohexane as a central structure, and is connected with a benzene ring with aromaticity through ester groups or amide bonds, wherein one monomer is of an asymmetric structure, so that the requirement for preparing the colorless transparent polyimide can be better met.
Description
Technical Field
The invention belongs to the technical fields of chemical synthesis technology and organic polymer materials, and in particular relates to polyimide with low CTE and high light transmittance, diamine monomer thereof and a preparation method thereof.
Background
In recent years, with the development of electronic devices, the conventional transparent glass substrate has failed to meet the requirements of flexible devices, so colorless transparent polymers have been increasingly emphasized, and polyimide has been attracting more attention as a polymer excellent in various aspects.
Polyimide is a high-performance polymer with a plurality of imide five-membered heterocyclic rings, has the characteristics of unique electrochemical performance, radiation resistance, chemical corrosion resistance, excellent mechanical properties and the like, and is widely applied to the fields of aerospace, electronic appliances, fuel cells, optics, biological medicines and the like. Conventional polyimides are generally brown or brown transparent materials due to the presence of strong electron donors and electron acceptors in their molecular structure, which form strong charge transfer complexes within or between their molecular chains, allowing their strong absorption in the visible range.
Disclosure of Invention
The technical problem to be solved by the invention is to provide polyimide with low CTE and high light transmittance; the invention also provides a diamine monomer of polyimide with low CTE and high light transmittance; the invention also provides a preparation method of the diamine monomer; the invention also provides a preparation method of the polyimide with low CTE and high light transmittance.
In order to solve the technical problems, the structural general formula of the polyimide is shown as the following formulas (I), (II) and (III):
in the general formula, A and D are both selected from O and NH.
The structural general formula of the diamine monomer is shown in the following formulas (A), (B) and (C):
in the general formula, A and D are both selected from O and NH.
The preparation method of the diamine monomer comprises the following steps: adamantane-1, 3-diformyl chloride, p-nitrophenol and an acid-binding agent are used as raw materials, or adamantane-1, 3-diformyl chloride, 2-fluoro-4-nitroaniline and an acid-binding agent are used as raw materials, or 1, 4-cyclohexane diformyl chloride, 4-nitro-2-trifluoromethyl aniline and an acid-binding agent are used as raw materials, or 1, 4-cyclohexane diformyl chloride, 2-fluoro-4-nitroaniline and an acid-binding agent are used as raw materials, or p-nitrobenzoyl chloride, 4-nitro-3-trifluoromethyl aniline and an acid-binding agent are used as raw materials; acylating the raw materials to generate an intermediate; the intermediate is subjected to hydrogenation reaction under the action of a hydrogenation catalyst, so that the diamine monomer can be obtained.
Further, any one of the following method steps is adopted:
(1) Firstly, adamantane-1, 3-diformyl chloride and an acid binding agent are added into a solvent, stirred in an ice water bath, p-nitrophenol solution is added dropwise, and after the dropwise addition is finished, the reaction is carried out in the ice water bath; then reacting at 15-30 ℃; after the reaction, the reaction solution was filtered and dried to obtain an intermediate (A1-1):
The intermediate (A1-1) and the hydrogenation catalyst react under the conditions of 1-5 MPa of hydrogen and 60-75 ℃; after the reaction is finished, removing the catalyst from the reaction solution, concentrating, and dripping into deionized water to obtain diamine monomer (A1);
(2) Firstly, adding 2-fluoro-4-nitroaniline and an acid binding agent into a solvent, stirring under ice water bath, dropwise adding adamantane-1, 3-diformyl chloride solution, and reacting under ice water bath after the dropwise adding is finished; then reacting at 15-30 ℃; after the reaction, the reaction solution was filtered and dried to obtain an intermediate (A2-1):
the intermediate (A2-1) and the hydrogenation catalyst react under the conditions of 1-5 MPa of hydrogen and 60-75 ℃; after the reaction is finished, removing the catalyst from the reaction solution, concentrating, and dripping into deionized water to obtain diamine monomer (A2);
(3) Firstly, adding 1, 4-cyclohexanedicarboxylic acid chloride and an acid binding agent into a solvent, stirring under ice water bath, dropwise adding 4-nitro-2-trifluoromethyl aniline solution, and reacting under ice water bath after the dropwise adding is finished; then reacting at 15-30 ℃; after the reaction, the reaction solution was filtered and dried to obtain an intermediate (B1-1):
the intermediate (B1-1) reacts with a hydrogenation catalyst under the conditions of 1-5 MPa of hydrogen and 60-75 ℃; after the reaction is finished, removing the catalyst from the reaction solution, concentrating, and dripping into deionized water to obtain diamine monomer (B1);
(4) Firstly, adding 2-fluoro-4-nitroaniline and an acid binding agent into a solvent, stirring under ice water bath, dropwise adding 1, 4-cyclohexane diformyl chloride solution, and reacting under ice water bath after the dropwise adding is finished; then reacting at 15-30 ℃; after the reaction, the reaction solution was filtered and dried to obtain an intermediate (B2-1):
the intermediate (B2-1) reacts with a hydrogenation catalyst under the conditions of 1-5 MPa of hydrogen and 60-75 ℃; after the reaction is finished, removing the catalyst from the reaction solution, concentrating, and dripping into deionized water to obtain diamine monomer (B2);
(5) Firstly, adding 4-nitro-3-trifluoromethyl aniline and an acid binding agent into a solvent, stirring under ice water bath, dropwise adding p-nitrobenzoyl chloride solution, and reacting under ice water bath after the dropwise adding is finished; then reacting at 15-30 ℃; after the reaction, the reaction solution was filtered and dried to obtain (C1-1):
the intermediate (C1-1) and the hydrogenation catalyst react under the conditions of 1-5 MPa of hydrogen and 60-75 ℃; after the reaction, removing the catalyst from the reaction solution, concentrating, and dripping into deionized water to obtain the diamine monomer (C1).
Further, in the step (1), the molar ratio of the adamantane-1, 3-diformyl chloride, the p-nitrophenol and the acid binding agent is 1:2-2.5:2-4;
In the step (2), the molar ratio of the adamantane-1, 3-diformyl chloride to the 2-fluoro-4-nitroaniline to the acid binding agent is 1:1.5-3:2-4;
in the step (3), the molar ratio of the 1, 4-cyclohexanedicarboxylic acid chloride to the 4-nitro-2-trifluoromethylaniline to the acid binding agent is 1:2-2.5:1-3;
in the step (4), the molar ratio of the 1, 4-cyclohexanedicarboxylic acid chloride to the 2-fluoro-4-nitroaniline to the acid binding agent is 1:1.5-3:2-4;
in the step (5), the molar ratio of the paranitrobenzoyl chloride to the 4-nitro-3-trifluoromethyl aniline to the acid binding agent is 1:1-1.5:1.5-2.
The preparation method of the polyimide comprises the following steps: polymerization of diamine monomers with dianhydride monomers as described in claim 2.
Further, the following method steps are adopted: s1, carrying out condensation reaction on a diamine monomer and aliphatic dianhydride or aromatic dianhydride to obtain polyamic acid;
s2, adding a dehydrating agent and a catalyst to imidize the polyamide acid to obtain polyimide.
Further, in the step S1, the condensation reaction temperature is 15-30 ℃; in the step S2, the imidization temperature is 15-30 ℃.
The beneficial effects of adopting above-mentioned technical scheme to produce lie in: the polyimide takes adamantane or cyclohexane as an alicyclic structure, and simultaneously introduces a rigid aromatic structure and a strong electronegative group on the basis, so that the polyimide meets the colorless and transparent characteristics, and has good thermal performance.
The diamine monomer of the invention introduces strong electronegative groups, and the alicyclic structure, the large substituent groups, the asymmetric structure and the rigid non-coplanar structure are all beneficial to preparing colorless transparent polyimide. The diamine monomer can be used for preparing colorless transparent polyimide, the monomer takes adamantane or cyclohexane as a central structure, and is connected with a benzene ring with aromaticity through ester groups or amide bonds, wherein one monomer is of an asymmetric structure, so that the requirement for preparing the colorless transparent polyimide can be better met.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a nuclear magnetic resonance spectrum of the diamine monomer (A1) according to the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of the diamine monomer (A1) according to the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of the diamine monomer (A2) according to the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of the diamine monomer (B1) according to the present invention;
FIG. 5 is a nuclear magnetic resonance spectrum of the diamine monomer (B1) according to the present invention;
FIG. 6 is a nuclear magnetic resonance spectrum of the diamine monomer (C1) according to the present invention;
FIG. 7 is a nuclear magnetic resonance spectrum of the polyimide obtained in example 4 of the present invention;
FIG. 8 is a nuclear magnetic resonance spectrum of the polyimide obtained in example 7 of the present invention;
FIG. 9 is a graph showing the transmittance and wavelength relationship of the polyimide films obtained in examples 1, 4, 7 and 13 of the present invention.
Detailed Description
The polyimide with low CTE and high light transmittance, diamine monomer thereof and preparation method thereof are as follows:
1) Diamine monomer and preparation method thereof:
the diamine monomer is used for polymerizing polyimide, and the structural general formula is shown in the following formulas (A), (B) and (C):
in the general formula, A and D are both selected from O and NH.
Preferred diamine monomers are represented by the following formulas (A1) (A2) (B1) (B2) (C1), and the production methods of the respective diamine monomers are as follows:
1.1 Diamine monomer (A1) and preparation:
adamantane-1, 3-diformyl chloride, p-nitrophenol and an acid binding agent are used as raw materials; the acid-binding agent can be organic base or inorganic base, wherein the organic base can be any one of triethylamine, pyridine, DIEA (N, N-diisopropylethylamine), DIPEA (N, N-diisopropylethylamine) and DMAP (4-dimethylaminopyridine), the inorganic base can be sodium carbonate, potassium carbonate or potassium bicarbonate, and the acid-binding agent can be pyridine; the molar ratio of the adamantane-1, 3-diformyl chloride, the p-nitrophenol and the acid binding agent is 1:2-2.5:2-4; tetrahydrofuran, DMF (N, N-dimethylformamide), DMAC (N, N-dimethylacetamide) or toluene is used as a solvent, preferably tetrahydrofuran; firstly, adamantane-1, 3-diformyl chloride and an acid binding agent are added into a solvent, stirring is carried out for at least 20 minutes under ice water bath, then p-nitrophenol solution is slowly added dropwise, and the mixture reacts under ice water bath, and the dropwise addition is completed within 1 hour; then removing the ice water bath to react for 8 to 12 hours at the temperature of 15 to 30 ℃; after the reaction is finished, filtering the reaction solution, repeatedly pulping a filter cake with deionized water for a plurality of times, pulping the filter cake with a potassium carbonate solution after the filtration, further purifying, filtering and drying to obtain an intermediate (A1-1):
The reaction formula of the above process is as follows:
adding the intermediate (A1-1) and the hydrogenation catalyst into a high-pressure reaction kettle according to the mass ratio of 0.5-5:1-2; the solvent is tetrahydrofuran, DMF, DMAC, ethanol, methanol and/or isopropanol, preferably tetrahydrofuran; the hydrogenation catalyst adopts a nickel-containing catalyst, pd/C or Raney nickel, and preferably Raney nickel; the high-pressure reaction kettle is filled with 1-5 MPa hydrogen after air is replaced by nitrogen, and magnetically stirred and reacted for 10-18 hours at the temperature of 60-75 ℃; after the reaction is finished, removing the catalyst by suction filtration, concentrating the reaction solution by 40-70 vol%, and slowly dripping the concentrated solution into deionized water with the volume of 5-10 times to obtain the diamine monomer (A1). The nuclear magnetic hydrogen spectrum of the obtained diamine monomer (A1) is shown in figure 1, the nuclear magnetic carbon spectrum is shown in figure 2, and the structural formula of the obtained diamine monomer (A1) is shown as the following formula (A1):
the reaction formula of the above process is as follows:
1.2 Diamine monomer (A2) and preparation:
adamantane-1, 3-diformyl chloride, 2-fluoro-4-nitroaniline and an acid binding agent are used as raw materials; the acid-binding agent can be organic base or inorganic base, wherein the organic base can be any one of triethylamine, pyridine and DIEA, DIPEA, DMAP, the inorganic base can be sodium carbonate, potassium carbonate or potassium bicarbonate, and the acid-binding agent is preferably potassium carbonate; the molar ratio of the adamantane-1, 3-diformyl chloride to the 2-fluoro-4-nitroaniline to the acid binding agent is 1:1.5-3:2-4. Tetrahydrofuran, DMF (N, N-dimethylformamide), DMAC (N, N-dimethylacetamide) or toluene is used as a solvent, preferably tetrahydrofuran; firstly adding 2-fluoro-4-nitroaniline and an acid-binding agent into a solvent, stirring for at least 20 minutes in an ice water bath, slowly dropwise adding adamantane-1, 3-diformyl chloride, reacting in the ice water bath, finishing dropwise adding within 1.5 hours, and then removing the ice water bath to react for 8-12 hours at 15-30 ℃; after the reaction is finished, filtering the reaction solution, repeatedly pulping a filter cake with deionized water for a plurality of times, filtering, and drying to obtain an intermediate (A2-1):
The reaction formula of the above process is as follows:
adding the intermediate (A2-1) and the hydrogenation catalyst into a high-pressure reaction kettle according to the mass ratio of 0.5-5:1-2; the solvent is tetrahydrofuran, DMF, DMAC, ethanol, methanol and/or isopropanol, preferably tetrahydrofuran; the hydrogenation catalyst is nickel-containing catalyst, pd/C or Raney nickel, preferably Raney nickel; after the nitrogen replaces air, 1-5 MPa hydrogen is filled, and the magnetic stirring reaction is carried out for 10-18 hours at the temperature of 60-75 ℃; after the reaction is finished, removing the catalyst by suction filtration, concentrating the reaction solution by 40-70 vol%, and slowly dripping the concentrated solution into deionized water with the volume of 5-10 times to obtain the diamine monomer (A2). The nuclear magnetic resonance spectrum of the obtained diamine monomer (A2) is shown in fig. 3, and the structural formula of the obtained diamine monomer (A2) is shown as the following formula (A2):
the reaction formula of the above process is as follows:
1.3 Diamine monomer (B1) and preparation:
1, 4-cyclohexanedicarboxylic acid chloride, 4-nitro-2-trifluoromethyl aniline and an acid binding agent are taken as raw materials; the acid-binding agent can be organic base or inorganic base, wherein the organic base can be any one of triethylamine, pyridine, DIEA, DIPEA (N, N-diisopropylethylamine) and DMAP (4-dimethylaminopyridine), the inorganic base can be sodium carbonate, potassium carbonate or potassium bicarbonate, and the acid-binding agent is pyridine; the molar ratio of the 1, 4-cyclohexanedicarboxylic acid chloride to the 4-nitro-2-trifluoromethyl aniline to the acid binding agent is 1:2-2.5:1-3. Tetrahydrofuran, DMF, DMAC or toluene is used as solvent, preferably tetrahydrofuran; firstly, adding 1, 4-cyclohexane diformyl chloride into a solvent, slowly dropwise adding a mixed solution of 4-nitro-2-trifluoromethyl aniline and pyridine under the condition of ice water bath, after dropwise adding is completed within 1.5 hours, removing the ice water bath, and reacting for 8-12 hours at 15-30 ℃; after the reaction is finished, filtering the reaction solution, repeatedly pulping a filter cake with deionized water, filtering again, pulping the filter cake with 10% potassium carbonate solution for further purification, carrying out suction filtration, recrystallizing the filter cake with DMF, filtering, and drying to obtain a pale yellow intermediate (B1-1) shown in the formula (B1-1):
The reaction formula of the above process is as follows:
adding the intermediate (B1-1) and the hydrogenation catalyst into a high-pressure reaction kettle according to the mass ratio of 0.5-5:1-2; the solvent is tetrahydrofuran, DMF, DMAC, ethanol, methanol and/or isopropanol, preferably tetrahydrofuran; the hydrogenation catalyst is nickel-containing catalyst, pd/C or Raney nickel, preferably Raney nickel; after the nitrogen replaces air, 1-5 MPa hydrogen is filled, and the magnetic stirring reaction is carried out for 10-18 hours at the temperature of 60-75 ℃; after the reaction is finished, removing the catalyst by suction filtration, concentrating the reaction solution by 40-70 vol%, and slowly dripping the concentrated solution into deionized water with the volume of 5-10 times to obtain the diamine monomer (B1). The nuclear magnetic hydrogen spectrum of the diamine monomer (B1) is shown in fig. 4, the nuclear magnetic carbon spectrum is shown in fig. 5, and the structural formula of the diamine monomer (B1) is shown as the following formula (B1):
the reaction formula of the above process is as follows:
1.4 Diamine monomer (B2) and preparation:
1, 4-cyclohexanedicarboxylic acid chloride, 2-fluoro-4-nitroaniline and an acid binding agent are taken as raw materials; the acid-binding agent can be organic base or inorganic base, wherein the organic base can be any one of triethylamine, pyridine and DIEA, DIPEA, DMAP, the inorganic base can be sodium carbonate, potassium carbonate or potassium bicarbonate, and the acid-binding agent is preferably potassium carbonate; the molar ratio of the 1, 4-cyclohexanedicarboxylic acid chloride to the 2-fluoro-4-nitroaniline to the acid binding agent is 1:1.5-3:2-3. Tetrahydrofuran, DMF, DMAC or toluene is used as solvent, preferably tetrahydrofuran; firstly, adding 2-fluoro-4-nitroaniline and an acid binding agent into a solvent, slowly dropwise adding a 1, 4-cyclohexane diformyl chloride solution under the condition of ice water bath, after dropwise adding in 1.5 hours, removing the ice water bath, and reacting for 8-12 hours at 15-30 ℃; after the reaction is finished, filtering the reaction solution, repeatedly pulping a filter cake with deionized water, filtering again, recrystallizing the filter cake with a mixed solution of DMF and THF, filtering, and drying to obtain a pale yellow intermediate (B2-1) shown in the formula (B2-1):
The reaction formula of the above process is as follows:
adding the intermediate (B2-1) and the hydrogenation catalyst into a high-pressure reaction kettle according to the mass ratio of 0.5-5:1-2; the solvent is tetrahydrofuran, DMF, DMAC, ethanol, methanol and/or isopropanol, preferably tetrahydrofuran; the hydrogenation catalyst is nickel-containing catalyst, pd/C or Raney nickel, preferably Raney nickel; after the nitrogen replaces air, 1-5 MPa hydrogen is filled, and the magnetic stirring reaction is carried out for 10-18 hours at the temperature of 60-75 ℃; after the reaction is finished, removing the catalyst by suction filtration, concentrating the reaction solution by 40-70 vol%, and slowly dripping the concentrated solution into deionized water with the volume of 5-10 times to obtain the diamine monomer (B2). The structural formula of the diamine monomer (B2) is shown as follows:
the reaction formula of the above process is as follows:
1.5 Diamine monomer (C1) and preparation:
p-nitrobenzoyl chloride, 4-nitro-3-trifluoromethyl aniline and an acid binding agent are taken as raw materials; the acid-binding agent can be organic base or inorganic base, wherein the organic base can be any one of triethylamine, pyridine and DIEA, DIPEA, DMAP, the inorganic base can be sodium carbonate, potassium carbonate or potassium bicarbonate, and the acid-binding agent is preferably pyridine; the molar ratio of the paranitrobenzoyl chloride to the 4-nitro-3-trifluoromethyl aniline to the acid binding agent is 1:1-1.5:1.5-2. Tetrahydrofuran, DMF, DMAC or toluene is used as solvent, preferably tetrahydrofuran; firstly, adding 4-nitro-3-trifluoromethyl aniline and an acid binding agent into a solvent, slowly dropwise adding the 4-nitro-3-trifluoromethyl aniline under the condition of ice water bath, after dropwise adding in 1 hour, removing the ice water bath, and reacting for 8-12 hours at 15-30 ℃; after the reaction is finished, the reaction solution is filtered, the filter cake is repeatedly pulped by deionized water, filtered again and dried to obtain a pale yellow intermediate (C1-1) shown in the formula (C1-1):
The reaction formula of the above process is as follows:
adding the intermediate (C1-1) and the hydrogenation catalyst into a high-pressure reaction kettle according to the mass ratio of 0.5-5:1-2; the solvent is tetrahydrofuran, DMF, DMAC, ethanol, methanol and/or isopropanol, preferably tetrahydrofuran; the hydrogenation catalyst is nickel-containing catalyst, pd/C or Raney nickel, preferably Raney nickel; after the nitrogen replaces air, 1-5 MPa hydrogen is filled, and the magnetic stirring reaction is carried out for 10-18 hours at the temperature of 60-75 ℃; after the reaction is finished, removing the catalyst by suction filtration, concentrating the reaction solution by 40-70 vol%, and slowly dripping the concentrated solution into deionized water with the volume of 5-10 times to obtain the diamine monomer (C1). The nuclear magnetic resonance spectrum of the obtained diamine monomer (C1) is shown in FIG. 6, and the structural formula of the obtained diamine monomer (C1) is shown as follows:
the reaction formula of the above process is as follows:
2) Polyimide and a preparation method thereof:
the polyimide is polymerized by the diamine monomer and the dianhydride monomer; diamine monomers shown in general formulas (A), (B) and (C) are polymerized with dianhydride monomers respectively, and the structural general formulas of the obtained polyimide are shown in the following formulas (I), (II) and (III) respectively:
in the general formula, A and D are both selected from O and NH.
The preparation method of the polyimide comprises the following steps:
S1, after air in a 100mL three-neck flask is replaced by argon flow, the flow rate of gas is regulated, the air tightness is checked, a hot air gun blows the flask for at least 2 minutes to thoroughly dry the flask, the dried diamine monomer is accurately weighed and added into solvent anhydrous DMAC to be completely dissolved in ice water bath, the dried dianhydride monomer is accurately weighed and added into diamine solution, wherein the molar ratio of diamine to dianhydride is preferably controlled to be 1:1, and the bottle mouth is flushed by the solvent. Stirring in ice water bath for at least 2 hours, removing the ice water bath, and stirring at 15-30 ℃ for reaction for 20-30 hours; the reaction liquid is colorless and transparent, and has high viscosity. The dianhydride monomer may be aliphatic dianhydride such as H' -PMDA (hydrogenated pyromellitic dianhydride) or 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, or aromatic dianhydride such as: 4,4 '-biphenic ether dianhydride, PMDA (pyromellitic dianhydride) or 6FDA (2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride).
S2, adding a catalyst and a dehydrating agent into the reaction solution of the S1, wherein the molar ratio of the diamine to the catalyst to the dehydrating agent is 1:1-5:5-10, and after the reaction solution is added, the color of the reaction solution turns yellow briefly, and the reaction is continuously stirred for 20-30 hours at 15-30 ℃. Stopping the reaction, slowly adding the reaction solution into methanol for washing, separating out the solid into white fiber, cutting the white fiber into small sections by using an operation, carrying out suction filtration, washing the solid by using deionized water, carrying out suction filtration, washing the solid by using methanol again, carrying out suction filtration, and drying to obtain the white fiber solid, namely polyimide. The catalyst can be pyridine, trimethylpyridine, quinoline or isoquinoline, and the dehydrating agent can be acetic anhydride.
The polyimide can be used for preparing polyimide films, and the preparation method comprises the following steps: dissolving the polyimide into a solvent, centrifugally settling, sucking supernatant, coating the supernatant on a glass plate, evaporating the solvent for 6-16 hours at the temperature of 60-90 ℃, finally placing the glass plate into deionized water, and stripping the film to obtain the colorless transparent polyimide film.
Example 1: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps:
into a 250mL flask, 12.31g (47.14 mmol) of adamantane-1, 3-dicarboxylic acid chloride and 35mL of anhydrous tetrahydrofuran were added, 11.4mL (141.41 mmol) of pyridine was added as an acid-binding agent, 13.12g (94.28 mmol) of p-nitrophenol and 30mL of anhydrous tetrahydrofuran were prepared into a solution, the p-nitrophenol solution was slowly dropped into the flask under the ice water bath condition, the dropping was completed within 1 hour, then the ice water bath was removed for reaction at 25℃and TLC was monitored for reaction completion, and the reaction was completed for 9.5 hours. The reaction solution is pumped and filtered, 150mL of water is used for pulping the filter cake, 100mL of 10% potassium carbonate solution is used for pulping the filter cake for further purification after the filtration, the filter cake is filtered, and 18.2g of light yellow dinitro compound is obtained after the filter cake is dried in vacuum, and the yield is 83%, namely the intermediate (A1-1).
2.57g (5.51 mmol) of the intermediate (A1-1) and 20mL of tetrahydrofuran are added into a 100mL hydrogenation reaction kettle with magnetic stirring, 30mL of ethanol and 20mL of tetrahydrofuran are added as solvents, 1.01g of Raney nickel with wet weight is added as a catalyst, a kettle cover is screwed up, nitrogen is filled to replace air, 3MPa of hydrogen is filled, and the temperature of the reaction kettle is raised to 70 ℃ for reaction for 10 hours until the hydrogen pressure is not reduced any more. After pressure release, sampling was performed, and TLC monitoring was completed. Filtering the reaction solution to remove the catalyst, adding 0.5g of alkaline active carbon for decoloring, filtering to remove the active carbon, concentrating the reaction solution to 50%, slowly dripping the concentrated solution into 120mL of deionized water, separating out a white solid product, filtering, pulping with 100mL of deionized water again, filtering, and vacuum drying to obtain 1.90g of the product with the yield of 85%, wherein the product is diamine monomer (A1), and the nuclear magnetic hydrogen spectrum of the diamine monomer (A1) is shown in figure 1 and the nuclear magnetic carbon spectrum is shown in figure 2.
(2) The preparation process of polyimide comprises the following steps:
after air in the three-neck flask is replaced by argon flow, the flow speed of the air is regulated, the flask is dried for 2 minutes at the temperature of 300 ℃ by a hot air gun, 1.9894g (4.8942 mmol) of the dried diamine monomer (A1) is accurately weighed, 10.0mL of anhydrous DMAc is added, the mixture is stirred until diamine is completely dissolved, 6FDA 2.1742g (4.8942 mmol) of the accurately weighed and dried dianhydride monomer is added into the diamine solution in three times under ice water bath, 10.8mL of anhydrous DMAc is measured, and the solid content of the reaction liquid is controlled to be 20%. After stirring for 2 hours in an ice water bath, the ice water bath was removed. The reaction was stirred at room temperature for 24 hours. Then, 0.41mL (4.8942 mmol) of pyridine was added as a catalyst, 4.8mL (48.94 mmol) of acetic anhydride was added as a dehydrating agent, and the reaction was terminated by stirring at room temperature for 24 hours. The reaction solution is slowly added into 100mL of methanol for washing, solid precipitation, filtration, washing of a filter cake by 100mL of deionized water, filtration, washing of the solid by 50mL of methanol again, filtration and vacuum drying, and 3.57g of white solid is obtained, namely polyimide shown in the general formula (I). The reaction formula of the above process is as follows:
(3) The preparation process of the polyimide film comprises the following steps:
weighing 0.8076g of the polyimide polymer, dissolving in 10.0mL of anhydrous DMAc, placing in a 50mL centrifuge tube with the solid content of 8%, centrifuging for 2 minutes at 5000r/min, absorbing supernatant, coating the supernatant on a glass plate, placing the glass plate on a constant-temperature heating table, heating at 70 ℃ for 8 hours to evaporate the solvent, cooling to room temperature, placing the glass plate in water, and peeling off the film to obtain a polyimide film; cutting and testing; the transmittance and wavelength of the obtained polyimide film are shown in FIG. 9, and the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Example 2: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps: example 1 was repeated except for the following procedure.
The acid binding agent adopts DIPEA and toluene as solvents; adamantane-1, 3-dicarboxyl chloride p-nitrophenol acid binding agent = 1:2.5:4 (molar ratio); after removing the ice-water bath, the reaction was carried out at 30℃for 8 hours.
The hydrogenation catalyst adopts a nickel-containing catalyst, and the solvent adopts DMAC; the intermediate (A1-1) is a hydrogenation catalyst 5:1 (mass ratio); 5MPa hydrogen is filled in, and the reaction is magnetically stirred for 15 hours at 60 ℃.
(2) The preparation process of polyimide comprises the following steps: example 1 was repeated except for the following procedure.
The dianhydride monomer adopts H' -PMDA; after stirring for 2.5 hours in an ice-water bath, the ice-water bath was removed, and the reaction was stirred at 15℃for 30 hours. The catalyst adopts isoquinoline, diamine monomer and catalyst, wherein the dehydrating agent=1:5:8 (molar ratio); the reaction was stirred at 30℃for 20 hours. Obtaining polyimide shown in the general formula (I).
(3) The preparation process of the polyimide film comprises the following steps: example 1 was repeated except for the following procedure.
After the polyimide polymer was coated on the glass plate, the solvent was evaporated at 60 ℃ for 16 hours; the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Example 3: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps: example 1 was repeated except for the following procedure.
The acid binding agent adopts sodium carbonate and DMF as solvents; the adamantane-1, 3-dicarboxyl chloride p-nitrophenol acid binding agent = 1:2.2:2 (molar ratio); after removing the ice-water bath, the reaction was carried out at 15℃for 12 hours.
Pd/C is adopted as the hydrogenation catalyst, and isopropanol is adopted as the solvent; the intermediate (A1-1) is hydrogenation catalyst 0.5:1 (mass ratio); 1MPa hydrogen is filled in, and the reaction is magnetically stirred for 18 hours at 75 ℃.
(2) The preparation process of polyimide comprises the following steps: example 1 was repeated except for the following procedure.
The dianhydride monomer adopts PMDA; after stirring for 3 hours in an ice-water bath, the ice-water bath was removed, and the reaction was stirred at 30℃for 20 hours. The catalyst adopts trimethyl pyridine, diamine monomer and catalyst, wherein the dehydrating agent=1:2:5 (molar ratio); the reaction was stirred for 30 hours at 15 ℃. Obtaining polyimide shown in the general formula (I).
(3) The preparation process of the polyimide film comprises the following steps: example 1 was repeated except for the following procedure.
After the polyimide polymer was coated on the glass plate, the solvent was evaporated at 90 ℃ for 6 hours; the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Example 4: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps:
into a 250mL flask, 10.15g (65.06 mmol) of 2-fluoro-4-nitroaniline and 30mL of anhydrous tetrahydrofuran were added, 13.22g (95.65 mmol) of potassium carbonate was added as an acid-binding agent, 10.00g (38.28 mmol) of adamantane-1, 3-dicarboxylic acid chloride and 30mL of anhydrous tetrahydrofuran were prepared into a solution, and the adamantane-1, 3-dicarboxylic acid chloride solution was slowly dropped into the flask under ice-water bath conditions, after the dropping was completed within 1.5 hours, then the ice-water bath was removed and reacted at 25℃with TLC monitoring, and the reaction was completed for 10 hours. The reaction solution is pumped and filtered, the filter cake is pulped by 500mL of water, and after the filtration is carried out again, 13.5g of light yellow dinitro compound is obtained after the filter cake is dried in vacuum, and the yield is 83%, namely the intermediate (A2-1).
2.60g (5.20 mmol) of the intermediate (A2-1) is added into a 100mL hydrogenation reaction kettle with magnetic stirring, 30mL of ethanol and 20mL of tetrahydrofuran are added as solvents, 1.01g of Raney nickel with wet weight is added as a catalyst, a kettle cover is screwed up, nitrogen is filled to replace air, 3MPa of hydrogen is filled, the temperature of the reaction kettle is raised to 70 ℃ for reaction for 10 hours until the hydrogen pressure is not reduced any more. After pressure release, sampling was performed, and TLC monitoring was completed. Filtering the reaction solution to remove the catalyst, adding 0.5g of alkaline active carbon for decoloring, filtering to remove the active carbon, concentrating the reaction solution to 50%, slowly dripping the concentrated solution into 120mL of deionized water, separating out a white solid product, filtering, pulping with 100mL of deionized water again, filtering, and vacuum drying to obtain 1.90g of the product with 85% yield, wherein the product is diamine monomer (A2), and the nuclear magnetic hydrogen spectrum of the diamine monomer (A2) is shown in figure 3.
(2) The preparation process of polyimide comprises the following steps:
after replacing air in the three-neck flask with argon flow, adjusting the flow rate of the air, blow-drying the flask for 2 minutes at the temperature of 300 ℃ by a hot air gun, accurately weighing 1.8997g (4.3155 mmol) of dried diamine monomer (A2), adding 10.0mL of anhydrous DMAc, stirring until diamine is completely dissolved, accurately weighing 1.9171g (4.3175 mmol) of dried dianhydride monomer 6FDA under ice water bath, adding the three times of the dry diamine monomer into the diamine solution, measuring 9mL of anhydrous DMAc, and controlling the solid content of the reaction liquid to be 20%; stirring in ice water bath for 2 hours, and removing the ice water bath; the reaction was stirred at room temperature for 24 hours. Then, 0.314mL (4.3175 mmol) of pyridine was added as a catalyst, 4.05mL (43.175 mmol) of acetic anhydride was added as a dehydrating agent, and the reaction was terminated by stirring at room temperature for 24 hours. The reaction solution is slowly added into 100mL of methanol for washing, solid precipitation, filtration, washing of a filter cake with 100mL of deionized water, filtration, washing of the solid with 50mL of methanol again, filtration and vacuum drying, and the polyimide shown in the general formula (I) is obtained, wherein 3.52g of white fibrous solid with 93% yield is obtained. The nuclear magnetic hydrogen spectrum of the obtained polyimide is shown in fig. 7, and the reaction formula of the above process is shown as follows:
(3) The preparation process of the polyimide film comprises the following steps:
weighing 0.4005g of polyimide, dissolving in 5.0ml of anhydrous DMAc, placing in a 15ml centrifuge tube with solid content of 8%, centrifuging at 4000r/min for 3 min, absorbing supernatant, coating on a glass plate, placing the glass plate in a blast drying oven, heating at 80deg.C for 14h to form a film, cooling to room temperature, placing the glass plate in water, and stripping the film to obtain a polyimide film; the transmittance and wavelength relationships of the obtained polyimide films were cut and tested as shown in fig. 9, and the properties of the obtained polyimide films are shown in the following tables 1 and 2.
Example 5: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps: example 4 was repeated except for the following procedure.
The acid binding agent adopts potassium bicarbonate and DMAC as solvents; 2-fluoro-4-nitroaniline, adamantane-1, 3-dicarboxyl chloride, acid-binding agent = 1:1.5:2 (molar ratio); after removing the ice-water bath, the reaction was carried out at 30℃for 8 hours.
The hydrogenation catalyst adopts a nickel-containing catalyst, and the solvent adopts methanol; the intermediate (A2-1) is a hydrogenation catalyst of 5:2 (mass ratio); 5MPa hydrogen is filled in, and the reaction is magnetically stirred for 18 hours at 60 ℃.
(2) The preparation process of polyimide comprises the following steps: example 4 was repeated except for the following procedure.
The dianhydride monomer adopts 4,4' -diphenyl ether dianhydride; the reaction was stirred at 15℃for 30 hours. The catalyst adopts quinoline and diamine monomer, and the catalyst is a dehydrating agent=1:5:8 (molar ratio); the reaction was stirred at 30℃for 20 hours. Obtaining polyimide shown in the general formula (I).
(3) The preparation process of the polyimide film comprises the following steps: example 4 was repeated except for the following procedure.
After the polyimide polymer was coated on the glass plate, the solvent was evaporated at 60 ℃ for 16 hours; the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Example 6: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps: example 4 was repeated except for the following procedure.
The acid binding agent adopts DMAP and DMF as solvents; 2-fluoro-4-nitroaniline, adamantane-1, 3-dicarboxyl chloride, acid-binding agent = 1:3:4 (molar ratio); after removing the ice-water bath, the reaction was carried out at 15℃for 12 hours.
Pd/C is adopted as the hydrogenation catalyst, and tetrahydrofuran is adopted as the solvent; the intermediate (A2-1) is hydrogenation catalyst 0.5:1 (mass ratio); 1MPa hydrogen is filled in, and the reaction is magnetically stirred for 16 hours at 75 ℃.
(2) The preparation process of polyimide comprises the following steps: example 4 was repeated except for the following procedure.
The dianhydride monomer adopts 1,2,3, 4-cyclobutane tetracarboxylic dianhydride; after stirring for 2.5 hours in an ice-water bath, the ice-water bath was removed, and the reaction was stirred at 30℃for 20 hours. The diamine monomer: catalyst: dehydrating agent = 1:2:5 (molar ratio); the reaction was stirred for 30 hours at 15 ℃. Obtaining polyimide shown in the general formula (I).
(3) The preparation process of the polyimide film comprises the following steps: example 4 was repeated except for the following procedure.
After the polyimide polymer was coated on the glass plate, the solvent was evaporated at 90 ℃ for 6 hours; the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Example 7: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps:
in a 100mL flask with magnetic stirring, 17.92g (104.08 mmol) of 1, 4-cyclohexanedicarboxylic acid (cis-trans isomer mixture) and 20.2mL of thionyl chloride were added, 0.5mL of DMF was added as a catalyst, and the reaction was refluxed at 80℃for 7 hours, and the reaction was completed as monitored by phosphomolybdic acid TLC. The excess thionyl chloride was distilled off to give 20.02g of a white solid in 92% yield, i.e. 1, 4-cyclohexanedicarboxylic acid chloride. The reaction formula is shown in the figure:
Into a 250mL flask with magnetic stirring, 10.34g (49.45 mmol) of 1, 4-cyclohexanedicarboxylic acid chloride and 50mL of anhydrous tetrahydrofuran were added, 20.39g (98.91 mmol) of 4-nitro-2-trifluoromethylaniline, 11.9mL (148.37 mmol) of pyridine and 80mL of anhydrous tetrahydrofuran were prepared as a solution, and a mixed solution of 4-nitro-2-trifluoromethylaniline and pyridine was slowly dropped into the flask under ice-water bath conditions, after the completion of the dropping in 1.5 hours, then the ice-water bath was removed to react at 25℃and TLC was monitored to complete the reaction. The reaction solution is filtered, the filter cake is pulped by 500mL of water, after the filtration is carried out again, the filter cake is pulped by 250mL of 10% potassium carbonate solution for further purification, the suction filtration is carried out, the filter cake is recrystallized by DMF, the filtration is carried out, and the filter cake is dried in vacuum to obtain 22.51g of light yellow dinitro compound, the yield is 83%, namely the intermediate (B1-1).
3.57g (6.51 mmol) of intermediate (B1-1) and 30mL of tetrahydrofuran are added into a 100mL hydrogenation reaction kettle, 20mL of ethanol and 30mL of tetrahydrofuran are taken as solvents, 1.07g of Raney nickel with wet weight is taken as a catalyst, a kettle cover is screwed up, nitrogen is filled to replace air, 2.7MPa of hydrogen is filled, the temperature of the reaction kettle is raised to 70 ℃ for reaction for 12 hours until the hydrogen pressure is not reduced. After pressure release, sampling was performed, and TLC monitoring was completed. Filtering the reaction solution to remove the catalyst, adding 0.6g of alkaline active carbon for decoloring, filtering to remove the active carbon, concentrating the reaction solution to 50%, slowly dripping the concentrated solution into 150mL of deionized water, separating out a white solid product, filtering, pulping with 100mL of deionized water again, filtering, and vacuum drying to obtain 2.67g of the product with the yield of 84%, namely the diamine monomer (B1), wherein the nuclear magnetic hydrogen spectrum of the diamine monomer (B1) is shown in figure 4, and the nuclear magnetic carbon spectrum is shown in figure 5.
(2) The preparation process of polyimide comprises the following steps:
after air in the three-neck flask is replaced by argon flow, the flow speed of the air is regulated, the flask is dried for 2 minutes at the temperature of 300 ℃ by a hot air gun, 2.1064g (4.3125 mmol) of the dried diamine monomer (B1) is accurately weighed, 10.2mL of anhydrous DMAc is added, the mixture is stirred until diamine is completely dissolved, 1.9158g (4.3125 mmol) of the dried dianhydride monomer (6 FDA) is accurately weighed and added into the diamine solution for three times under ice water bath, 10.0mL of anhydrous DMAc is measured, and the solid content of the reaction liquid is controlled at 20%. After stirring for 2 hours in an ice water bath, the ice water bath was removed. The reaction was stirred at room temperature for 24 hours. Then, 0.35mL (4.3125 mmol) of pyridine was added as a catalyst, 4.00mL (43.12 mmol) of acetic anhydride was added as a dehydrating agent, and the reaction was terminated by stirring at room temperature for 24 hours. Slowly adding the reaction solution into 100mL of methanol for washing, separating out solids, filtering, washing a filter cake with 100mL of deionized water, filtering, washing the solids with 50mL of methanol again, filtering, and vacuum drying to obtain 3.74g of white solid, namely polyimide shown in a general formula (II); the nuclear magnetic hydrogen spectrum of the obtained polyimide is shown in figure 8. The reaction formula of the above process is as follows:
(3) The preparation process of the polyimide film comprises the following steps:
Weighing 0.8016g of the polyimide polymer, dissolving in 10.0mL of anhydrous DMAc, placing in a 50mL centrifuge tube with the solid content of 8%, centrifuging for 2 minutes at 5000r/min, sucking the supernatant, coating the supernatant on a glass plate, placing the glass plate on a constant-temperature heating table, heating at 70 ℃ for 8 hours, cooling to room temperature, placing the glass plate in water, and stripping the film to obtain a polyimide film; the transmittance and wavelength relationships of the obtained polyimide films were cut and tested as shown in fig. 9, and the properties of the obtained polyimide films are shown in the following tables 1 and 2.
Example 8: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps: example 7 was repeated except for the following procedure.
The acid binding agent adopts triethylamine; the 1, 4-cyclohexanedicarboxylic acid chloride is 4-nitro-2-trifluoromethylaniline and acid binding agent=1:2.5:2 (molar ratio); after removing the ice-water bath, the reaction was carried out at 30℃for 8 hours.
The hydrogenation catalyst adopts a nickel-containing catalyst, and the solvent adopts methanol; the intermediate (B1-1) is a hydrogenation catalyst of 5:2 (mass ratio); 5MPa hydrogen is filled in, and the reaction is carried out for 10 hours under the magnetic stirring at the temperature of 75 ℃.
(2) The preparation process of polyimide comprises the following steps: example 1 was repeated except for the following procedure.
The dianhydride monomer adopts 1,2,3, 4-cyclobutane tetracarboxylic dianhydride; after stirring for 3 hours in an ice-water bath, the ice-water bath was removed, and the reaction was stirred at 15℃for 30 hours. The catalyst adopts trimethyl pyridine, diamine monomer and catalyst, wherein the dehydrating agent=1:5:8 (molar ratio); the reaction was stirred for 30 hours at 15 ℃. Obtaining polyimide shown in a general formula (II).
(3) The preparation process of the polyimide film comprises the following steps: example 1 was repeated except for the following procedure.
After the polyimide polymer was coated on the glass plate, the solvent was evaporated at 60 ℃ for 16 hours; the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Example 9: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps: example 7 was repeated except for the following procedure.
The acid binding agent adopts DIEA and toluene as solvents; the 1, 4-cyclohexanedicarboxylic acid chloride is 4-nitro-2-trifluoromethylaniline and acid binding agent=1:2.2:1 (molar ratio); after removing the ice-water bath, the reaction was carried out at 15℃for 12 hours.
Pd/C is adopted as the hydrogenation catalyst, and DMF is adopted as the solvent; the intermediate (B1-1) is hydrogenation catalyst 0.5:1 (mass ratio); 1MPa hydrogen is filled in, and the reaction is magnetically stirred for 18 hours at 60 ℃.
(2) The preparation process of polyimide comprises the following steps: example 1 was repeated except for the following procedure.
The dianhydride monomer adopts PMDA; after stirring for 3 hours in an ice-water bath, the ice-water bath was removed, and the reaction was stirred at 30℃for 20 hours. The catalyst adopts trimethyl pyridine, diamine monomer and catalyst, wherein the dehydrating agent=1:2:5 (molar ratio); the reaction was stirred at 30℃for 20 hours. Obtaining polyimide shown in a general formula (II).
(3) The preparation process of the polyimide film comprises the following steps: example 1 was repeated except for the following procedure.
After the polyimide polymer was coated on the glass plate, the solvent was evaporated at 90 ℃ for 6 hours; the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Example 10: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps:
10.15g (62.65 mmol) of 2-fluoro-4-nitroaniline and 30mL of anhydrous tetrahydrofuran are added into a 250mL flask, 13.22g (95.80 mmol) of potassium carbonate is added as an acid binding agent, 10.08g (38.28 mmol) of 1, 4-cyclohexanedicarboxylic acid chloride and 20mL of anhydrous tetrahydrofuran are prepared into a solution, the 1, 4-cyclohexanedicarboxylic acid chloride solution is slowly dripped into the flask under the ice water bath condition, the dripping is completed within 1.5 hours, then the ice water bath is removed for reaction at 25 ℃, and the TLC monitors the reaction, and the reaction is completed for 10 hours. The reaction solution is filtered, the filter cake is pulped by 500mL of water, after filtering again, suction filtration is carried out, the filter cake is recrystallized by using a mixed solution of DMF and THF, filtering is carried out, and 16.1g of light yellow dinitro compound is obtained after the filter cake is dried in vacuum, and the yield is 84%, namely the intermediate (B2-1).
2.60g (5.80 mmol) of the intermediate (B2-1) is added into a 100mL hydrogenation reaction kettle with magnetic stirring, 30mL of ethanol and 20mL of tetrahydrofuran are added as solvents, 1.01g of Raney nickel with wet weight is added as a catalyst, a kettle cover is screwed up, nitrogen is filled to replace air, 3MPa of hydrogen is filled, and the temperature of the reaction kettle is raised to 70 ℃ for reaction for 10 hours until the hydrogen pressure is not reduced any more. After pressure release, sampling was performed, and TLC monitoring was completed. Filtering the reaction solution to remove the catalyst, adding 0.5g of alkaline active carbon for decoloring, filtering to remove the active carbon, concentrating the reaction solution to 50%, slowly dripping the concentrated solution into 120mL of deionized water, separating out a white solid product, filtering, pulping with 100mL of deionized water again, filtering, and vacuum drying to obtain 1.91g of the product with 85% yield, wherein the product is diamine monomer (B2).
(2) The preparation process of polyimide comprises the following steps:
after air in the three-neck flask is replaced by argon flow, the flow speed of the air is regulated, the flask is dried for 2 minutes at the temperature of 300 ℃ by a hot air gun, 1.8998g (4.8942 mmol) of dried diamine monomer (B2) is accurately weighed, 10.0mL of anhydrous DMAc is added, the mixture is stirred until diamine is completely dissolved, 6FDA 2.1742g (4.8942 mmol) of dried dianhydride monomer is accurately weighed and added into the diamine solution in three times under ice water bath, 10.4mL of anhydrous DMAc is measured, and the solid content of the reaction liquid is controlled to be 20%. After stirring for 2 hours in an ice water bath, the ice water bath was removed. The reaction was stirred at room temperature for 24 hours. Then 0.460mL (4.8942 mmol) pyridine is added as a catalyst, 3.94mL (48.942 mmol) acetic anhydride is added as a dehydrating agent, the reaction is continuously stirred at room temperature for 24 hours, the reaction solution is added into 100mL of methanol for washing, solids are separated out, filtration is carried out, a filter cake is washed with 100mL of deionized water, filtration is carried out, the solids are washed with 50mL of methanol again, and after filtration, vacuum drying is carried out, thus obtaining white polyimide solids.
The reaction formula of the above process is as follows:
(3) The preparation process of the polyimide film comprises the following steps:
0.4010g of the polyimide is weighed, dissolved in 5.0ml of anhydrous DMAc, the solid content is 8%, placed in a 15ml centrifuge tube, centrifuged for 3 minutes at 4000r/min, the supernatant is sucked and coated on a glass plate, the glass plate is placed in a blast drying oven, heated at 80 ℃ for 14 hours to form a film, cooled to room temperature, the glass plate is placed in water to strip the film, and the polyimide film is obtained, cut and tested, and the performance of the obtained polyimide film is shown in the following tables 1 and 2.
Example 11: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps: example 10 was repeated except for the following procedure.
The acid binding agent adopts potassium bicarbonate and toluene as solvents; 2-fluoro-4-nitroaniline of 1, 4-cyclohexanedicarboxylic acid chloride with acid binding agent=1:1.5:2 (molar ratio); after removing the ice-water bath, the reaction was carried out at 30℃for 8 hours.
The hydrogenation catalyst adopts a nickel-containing catalyst, and the solvent adopts isopropanol; the intermediate (B2-1) is a hydrogenation catalyst of 5:2 (mass ratio); 5MPa hydrogen is filled in, and the reaction is magnetically stirred for 12 hours at 75 ℃.
(2) The preparation process of polyimide comprises the following steps: example 1 was repeated except for the following procedure.
The dianhydride monomer adopts 1,2,3, 4-cyclobutane tetracarboxylic dianhydride; after stirring for 3 hours in an ice-water bath, the ice-water bath was removed, and the reaction was stirred at 15℃for 30 hours. The catalyst adopts trimethyl pyridine, diamine monomer and catalyst, wherein the dehydrating agent=1:5:8 (molar ratio); the reaction was stirred for 30 hours at 15 ℃. Obtaining polyimide shown in a general formula (II).
(3) The preparation process of the polyimide film comprises the following steps: example 1 was repeated except for the following procedure.
After the polyimide polymer was coated on the glass plate, the solvent was evaporated at 60 ℃ for 16 hours; the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Example 12: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps: example 10 was repeated except for the following procedure.
The acid binding agent adopts triethylamine and DMF as solvents; 4-nitro-2-trifluoromethyl-aniline, 1, 4-cyclohexanedicarboxylic acid chloride, 1:3:3 (molar ratio); after removing the ice-water bath, the reaction was carried out at 15℃for 12 hours.
Pd/C is adopted as the hydrogenation catalyst, and DMF is adopted as the solvent; the intermediate (B2-1) is hydrogenation catalyst 0.5:1 (mass ratio); 1MPa hydrogen is filled in, and the reaction is magnetically stirred for 18 hours at 60 ℃.
(2) The preparation process of polyimide comprises the following steps: example 1 was repeated except for the following procedure.
The dianhydride monomer adopts PMDA; after stirring for 2.5 hours in an ice-water bath, the ice-water bath was removed, and the reaction was stirred at 30℃for 20 hours. The catalyst adopts trimethyl pyridine, diamine monomer and catalyst, wherein the dehydrating agent=1:2:5 (molar ratio); the reaction was stirred at 30℃for 20 hours. Obtaining polyimide shown in a general formula (II).
(3) The preparation process of the polyimide film comprises the following steps: example 1 was repeated except for the following procedure.
After the polyimide polymer was coated on the glass plate, the solvent was evaporated at 90 ℃ for 6 hours; the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Example 13: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps:
5.02g (24.27 mmol) of 4-nitro-3-trifluoromethylaniline and 20mL of THF (tetrahydrofuran) were placed in a 100mL single neck flask, and 4mL (49.46 mmol) of pyridine was added as an acid-binding agent and stirred. 4.51g (24.27 mmol) of paranitrobenzoyl chloride was dissolved in 15mL of THF and placed in a constant pressure dropping funnel, and slowly dropped into the flask under ice water bath conditions, after the dropping was completed within 1.5h, the ice water bath was removed, the reaction was performed at room temperature, the temperature was raised to reflux, the solution was not alkaline, and the reaction was performed for 12h, to obtain intermediate (C1-1).
1.98g (5.61 mmol) of intermediate (C1-1) is added into a 100mL hydrogenation reaction kettle, 40mL of absolute ethyl alcohol is added as a solvent, 1.04g of Raney nickel with wet weight is added as a catalyst, a kettle cover is screwed up, nitrogen is firstly filled to replace air, then hydrogen is filled to 3.1MPa, the reaction kettle is heated to 60 ℃ and then the hydrogen pressure is not reduced any more, and the reaction is carried out for 15 hours. After pressure release, sampling is carried out, and TLC detection is finished. Removing the catalyst by suction filtration, adding 0.40g of alkaline active carbon for decoloring, removing the active carbon by suction filtration, concentrating the reaction solution to 50%, slowly dripping the concentrated solution into 50mL of deionized water, separating out solid products, suction-filtering, and vacuum-drying to obtain 1.32g of off-white powdery solid with the yield of 79.52%; the product is diamine monomer (C1), and the nuclear magnetic hydrogen spectrum of the obtained diamine monomer (C1) is shown in figure 6.
(2) The preparation process of polyimide comprises the following steps:
after the air in a 100mL three-neck flask is replaced by argon flow, the flow rate of the air is regulated, the air tightness is checked, a hot air gun blows the flask for three minutes to thoroughly dry the flask, 2.6005g (8.812 mmol) of the dried diamine monomer is accurately weighed, the diamine monomer is added into 17mL anhydrous DMAc and stirred under ice water bath to completely dissolve the diamine monomer, 6FDA 3.915g (8.812 mmol) of the dried dianhydride monomer is accurately weighed, the diamine solution is added, 15.5mL anhydrous DMAc is added, the mixture is stirred under ice water bath for 2 hours, and then the ice water bath is removed. Stirred at 25℃for 24h at room temperature. The reaction liquid is yellowish transparent and has high viscosity. 0.709ml (8.812 mmol) of pyridine is added as a catalyst, 8.27ml of acetic anhydride is added as a dehydrating agent, stirring is continued for 24 hours at room temperature and 25 ℃, the reaction solution is light yellow and transparent and has a higher viscosity, and the reaction is terminated. Slowly adding the reaction solution into 100ml of methanol for washing to separate out white fibrous solid, cutting the fibrous solid, performing suction filtration to obtain a solid, washing the solid twice with 100ml of deionized water, washing the solid with 100ml of methanol, performing suction filtration, and drying the solid in a 100-DEG C vacuum drying oven for 8 hours to obtain 6.38g of white fibrous solid with the yield of 98%, namely the polyimide shown in the general formula (III).
The reaction formula of the above process is as follows:
(3) The preparation process of the polyimide film comprises the following steps:
weighing 0.4005g of polyimide, dissolving in 5.0ml of anhydrous DMAC, placing in a 15ml centrifuge tube with solid content of 8%, centrifuging at 4000r/min for 3 min, absorbing supernatant, coating on a glass plate, placing the glass plate in a blast drying oven, heating at 80 ℃ for 14h to form a film, cooling to room temperature, placing the glass plate in water, and stripping the film to obtain a polyimide film; the transmittance and wavelength relationships of the obtained polyimide films were cut and tested as shown in fig. 9, and the properties of the obtained polyimide films are shown in the following tables 1 and 2.
Example 14: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps: example 10 was repeated except for the following procedure.
The acid binding agent adopts DMAP; 4-nitro-3-trifluoromethyl aniline as acid binding agent=1:1.2:1.5 (molar ratio); after removing the ice-water bath, the reaction was carried out at 30℃for 8 hours.
The hydrogenation catalyst adopts a nickel-containing catalyst, and the solvent adopts isopropanol; the intermediate (C1-1) is a hydrogenation catalyst of 5:2 (mass ratio); 1MPa hydrogen is filled in, and the reaction is magnetically stirred for 18 hours at 70 ℃.
(2) The preparation process of polyimide comprises the following steps: example 1 was repeated except for the following procedure.
The dianhydride monomer adopts PMDA; the reaction was stirred at 30℃for 20 hours. The catalyst adopts trimethyl pyridine, diamine monomer and catalyst, wherein the dehydrating agent=1:5:8 (molar ratio); the reaction was stirred for 30 hours at 15 ℃. Obtaining polyimide shown in a general formula (III).
(3) The preparation process of the polyimide film comprises the following steps: example 1 was repeated except for the following procedure.
After the polyimide polymer was coated on the glass plate, the solvent was evaporated at 60 ℃ for 16 hours; the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Example 15: the low CTE, high light transmittance polyimide and diamine monomer and method of preparation are described below.
(1) The preparation process of the diamine monomer comprises the following steps: example 10 was repeated except for the following procedure.
The acid binding agent adopts potassium bicarbonate and toluene as solvents; 4-nitro-3-trifluoromethyl aniline as acid binding agent=1:1.5:1.8 (molar ratio); after removing the ice-water bath, the reaction was carried out at 15℃for 12 hours.
Pd/C is adopted as the hydrogenation catalyst, and DMF is adopted as the solvent; the intermediate (C1-1) is hydrogenation catalyst 0.5:1 (mass ratio); 5MPa hydrogen is filled in, and the reaction is carried out for 10 hours under the magnetic stirring at the temperature of 75 ℃.
(2) The preparation process of polyimide comprises the following steps: example 1 was repeated except for the following procedure.
The dianhydride monomer adopts H' -PMDA; the reaction was stirred at 15℃for 30 hours. The catalyst adopts isoquinoline, diamine monomer and catalyst, wherein the dehydrating agent is=1:2:5 (molar ratio); the reaction was stirred at 30℃for 20 hours. Obtaining polyimide shown in a general formula (III).
(3) The preparation process of the polyimide film comprises the following steps: example 1 was repeated except for the following procedure.
After the polyimide polymer was coated on the glass plate, the solvent was evaporated at 90 ℃ for 6 hours; the properties of the obtained polyimide film are shown in tables 1 and 2 below.
Table 1: optical Properties and thermal Properties of polyimide films obtained in the examples
In Table 1, cut off is the initial transmission wavelength; t450 is the light transmittance of 450nm wavelength; t550 is the light transmittance of 550nm wavelength; tavg is average light transmittance of 450 nm-550 nm; CTE is the coefficient of thermal expansion (temperature from 50 ℃ C. To 120-200 ℃ C.), and Tg is the glass transition temperature.
Table 2: mechanical Properties of polyimide films obtained in examples
Claims (8)
1. The polyimide with low CTE and high light transmittance is characterized in that the structural general formula is shown as the following formulas (I), (II) and (III):
in the general formula, A and D are both selected from O and NH.
2. The diamine monomer of the low CTE, high light transmittance polyimide of claim 1, having the structural formula (a) (B) (C):
in the general formula, A and D are both selected from O and NH.
3. The process for producing a diamine monomer as claimed in claim 2, wherein: adamantane-1, 3-diformyl chloride, p-nitrophenol and an acid-binding agent are used as raw materials, or adamantane-1, 3-diformyl chloride, 2-fluoro-4-nitroaniline and an acid-binding agent are used as raw materials, or 1, 4-cyclohexane diformyl chloride, 4-nitro-2-trifluoromethyl aniline and an acid-binding agent are used as raw materials, or 1, 4-cyclohexane diformyl chloride, 2-fluoro-4-nitroaniline and an acid-binding agent are used as raw materials, or p-nitrobenzoyl chloride, 4-nitro-3-trifluoromethyl aniline and an acid-binding agent are used as raw materials; acylating the raw materials to generate an intermediate; the intermediate is subjected to hydrogenation reaction under the action of a hydrogenation catalyst, so that the diamine monomer can be obtained.
4. The method for producing a diamine monomer as described in claim 3, wherein any one of the following method steps is employed:
(1) Firstly, adamantane-1, 3-diformyl chloride and an acid binding agent are added into a solvent, stirred in an ice water bath, p-nitrophenol solution is added dropwise, and after the dropwise addition is finished, the reaction is carried out in the ice water bath; then reacting at 15-30 ℃; after the reaction, the reaction solution was filtered and dried to obtain an intermediate (A1-1):
The intermediate (A1-1) and the hydrogenation catalyst react under the conditions of 1-5 MPa of hydrogen and 60-75 ℃; after the reaction is finished, removing the catalyst from the reaction solution, concentrating, and dripping into deionized water to obtain diamine monomer (A1);
(2) Firstly, adding 2-fluoro-4-nitroaniline and an acid binding agent into a solvent, stirring under ice water bath, dropwise adding adamantane-1, 3-diformyl chloride solution, and reacting under ice water bath after the dropwise adding is finished; then reacting at 15-30 ℃; after the reaction, the reaction solution was filtered and dried to obtain an intermediate (A2-1):
the intermediate (A2-1) and the hydrogenation catalyst react under the conditions of 1-5 MPa of hydrogen and 60-75 ℃; after the reaction is finished, removing the catalyst from the reaction solution, concentrating, and dripping into deionized water to obtain diamine monomer (A2);
(3) Firstly, adding 1, 4-cyclohexanedicarboxylic acid chloride and an acid binding agent into a solvent, stirring under ice water bath, dropwise adding 4-nitro-2-trifluoromethyl aniline solution, and reacting under ice water bath after the dropwise adding is finished; then reacting at 15-30 ℃; after the reaction, the reaction solution was filtered and dried to obtain an intermediate (B1-1):
the intermediate (B1-1) reacts with a hydrogenation catalyst under the conditions of 1-5 MPa of hydrogen and 60-75 ℃; after the reaction is finished, removing the catalyst from the reaction solution, concentrating, and dripping into deionized water to obtain diamine monomer (B1);
(4) Firstly, adding 2-fluoro-4-nitroaniline and an acid binding agent into a solvent, stirring under ice water bath, dropwise adding 1, 4-cyclohexane diformyl chloride solution, and reacting under ice water bath after the dropwise adding is finished; then reacting at 15-30 ℃; after the reaction, the reaction solution was filtered and dried to obtain an intermediate (B2-1):
the intermediate (B2-1) reacts with a hydrogenation catalyst under the conditions of 1-5 MPa of hydrogen and 60-75 ℃; after the reaction is finished, removing the catalyst from the reaction solution, concentrating, and dripping into deionized water to obtain diamine monomer (B2);
(5) Firstly, adding 4-nitro-3-trifluoromethyl aniline and an acid binding agent into a solvent, stirring under ice water bath, dropwise adding p-nitrobenzoyl chloride solution, and reacting under ice water bath after the dropwise adding is finished; then reacting at 15-30 ℃; after the reaction, the reaction solution was filtered and dried to obtain (C1-1):
the intermediate (C1-1) and the hydrogenation catalyst react under the conditions of 1-5 MPa of hydrogen and 60-75 ℃; after the reaction, removing the catalyst from the reaction solution, concentrating, and dripping into deionized water to obtain the diamine monomer (C1).
5. The method for producing a diamine monomer as described in claim 4, wherein: in the step (1), the molar ratio of the adamantane-1, 3-diformyl chloride, the p-nitrophenol and the acid binding agent is 1:2-2.5:2-4;
In the step (2), the molar ratio of the adamantane-1, 3-diformyl chloride to the 2-fluoro-4-nitroaniline to the acid binding agent is 1:1.5-3:2-4;
in the step (3), the molar ratio of the 1, 4-cyclohexanedicarboxylic acid chloride to the 4-nitro-2-trifluoromethylaniline to the acid binding agent is 1:2-2.5:1-3;
in the step (4), the molar ratio of the 1, 4-cyclohexanedicarboxylic acid chloride to the 2-fluoro-4-nitroaniline to the acid binding agent is 1:1.5-3:2-4;
in the step (5), the molar ratio of the paranitrobenzoyl chloride to the 4-nitro-3-trifluoromethyl aniline to the acid binding agent is 1:1-1.5:1.5-2.
6. The method for preparing polyimide with low CTE and high light transmittance according to claim 1, wherein: polymerization of diamine monomers with dianhydride monomers as described in claim 2.
7. The method of preparing a low CTE, high light transmittance polyimide as defined by claim 6, wherein the method steps of: s1, carrying out condensation reaction on a diamine monomer and aliphatic dianhydride or aromatic dianhydride to obtain polyamic acid;
s2, adding a dehydrating agent and a catalyst to imidize the polyamide acid to obtain polyimide.
8. The method of producing a low CTE, high light transmittance polyimide as defined by claim 7, wherein: in the step S1, the condensation reaction temperature is 15-30 ℃; in the step S2, the imidization temperature is 15-30 ℃.
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