CN115322156B - Non-coplanar benzimidazole diamine and preparation method and application thereof - Google Patents
Non-coplanar benzimidazole diamine and preparation method and application thereof Download PDFInfo
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- CN115322156B CN115322156B CN202211082087.2A CN202211082087A CN115322156B CN 115322156 B CN115322156 B CN 115322156B CN 202211082087 A CN202211082087 A CN 202211082087A CN 115322156 B CN115322156 B CN 115322156B
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- -1 benzimidazole diamine Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001721 polyimide Polymers 0.000 claims abstract description 33
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 24
- 239000004642 Polyimide Substances 0.000 claims description 19
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 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 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 10
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ZESWUEBPRPGMTP-UHFFFAOYSA-N 4-nitrobenzamide Chemical compound NC(=O)C1=CC=C([N+]([O-])=O)C=C1 ZESWUEBPRPGMTP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- AUBMXHPHQUKKHB-UHFFFAOYSA-N CC(C=C(C=C1)N)=C1C1=NC(C=C(C=C2)N)=C2N1C1=CC=CC=C1 Chemical compound CC(C=C(C=C1)N)=C1C1=NC(C=C(C=C2)N)=C2N1C1=CC=CC=C1 AUBMXHPHQUKKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 6
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 abstract description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 27
- 238000002156 mixing Methods 0.000 description 23
- 238000012360 testing method Methods 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 239000003495 polar organic solvent Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000005917 acylation reaction Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000002798 polar solvent Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 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 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
-
- 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
- C08G73/1075—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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to non-coplanar benzimidazole diamine, and a preparation method and application thereof. The invention provides non-coplanar benzimidazole diamine, which has a structure shown in a formula I. The invention provides a novel benzimidazole diamine with side groups on benzimidazole and benzene rings, wherein the introduction of double side groups promotes the torsion of the benzimidazole rings and the benzene rings to form a non-coplanar structure; in addition, the transparent polyimide film prepared by taking the non-coplanar benzimidazole diamine provided by the invention as a monomer has excellent heat resistance on the basis of low thermal expansion coefficient.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to non-coplanar benzimidazole diamine, and a preparation method and application thereof.
Background
The diamine compound is an important chemical raw material or intermediate, and can be used as a monomer to react with dianhydride to synthesize polyimide, polyamide or polyurea with excellent performance. The side chain group is introduced into the N atom in the diamine compound, so that the steric hindrance and the electronic effect of the side chain group can effectively reduce the charge effect between polymer molecules, and the obtained film is colorless and transparent. However, the flexibility of the molecular chain is too high, the rigidity is reduced, the molecular chain is not firm, and the thermal expansion coefficient is too high.
The coefficient of thermal expansion is an important property of a transparent polyimide (CPI) film and is an important index for measuring the good thermal stability of the CPI film. In the prior art, the thermal expansion coefficient of the CPI film can be obviously reduced by introducing a rigid amide bond into the molecular structure of the CPI; at the same time the amide bonds allow CPI films to have higher glass transition temperatures by forming strong intramolecular or intermolecular hydrogen bonds in the polymer chains. For example, patent document "Hasegawa M,Watanabe Y,Tsukuda S,et al.Solution-processable colorless polyimides with ultralow coefficients of thermal expansion for optoelectronic applications[J].Polymer International,2016,65(9):1063～1073" discloses that the thermal expansion coefficient of a polyimide film can be significantly reduced after an amide bond is introduced, but the obtained film still has the defect of poor heat resistance.
Disclosure of Invention
The invention aims to provide non-coplanar benzimidazole diamine, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides non-coplanar benzimidazole diamine, which has a structure shown in formula I:
the X is-CH 3、-CF3、-C2H5,
The Y is-CH 3、-CF3, -F, -Cl, -Br,
Preferably, the non-coplanar benzimidazole diamine has a structure represented by formula II or formula III:
the invention also provides a preparation method of the non-coplanar benzimidazole diamine, which comprises the following steps:
First mixing a compound with a structure shown in a formula IV, paranitrobenzoyl chloride, an acid binding agent and a first polar organic solvent, and performing condensation acylation reaction to obtain a compound with a structure shown in a formula V;
the species of X and Y in formulas IV and V are the same as those in formula I;
and (3) carrying out a reduction reaction on the compound with the structure shown in the formula V, a hydrogenation catalyst, a reducing agent and a second polar solvent in a second mixing manner to obtain the compound with the structure shown in the formula I.
Preferably, the first polar solvent comprises one or more of dichloroethane, dichloromethane, benzene, toluene, chloroform, carbon tetrachloride and tetrahydrobarking;
The acid binding agent comprises one or more of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate and potassium carbonate.
Preferably, the molar ratio of the compound with the structure shown in the formula IV, the paranitrobenzoyl chloride and the acid binding agent is 1: (2-6): (1.5-6);
the dosage ratio of the compound with the structure shown in the formula IV to the first polar organic solvent is 1g: 10-50 mL.
Preferably, the temperature of the condensation acylation is between-20 ℃ and 40 ℃ and the time is between 12 and 24 hours.
Preferably, the hydrogenation catalyst comprises one or more of palladium carbon, platinum carbon, active nickel and rhodium carbon;
The second polar organic solvent comprises one or more of tetrahydrofuran, ethanol, methanol, isopropanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1, 4-dioxane, acetic acid ethyl acetate, benzene, toluene and xylene;
The reducing agent comprises one or more of tin, stannous chloride, hydrazine hydrate, formic acid and formamidine sulfinic acid.
Preferably, the molar ratio of the compound having the structure shown in formula v, the reducing agent and the hydrogenation catalyst is 1: (5-20): (0.5-1.5);
the dosage ratio of the compound with the structure shown in the formula V to the second polar solvent is 1g: 7-15 mL.
Preferably, the temperature of the reduction reaction is 40-100 ℃, the time is 8-24 h, and the pressure is 0.5-3.0 MPa.
The invention also provides the application of the non-coplanar benzimidazole diamine prepared by the technical scheme or the preparation method of the technical scheme in the synthesis of polyimide, polyamide or polyurea.
The invention provides non-coplanar benzimidazole diamine, which has a structure shown in a formula I. The compound provided by the invention is a novel benzimidazole diamine with side groups on benzimidazole and benzene rings, and the introduction of double side groups promotes the benzimidazole ring and the benzene rings to twist to form a non-coplanar structure, so that the conjugation effect of diamine molecules can be reduced; furthermore, the benzimidazole diamine provided by the invention can be used as a monomer to prepare the transparent polyimide film by introducing the benzimidazole structure and the bisamide structure into the polyimide structural formula, so that the transparent polyimide film has excellent heat resistance on the basis of having a lower thermal expansion coefficient.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of N- (2- (2-methyl-4- (4-nitrobenzamide) phenyl) -1-phenyl-1H-benzimidazol-5-yl) -4-nitrobenzamide obtained in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of 4-amino-N- (4- (5- (4-aminobenzamide) -1-phenyl-1H-benzoimidazol-2-yl) -3-methylphenyl) benzamide obtained in example 1;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of N- (1-methyl-2- (2-methyl-4- (4-nitrobenzamide) phenyl) -1H-benzimidazol-5-yl) -4-nitrobenzamide obtained in example 2;
FIG. 4 is a nuclear magnetic resonance spectrum of 4-amino-N- (4- (5- (4-aminobenzamide) -1-methyl-1H-benzimidazol-2-yl) -3-methylphenyl) benzamide obtained in example 2;
FIG. 5 is a thermal stability test result of a self-supporting transparent polyimide film obtained in the application example;
FIG. 6 shows the glass transition temperature test results of the self-supporting transparent polyimide film obtained in the application example;
FIG. 7 shows the results of the thermal expansion coefficient test of the self-supporting transparent polyimide film obtained in the application example.
Detailed Description
The invention provides non-coplanar benzimidazole diamine, which has a structure shown in formula I:
the X is-CH 3、-CF3、-C2H5,
The Y is-CH 3、-CF3, -F, -Cl, -Br,
In particular embodiments of the present invention, the non-coplanar benzimidazole diamine preferably has a structure represented by formula II or formula III:
the invention also provides a preparation method of the non-coplanar benzimidazole diamine, which comprises the following steps:
First mixing a compound with a structure shown in a formula IV, paranitrobenzoyl chloride, an acid binding agent and a first polar organic solvent, and performing condensation acylation reaction to obtain a compound with a structure shown in a formula V;
the species of X and Y in formulas IV and V are the same as those in formula I;
and (3) carrying out a reduction reaction on the compound with the structure shown in the formula V, a hydrogenation catalyst, a reducing agent and a second polar solvent in a second mixing manner to obtain the compound with the structure shown in the formula I.
In the embodiment of the invention, the synthetic route for synthesizing the non-coplanar benzimidazole diamine is shown as a formula VI:
in the formula VI, the species of X and Y are identical to those of the formula I, and are not described in detail herein.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise
The method comprises the steps of firstly mixing a compound with a structure shown in a formula IV, paranitrobenzoyl chloride, an acid binding agent and a first polar organic solvent, and carrying out condensation acylation reaction to obtain a compound with a structure shown in a formula V;
the species of X and Y in formula IV and formula V are the same as those in formula I.
In the present invention, the acid-binding agent preferably includes one or more of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate and potassium carbonate; when the acid-binding agent is two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited, and the specific substances may be mixed in any ratio.
In the present invention, the first polar solvent preferably includes one or more of dichloroethane, dichloromethane, benzene, toluene, chloroform, carbon tetrachloride and tetrahydrobarking; when the first polar organic solvent is two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited, and the specific substances may be mixed in any ratio.
In the invention, the molar ratio of the compound with the structure shown in the formula IV, the paranitrobenzoyl chloride and the acid binding agent is preferably 1: (2-6): (1.5 to 6), more preferably 1: (2.5-5.5): (2.0 to 5.5), more preferably 1: (3.0-5.0): (2.5-5.0). In the present invention, the ratio of the compound having the structure represented by formula iv to the first polar organic solvent is preferably 1g:10 to 50mL, more preferably 1g:20 to 40mL, more preferably 1g: 25-30 mL.
In the present invention, the first mixing process is preferably: premixing a compound with a structure shown in a formula IV, an acid binding agent and part of a first polar organic solvent, and reducing the temperature of the obtained mixture to 5-10 ℃ by adopting an ice-water bath to obtain a premix;
And dissolving the paranitrobenzoyl chloride in the residual first polar organic solvent, and dropwise adding the obtained paranitrobenzoyl chloride solution into the premix.
In the present invention, the mass concentration of the compound having the structure represented by formula iv in the premix is preferably 4 to 15%, more preferably 5 to 12%, still more preferably 8 to 10%. In the present invention, the mass concentration of paranitrobenzoyl chloride in the paranitrobenzoyl chloride solution is preferably 8 to 20%, more preferably 10 to 15%.
The process of premixing and remixing is not particularly limited in the present invention, and may be performed by a process well known to those skilled in the art.
In the present invention, the dropping speed of the dropping is preferably 0.5 to 1.5mL/min, and the time is preferably 0.7 to 1.2mL/min. The temperature of the premix is preferably controlled to be 0-20 ℃ in the dripping process. The method of controlling the temperature of the present invention is not particularly limited, and may be carried out according to methods well known to those skilled in the art.
In the present invention, the temperature of the condensation acylation reaction is preferably-20 to 40 ℃, further preferably 0 to 20 ℃; the time is preferably 12 to 24 hours, more preferably 16 to 20 hours. In a specific embodiment of the invention, the condensation acylation reaction is carried out at room temperature.
In embodiments of the present invention, TLC is preferably used to monitor the end of the reaction.
After the condensation acylation reaction is finished, the invention also preferably comprises post-treatment of a product obtained by the reaction; the post-treatment is preferably:
Carrying out first reduced pressure suction filtration on a product obtained by the condensation and acylation reaction to obtain a crude product;
mixing the crude product with methanol, performing second reduced pressure suction filtration, and repeating for 3-4 times;
And drying the solid product obtained by the second suction filtration.
The first reduced pressure suction filtration process is not particularly limited, and may be performed by a process known to those skilled in the art.
In the present invention, the mixing is performed under stirring, and the stirring time is preferably 2 to 3 hours. The stirring speed is not particularly limited, and may be carried out as known to those skilled in the art.
The drying process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In an embodiment of the present invention, the yield of the compound having the structure of formula v is specifically 84%.
After the compound with the structure shown in the formula V is obtained, the compound with the structure shown in the formula V, a hydrogenation catalyst, a reducing agent and a second polar solvent are mixed for a second time, and a reduction reaction is carried out, so that the compound with the structure shown in the formula I is obtained.
In the present invention, the hydrogenation catalyst preferably comprises one or more of palladium carbon, platinum carbon, active nickel and rhodium carbon; when the hydrogenation catalyst is two or more of the above-mentioned choices, the ratio of the specific substances is not particularly limited in the present invention, and the specific substances may be mixed in any ratio.
In the present invention, the second polar organic solvent preferably includes one or more of tetrahydrobarking, ethanol, methanol, isopropanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1, 4-dioxane, acetic acid ethyl acetate, benzene, toluene and xylene; when the second polar organic solvent is two or more of the above-mentioned choices, the proportion of the specific substances in the present invention is not particularly limited, and the specific substances may be mixed in any proportion.
In the present invention, the reducing agent preferably includes one or more of tin, stannous chloride, hydrazine hydrate, formic acid and formamidine sulfinic acid. In the invention, the reducing agent is preferably added in the form of an aqueous reducing agent solution; the concentration of the aqueous solution of the reducing agent is not particularly limited, and may be known to those skilled in the art. In a specific embodiment of the present invention, the mass concentration of hydrazine hydrate in the aqueous solution of hydrazine hydrate is preferably 80%.
In the present invention, the molar ratio of the compound having the structure of formula v, the reducing agent and the hydrogenation catalyst is preferably 1: (5-20): (0.5 to 1.5), more preferably 1: (10-15): (1.0-1.2).
In the present invention, the ratio of the compound having the structure of formula V to the second polar solvent is preferably 1g:7 to 15mL, more preferably 1g: 10-12 mL.
In the present invention, the second mixing process is preferably: and mixing the compound with the structure shown in the formula V, a hydrogenation catalyst and a second polar organic solvent, and then dropwise adding a reducing agent solution. In the present invention, the dropping speed of the reducing agent solution is preferably 0.3 to 0.7mL/min, and the time is preferably 0.4 to 0.6mL/min.
In the present invention, the temperature of the reduction reaction is preferably 40 to 100 ℃, more preferably 50 to 90 ℃, still more preferably 60 to 80 ℃; the time is preferably 8-24 hours; the pressure is preferably 0.5 to 3.0MPa. In the present invention, the reduction reaction is preferably carried out in a vessel filled with an inert gas.
In embodiments of the present invention, TLC is preferably used to monitor the end of the reaction.
After the reduction reaction is completed, the invention also preferably comprises post-treatment of the obtained reduction product; the post-treatment is preferably:
Filtering a product obtained by the reduction reaction to obtain a recovered hydrogenation catalyst and filtrate respectively;
And mixing the filtrate with water, cooling and crystallizing, and drying after reduced pressure suction filtration to obtain the compound with the structure shown in the formula I.
In a specific embodiment of the invention, the pore size of the filter head used for the filtration is preferably 0.22 μm. In the present invention, the number of times of filtration is preferably 2 to 3. In the present invention, the hydrogenation catalyst in the product can be sufficiently recovered by filtration a plurality of times.
The process of mixing, vacuum filtration and drying is not particularly limited, and may be performed by a process well known to those skilled in the art.
The types of the side groups (namely X and Y groups) introduced on the benzimidazole ring and the benzene ring are changeable, the disadvantage of single structure of the diamine monomer can be overcome, and the diamine monomer can be applied to the synthesis of the polymeric material to obtain a plurality of polymeric materials with different structures, so that the method has wide application prospect.
The preparation method provided by the invention has the advantages of low-cost and easily-obtained raw materials, high process safety, simplicity and convenience in operation, lower production cost and higher reaction yield, and is suitable for industrial production.
The invention also provides the application of the non-coplanar benzimidazole diamine prepared by the technical scheme or the preparation method of the technical scheme in the synthesis of polyimide, polyamide or polyurea.
In the present invention, the preparation method of the polyimide preferably comprises the steps of:
Mixing non-coplanar benzimidazole diamine, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, isoquinoline and m-cresol, and carrying out polymerization reaction to obtain the polyimide.
In the present invention, the molar ratio of the non-coplanar benzimidazole diamine to 1,2,4, 5-cyclohexane tetracarboxylic dianhydride is preferably 1:1 to 1.3. In the present invention, the ratio of the amount of non-coplanar benzimidazole diamine to isoquinoline is preferably 1g: 0.3-0.5 mL. In the present invention, the solid content of the mixed liquid is preferably 15% to 20%.
In the present invention, the mixing process is preferably:
primary mixing of non-coplanar benzimidazole diamine and m-cresol to obtain primary mixed solution;
Mixing the primary mixed solution with 1,2,4, 5-cyclohexane tetracarboxylic dianhydride in a secondary mode to obtain a secondary mixed solution;
And mixing the secondary mixed solution with isoquinoline three-stage.
In the present invention, the primary mixing is preferably performed under stirring; the rotation speed of the stirring is preferably 400r/min; the time is preferably 6 to 8 hours. In the present invention, the primary mixing is preferably performed under a nitrogen atmosphere.
In the present invention, the secondary mixing is preferably performed under stirring. The stirring condition parameters are not particularly limited in the present invention, and those well known to those skilled in the art may be employed. In the present invention, the time of the secondary mixing is preferably 1 to 3 hours.
The process of the three-stage mixing is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the polymerization reaction is preferably carried out at a temperature of 180 to 220℃for a time of 6 to 10 hours. In the present invention, the polymerization is preferably carried out under stirring; the stirring speed is preferably 200-500 r/min.
After the polymerization reaction is completed, the invention also preferably comprises post-treatment of the obtained product; the post-treatment preferably includes cooling, precipitation, filtration, washing and drying which are sequentially performed.
The cooling process is not particularly limited, and may be performed by a process known to those skilled in the art.
In the present invention, the process of precipitation is preferably: and mixing the cooled product with ethanol, and carrying out precipitation. The amount of ethanol added in the present invention is not particularly limited, and can be any one known to those skilled in the art
The filtering process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the washing preferably includes sequentially performing ethanol washing and water washing. The processes of the ethanol washing and the water washing are not particularly limited, and those skilled in the art are familiar with the processes.
The drying process is not particularly limited, and may be performed as known to those skilled in the art.
After the polyimide is obtained, the invention also preferably comprises the steps of dissolving the polyimide in N-methyl pyrrolidone for sealing and preserving. In the invention, the mass ratio of the polyimide to the N-methylpyrrolidone is preferably 1:25.
For further explanation of the present invention, a non-coplanar benzimidazole diamine, a preparation method and application thereof, provided by the present invention, will be described in detail with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
In this example, the structure of the non-coplanar benzimidazole diamine (formula II) is shown below:
chinese name 4-amino-N- (4- (5- (4-aminobenzamide) -1-phenyl-1H-benzoimidazol-2-yl) -3-methylphenyl) benzamide;
The preparation method comprises the following steps:
After 10.0g of 2- (4-amino-2-methylphenyl) -1-phenyl-1H-benzimidazol-5-amine, 9.65g of triethylamine and 70mL of tetrahydrofuran were added to the reaction flask, the reaction system was cooled to 5℃with an ice-water bath to obtain a premix; 17.71g of paranitrobenzoyl chloride is dissolved in 130mL of tetrahydrofuran, and then is added into the premix in a dropwise manner at a dropwise speed of 1mL/min, and the dropwise addition is completed for 1h, so that the temperature of a reaction system in the dropwise addition process is ensured not to exceed 10 ℃; the reaction was carried out at room temperature for 16h, and the end of the reaction was determined by TLC. After the reaction is finished, carrying out vacuum filtration on the product in the reaction bottle to obtain 23.1g of crude product; 22.73g of crude product is added into a reaction bottle, 120mL of methanol is poured into the reaction bottle, stirring is carried out for 6 hours, suction filtration is carried out again, the product obtained by suction filtration is dried after 3 times of repetition, and 16.35g of N- (2- (2-methyl-4- (4-nitrobenzamide) phenyl) -1-phenyl-1H-benzimidazol-5-yl) -4-nitrobenzamide is obtained, the yield is 84%, the structure nuclear magnetism is confirmed, the nuclear magnetism hydrogen spectrum is shown in figure 1, and the structure is shown in a formula VII:
10.0g N- (2-methyl-4- (4-nitrobenzamide) phenyl) -1-phenyl-1H-benzimidazol-5-yl) -4-nitrobenzamide, 1g palladium on carbon and 100mL of ethanol are added into a reaction bottle, 6.54g of hydrazine hydrate with the mass concentration of 80% is dropwise added at the dropwise speed of 0.5mL/min after completion of 2H, the reaction is heated at 80 ℃ for 36H for reduction, and TLC determines the end of the reaction. After the completion of the reaction, palladium on carbon in the reaction mixture was filtered by a 0.22 μm filter head and repeated 3 times to ensure complete filtration. 400mL of water was added to the reaction solution after filtration for cooling crystallization, and the obtained crystals were subjected to suction filtration under reduced pressure and dried to obtain 7.39g of 4-amino-N- (4- (5- (4-aminobenzamide) -1-phenyl-1H-benzimidazol-2-yl) -3-methylphenyl) benzamide (structure represented by formula II) with a yield of 82%, and a nuclear magnetic resonance spectrum of the structure was confirmed as shown in FIG. 2.
Example 2
In this example, the structure of the non-coplanar benzimidazole diamine (formula III) is shown below:
Chinese name 4-amino-N- (4- (5- (4-aminobenzamide) -1-methyl-1H-benzoimidazol-2-yl) -3-methylphenyl) benzamide;
The preparation method comprises the following steps:
after 10.0g of 2- (4-amino-2-methylphenyl) -1-methyl-1H-benzo [ d ] imidazol-5-amine, 9.65g of triethylamine and 70mL of tetrahydrofuran were added to the reaction flask, the reaction system was cooled to 5℃with an ice-water bath to obtain a premix; 17.71g of paranitrobenzoyl chloride is dissolved in 130mL of tetrahydrofuran, and then is added into the premix in a dropwise manner at a dropwise speed of 1mL/min, and the dropwise addition is completed for 1h, so that the temperature of a reaction system in the dropwise addition process is ensured not to exceed 10 ℃; the reaction was carried out at room temperature for 16h, and the end of the reaction was determined by TLC. After the reaction is finished, carrying out vacuum filtration on the product in the reaction bottle to obtain 23.1g of crude product; 23.1g of crude product is added into a reaction bottle, 120mL of methanol is poured into the bottle, stirring is carried out for 6 hours, suction filtration is carried out again, the product obtained by suction filtration is dried after 3 times of repetition, and 18.34g N- (1-methyl-2- (2-methyl-4- (4-nitrobenzamide) phenyl) -1H-benzimidazol-5-yl) -4-nitrobenzamide is obtained, the yield is 84%, the nuclear magnetism of the structure is confirmed, the nuclear magnetism hydrogen spectrum is shown in figure 3, and the structure is shown in formula VIII:
10.0g N- (1-methyl-2- (2-methyl-4- (4-nitrobenzamide) phenyl) -1H-benzimidazole-5-yl) -4-nitrobenzamide, 1g palladium on carbon and 100mL of ethanol are added into a reaction bottle, 7.28g of hydrazine hydrate with the mass concentration of 80% is dropwise added at the dropwise speed of 0.5mL/min, the dropwise addition is completed for 2 hours, the reaction is heated at 80 ℃ for 36 hours for reduction, and TLC determines the end of the reaction. After the completion of the reaction, palladium on carbon in the reaction mixture was filtered by a 0.22 μm filter head and repeated 3 times to ensure complete filtration. 400mL of water was added to the reaction solution after filtration for cooling crystallization, and the obtained crystals were subjected to suction filtration under reduced pressure and dried to obtain 7.39g of 4-amino-N- (4- (5- (4-aminobenzamide) -1-methyl-1H-benzimidazol-2-yl) -3-methylphenyl) benzamide (structure shown in formula III) with a yield of 82%, and the nuclear magnetic resonance of the structure was confirmed, and a nuclear magnetic resonance spectrum was shown in FIG. 4.
Application example
10G of 4-amino-N- (4- (5- (4-aminobenzamide) -1-phenyl-1H-benzimidazol-2-yl) -3-methylphenyl) benzamide obtained in example 1 and 49g of m-cresol were mixed and stirred under a nitrogen atmosphere at a stirring speed of 400r/min for 6 hours to obtain a first-order mixed solution; adding 4.056g of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride into the first-stage mixed solution, stirring for 60min, and obtaining a second-stage mixed solution after the solid powder is dissolved; adding 0.2g of isoquinoline into the secondary mixed solution, and reacting for 8 hours at the temperature of 200 ℃ at the rotating speed of 300 r/min; after the reaction is completed, the reaction system is cooled and poured into a large amount of ethanol, and after the precipitate is collected, the polyimide is obtained after the precipitate is fully washed by ethanol and water and dried.
10G of the polyimide obtained above was dissolved in 250g of N-methylpyrrolidone, and after complete dissolution, the polyimide was stored in a sealed state to obtain a uniform polyimide solution.
Performance testing
Coating the uniform polyimide solution obtained in the application example on a clean and flat glass sheet, wherein the thickness of a coating machine is controlled to be 20 mu m;
Transferring the coated glass sheet into a muffle furnace, and removing the solvent according to a heating program of 80 ℃/2h,150 ℃/2h and 250 ℃/2 h; after the muffle furnace is cooled to room temperature, taking out the glass plate, and putting the glass plate into hot water at 50 ℃, and stripping the obtained polyimide film from the glass plate to obtain a self-supporting transparent polyimide film;
Test example 1
(1) The self-supporting transparent polyimide film obtained was subjected to a thermal stability (T d5％) test under the following conditions: adopting TGA550, and under the condition of heating rate of 10 ℃/min in nitrogen atmosphere, the temperature interval is room temperature to 800 ℃; the test results are shown in fig. 5 and table 1;
(2) The glass transition temperature of the obtained self-supporting transparent polyimide film is tested under the following conditions: heating up at a heating rate of 10 ℃/min under an air atmosphere by using a Q800 type dynamic thermo-mechanical analyzer of the company TA of America, wherein the test frequency is 1Hz, and the peak value of a loss tangent tan delta curve is taken as the glass transition temperature of the polyimide film, and the test results are shown in FIG. 6 and Table 1;
(3) Testing the Coefficient of Thermal Expansion (CTE) of the resulting self-supporting transparent polyimide film; the test conditions were: heating was performed using a thermo-mechanical analyzer of the company TA company Q400 in the united states under nitrogen atmosphere at a temperature rise rate of 5 ℃/min, and the preload static force was set to 0.05N; before testing, annealing the sample at 20 ℃ below the glass transition temperature;
The coefficient of thermal expansion CTE is calculated according to the following formula:
CTE＝ΔL/(L·ΔT)；
Wherein L is the original length of the thin film spline; delta T is the temperature range (100-250 ℃) of the sample selection; ΔL is the amount of dimensional change of the film sample over the temperature range of 100-250 ℃;
The test results are shown in fig. 7 and table 1;
TABLE 1 self-supporting transparent polyimide film test results
| Td5％(℃) | Tg(℃) | CTE(ppm/K) | |
| Test results | 448 | 394 | 34 |
As can be seen from table 1 and fig. 5, 6,7, the polyimide synthesized from the non-coplanar benzimidazole diamine provided by the present invention as a monomer has excellent thermal properties.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (1)
1. Use of a non-coplanar benzimidazole diamine in the synthesis of a polyimide, wherein the non-coplanar benzimidazole diamine has a structure according to formula ii:
The preparation method of the non-coplanar benzimidazole diamine comprises the following steps:
After 10.0g of 2- (4-amino-2-methylphenyl) -1-phenyl-1H-benzimidazol-5-amine, 9.65g of triethylamine and 70mL of tetrahydrofuran were added to the reaction flask, the reaction system was cooled to 5℃with an ice-water bath to obtain a premix; 17.71g of paranitrobenzoyl chloride is dissolved in 130mL of tetrahydrofuran, and then is added into the premix in a dropwise manner at a dropwise speed of 1mL/min, and the dropwise addition is completed for 1h, so that the temperature of a reaction system in the dropwise addition process is ensured not to exceed 10 ℃; reacting for 16h at room temperature, and determining the end of the reaction by TLC; after the reaction is finished, carrying out vacuum filtration on the product in the reaction bottle to obtain 23.1g of crude product; 22.73g of the crude product was added to a reaction flask and poured into 120mL of methanol, stirred for 6 hours, suction filtered again, and after repeating 3 times, the product obtained by suction filtration was dried to obtain 16.35g of N- (2- (2-methyl-4- (4-nitrobenzamide) phenyl) -1-phenyl-1H-benzimidazol-5-yl) -4-nitrobenzamide with a yield of 84%, and the structure was shown in formula VII:
10.0g N- (2-methyl-4- (4-nitrobenzamide) phenyl) -1-phenyl-1H-benzimidazole-5-yl) -4-nitrobenzamide, 1g palladium carbon and 100mL of ethanol are added into a reaction bottle, 6.54g of hydrazine hydrate with the mass concentration of 80% is dropwise added at the dropwise speed of 0.5mL/min, the dropwise addition is completed for 2 hours, the reaction is heated at 80 ℃ for 36 hours for reduction, and TLC determines that the reaction is finished; after the reaction is finished, filtering palladium carbon in the reaction liquid by using a filter head with the diameter of 0.22 mu m, and repeating for 3 times to ensure that the filtration is complete; adding 400mL of water into the filtered reaction solution for cooling crystallization, and carrying out vacuum filtration and drying on the obtained crystal to obtain 7.39g of 4-amino-N- (4- (5- (4-aminobenzamide) -1-phenyl-1H-benzimidazole-2-yl) -3-methylphenyl) benzamide;
The application steps are as follows:
10g of 4-amino-N- (4- (5- (4-aminobenzamide) -1-phenyl-1H-benzimidazol-2-yl) -3-methylphenyl) benzamide and 49g of m-cresol were mixed and stirred under a nitrogen atmosphere at a stirring speed of 400r/min for 6 hours to obtain a primary mixed solution; adding 4.056g of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride into the first-stage mixed solution, stirring for 60min, and obtaining a second-stage mixed solution after the solid powder is dissolved; adding 0.2g of isoquinoline into the secondary mixed solution, and reacting for 8 hours at the temperature of 200 ℃ at the rotating speed of 300 r/min; after the reaction is completed, the reaction system is cooled and poured into a large amount of ethanol, and after the precipitate is collected, the polyimide is obtained after the precipitate is fully washed by ethanol and water and dried.
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| CN110577495A (en) * | 2019-08-28 | 2019-12-17 | 东华大学 | amide-containing N-substituted benzimidazole diamine and preparation method thereof |
| CN112608279A (en) * | 2020-12-11 | 2021-04-06 | 东华大学 | Non-coplanar benzimidazole diamine and preparation method thereof |
| CN112625239A (en) * | 2020-12-11 | 2021-04-09 | 东华大学 | Polyimide containing non-coplanar benzimidazole and preparation method thereof, and transparent polyimide film and preparation method and application thereof |
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| CN110577495A (en) * | 2019-08-28 | 2019-12-17 | 东华大学 | amide-containing N-substituted benzimidazole diamine and preparation method thereof |
| CN112608279A (en) * | 2020-12-11 | 2021-04-06 | 东华大学 | Non-coplanar benzimidazole diamine and preparation method thereof |
| CN112625239A (en) * | 2020-12-11 | 2021-04-09 | 东华大学 | Polyimide containing non-coplanar benzimidazole and preparation method thereof, and transparent polyimide film and preparation method and application thereof |
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