CN116354864A - Diamine containing intramolecular imide ring and aliphatic alkyl group, polyimide formed based on diamine, preparation method and application thereof - Google Patents
Diamine containing intramolecular imide ring and aliphatic alkyl group, polyimide formed based on diamine, preparation method and application thereof Download PDFInfo
- Publication number
- CN116354864A CN116354864A CN202310259608.5A CN202310259608A CN116354864A CN 116354864 A CN116354864 A CN 116354864A CN 202310259608 A CN202310259608 A CN 202310259608A CN 116354864 A CN116354864 A CN 116354864A
- Authority
- CN
- China
- Prior art keywords
- polyimide
- dianhydride
- diamine
- polyimide film
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 147
- 150000004985 diamines Chemical class 0.000 title claims abstract description 85
- 239000004642 Polyimide Substances 0.000 title claims abstract description 45
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000005462 imide group Chemical group 0.000 title claims abstract 7
- 125000001931 aliphatic group Chemical group 0.000 title claims description 25
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 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 abstract description 33
- -1 nitro anhydride Chemical class 0.000 claims abstract description 18
- 230000003287 optical effect Effects 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 93
- 238000006243 chemical reaction Methods 0.000 claims description 68
- 239000007787 solid Substances 0.000 claims description 65
- 239000012043 crude product Substances 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 35
- 239000007795 chemical reaction product Substances 0.000 claims description 34
- 229920005575 poly(amic acid) Polymers 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 32
- 239000012265 solid product Substances 0.000 claims description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 238000001291 vacuum drying Methods 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 10
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 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 6
- 239000002253 acid Substances 0.000 claims description 6
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 4
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 2
- DIUALWFQMYOAFP-UHFFFAOYSA-N 1,3,6,8-tetraoxofuro[3,4-e][2]benzofuran-4,5-dicarboxylic acid Chemical compound O=C1OC(=O)C2=C1C(C(=O)O)=C(C(O)=O)C1=C2C(=O)OC1=O DIUALWFQMYOAFP-UHFFFAOYSA-N 0.000 claims description 2
- ZBOLYDUBEGGDKS-UHFFFAOYSA-N 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=C(Cl)C=C(C(O)=O)C2=C(C(O)=O)C=C(Cl)C=1C1=C(Cl)C=C(C(O)=O)C2=C1C3=C(Cl)C=C2C(=O)O ZBOLYDUBEGGDKS-UHFFFAOYSA-N 0.000 claims description 2
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 claims description 2
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 claims description 2
- RSAGQQQIRZLFHJ-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-4-yl)diazenyl]-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2N=NC1=CC=CC2=C1C(=O)OC2=O RSAGQQQIRZLFHJ-UHFFFAOYSA-N 0.000 claims description 2
- POLIXZIAIMAECK-UHFFFAOYSA-N 4-[2-(2,6-dioxomorpholin-4-yl)ethyl]morpholine-2,6-dione Chemical compound C1C(=O)OC(=O)CN1CCN1CC(=O)OC(=O)C1 POLIXZIAIMAECK-UHFFFAOYSA-N 0.000 claims description 2
- YCXQKJXTGDYKIO-UHFFFAOYSA-N 4-nitro-2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=C([N+]([O-])=O)C=C1C1=CC=CC=C1 YCXQKJXTGDYKIO-UHFFFAOYSA-N 0.000 claims description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 2
- DGQOZCNCJKEVOA-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1CC(=O)OC1=O DGQOZCNCJKEVOA-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007868 Raney catalyst Substances 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 claims description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005591 trimellitate group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000003951 lactams Chemical group 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 34
- 150000003949 imides Chemical group 0.000 description 29
- 239000000203 mixture Substances 0.000 description 25
- 239000012299 nitrogen atmosphere Substances 0.000 description 25
- 238000006068 polycondensation reaction Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 238000007790 scraping Methods 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 11
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- DYGPKZRYPCCCLU-UHFFFAOYSA-N 2-(aminomethoxy)ethoxymethanamine Chemical compound NCOCCOCN DYGPKZRYPCCCLU-UHFFFAOYSA-N 0.000 description 2
- STMZGJLCKJFMLQ-UHFFFAOYSA-N 2-[3-(2-aminoethyl)cyclohexyl]ethanamine Chemical compound NCCC1CCCC(CCN)C1 STMZGJLCKJFMLQ-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OTKFKCIRTBTDKK-UHFFFAOYSA-N [3-(aminomethyl)-5-bicyclo[2.2.1]heptanyl]methanamine Chemical compound C1C(CN)C2C(CN)CC1C2 OTKFKCIRTBTDKK-UHFFFAOYSA-N 0.000 description 2
- VLGUBUHHNFCMKI-UHFFFAOYSA-N aminomethoxymethanamine Chemical compound NCOCN VLGUBUHHNFCMKI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- GGAUUQHSCNMCAU-UHFFFAOYSA-N butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)CC(O)=O GGAUUQHSCNMCAU-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 2
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002466 imines Chemical group 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- HFBHOAHFRNLZGN-LURJTMIESA-N (2s)-2-formamido-4-methylpentanoic acid Chemical compound CC(C)C[C@@H](C(O)=O)NC=O HFBHOAHFRNLZGN-LURJTMIESA-N 0.000 description 1
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 description 1
- LJVGYWLSCKCZQK-UHFFFAOYSA-N 2-[2-(2-aminoethyl)cyclohexyl]ethanamine Chemical compound NCCC1CCCCC1CCN LJVGYWLSCKCZQK-UHFFFAOYSA-N 0.000 description 1
- XUXZELZSNNYLRE-UHFFFAOYSA-N 2-[4-(2-aminoethyl)cyclohexyl]ethanamine Chemical compound NCCC1CCC(CCN)CC1 XUXZELZSNNYLRE-UHFFFAOYSA-N 0.000 description 1
- KRPRVQWGKLEFKN-UHFFFAOYSA-N 3-(3-aminopropoxy)propan-1-amine Chemical compound NCCCOCCCN KRPRVQWGKLEFKN-UHFFFAOYSA-N 0.000 description 1
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 description 1
- FVUIAOHMTFHVTE-UHFFFAOYSA-N 3-[2-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCOCCCN FVUIAOHMTFHVTE-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/62—Naphtho [c] pyrroles; Hydrogenated naphtho [c] pyrroles
- C07D209/66—Naphtho [c] pyrroles; Hydrogenated naphtho [c] pyrroles with oxygen atoms in positions 1 and 3
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses diamine containing a molecular lactam ring and aliphatic alkyl, polyimide formed based on diamine, and a preparation method and application thereof; diamine monomer is prepared by condensation reaction of nitro anhydride and diamine containing fatty alkyl, introduction of fatty alkyl and imide ring structure and reduction; the alkalinity of diamine monomer amino can be effectively weakened when polyimide is polymerized by monomer, the phenomenon that polymerization is difficult because of formation of precipitation caused by salification in the polymerization process is avoided, so that the polymerization degree is improved, the molecular weight and the mechanical property of polyimide are improved, meanwhile, the generation of a complex compound of charge transfer between a diamine electron donor and a dianhydride electron acceptor can be inhibited by introducing fatty alkyl, and the optical transparency of a polyimide film is improved; through tests, the polyimide film has mechanical properties obviously superior to those of the traditional polyimide film, has higher optical transparency, and has good prospect in the field of electronic products such as flexible electronic display devices, flexible circuit board matrix materials and the like.
Description
Technical Field
The invention relates to the technical field of materials, in particular to diamine containing a molecular imide ring and aliphatic alkyl, polyimide formed based on diamine, and a preparation method and application thereof.
Background
Polyimide (PI) is a high-performance polymer with a plurality of imide five-membered heterocyclic rings, and is widely applied to the fields of aerospace, electronic and electric appliances, gas separation, fuel cells, optics, biomedicine, sensors and the like (Fuel, 2012,96, 1:15-28) due to the unique properties of electrochemical performance, radiation resistance, chemical corrosion resistance, excellent mechanical properties and the like. Conventional wholly aromatic polyimide is generally yellow in color due to the influence of intermolecular and intramolecular Charge Transfer Complexes (CTCs), and thus is not suitable for the display field requiring high light transmittance, aliphatic polyimide, particularly wholly alicyclic polyimide, generally has high light transmittance, and the color of the film material can be made colorless, so that aliphatic alkyl polyimide is more suitable for transparent display materials (prog.polym.sci, 2008,33, 6:581-630).
Fatty alkyl polyimide refers to polyimide containing fatty alkyl structure in the polymer molecular chain. The fatty alkyl has no pi electron, so that CTC effect is difficult to form, and the light transmittance of polyimide is effectively improved (Polymer, 2018,151,325-333). The fatty alkyl can obviously destroy the order of polymer molecular chains, reduce intermolecular acting force, and enable solvent molecules to more easily penetrate between polymer chain segments, thereby improving the solubility of polyimide. And most of the aliphatic rings (five-membered aliphatic ring and six-membered aliphatic ring) have certain rigidity, and can endow polyimide with good thermal performance and mechanical performance. In addition, part of fatty alkyl has good hydrophobicity, which is beneficial to reducing the water absorption rate and dielectric constant of the polymer. Therefore, the polyimide containing the fatty alkyl group has the advantages of good thermal property, mechanical strength, solubility, light transmittance and the like (J.Photopolym. Sci. Tec,2017, 30:133-137).
Although the fatty alkyl polyimide has wide application prospect, the industrialized application examples are still few, mainly because fatty amine is easy to form salt to generate precipitate to prevent polymerization in the polyimide polymerization process, and a polymer with high molecular weight is difficult to obtain, so that the application and development of the fatty alkyl polyimide are greatly limited.
Disclosure of Invention
The invention aims to provide diamine containing a molecular imide ring and an aliphatic alkyl group and a preparation method thereof.
The invention also aims to provide polyimide prepared from the diamine containing the intramolecular imide ring and the aliphatic alkyl group and a preparation method thereof.
Another object of the present invention is to provide a polyimide film prepared from the above polyimide.
Another object of the present invention is to provide a polyimide or polyimide film as described above.
For this purpose, the technical scheme of the invention is as follows:
a diamine containing a molecular imide ring and an aliphatic alkyl group, which has the chemical structural formula:
wherein Ar is a benzene ring or a naphthalene ring; r is one of the formulas (1) to (10);
formula (1):
wherein m is an integer, and the value range is 2-7, preferably 2-5;
Formula (2):
wherein the method comprises the steps ofM and n are integers; m has a value ranging from 1 to 4, preferably from 1 to 2; the value range of n is 1-4, preferably 1-2;
formula (3):
wherein m is an integer, and the value range is 2-6, preferably 3-5;
formula (4):
wherein m is an integer, and the value range of m is 1-5, preferably 1-2;
formula (5):
formula (6):
wherein m and n are integers; m has a value ranging from 1 to 3, preferably 2; n is in the range of 1 to 3, preferably 2;
formula (7):
wherein m and n are integers; m has a value ranging from 1 to 5, preferably from 1 to 3; n is 1 to 5, preferably 1 to 3;
formula (8):
wherein m, n and o are integers; m is 1-3; n is 2-3; o has a value in the range of 1 to 3, preferably 2;
formula (9):
wherein m, n, o, p is an integer; m is 1-3; n is 2 to 3, preferably 2; o has a value in the range of 2 to 3, preferably 2; the value range of p is 1-3;
formula (10):
wherein m, n, o, p, q is an integer; m is 1-3; n is 2 to 3, preferably 2; o has a value in the range of 2 to 3, preferably 2; the value range of p is 2-3, preferably 2; q is in the range of 1 to 3.
A preparation method of diamine containing a molecular imide ring and an aliphatic alkyl group comprises the following preparation steps:
(1) Under the protection of inert gas, adding the monomer I and the monomer II into an organic solvent, mixing and stirring uniformly, reacting for 8-12 hours at room temperature, and then heating to 150-220 ℃ for reflux for 12-24 hours; naturally cooling the reaction product liquid until solid is separated out, filtering, washing the filtered precipitate with dilute hydrochloric acid and distilled water to neutrality, and washing with methanol for 2-5 times to obtain coarse product; recrystallizing the crude product by utilizing DMF, and vacuum drying the obtained solid at 50-100 ℃ to obtain a solid product;
(2) Dissolving the solid product obtained in the step (1) in an organic solvent, adding a catalyst, dropwise adding hydrazine hydrate into the solution under an ice water bath, and after the dropwise adding is finished, placing the mixed reaction solution at 20-90 ℃ for continuous reaction for 5-12 h to obtain a reaction product solution; filtering the obtained reaction product liquid while the reaction product liquid is hot, and concentrating the filtrate to separate out solids to obtain a crude product; recrystallizing the crude product by utilizing DMF, and vacuum drying the obtained solid at 0-50 ℃ to obtain diamine monomer;
preferably, in step (1), monomer I is
In particular, the monomers I are ethylenediamine, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diphenyl-2, 5-hexamethylenediamine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, trans-1, 4-diaminocyclohexane, 1, 2-bis (2-aminoethyl) cyclohexane, 1, 3-bis (2-aminoethyl) cyclohexane, 1, 4-bis (2-aminoethyl) cyclohexane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether [ (2-Aminomethoxy) ethyl radical]Ethers, bis [2- (2-aminoethoxy) ethyl]Ethers, 1, 2-bis (aminomethoxy) ethane, 1, 2-bis (aminoethoxy) ethane, 1, 2-bis [2- (aminomethoxy) ethoxy ]]Ethane, 1, 2-bis [2- (2-aminoethoxy) ethoxy ]]Ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, bis (4-aminocyclohexyl) methane, 2, 6-bis (aminomethyl) bicyclo [2.2.1]Heptane, 2, 5-bis (aminomethyl) bicyclo [2.2.1]At least one of heptane.
Preferably, monomer II is 4-nitroanhydride or 6-nitronaphthalene anhydride.
Preferably, in step (1), the molar ratio of monomer I to monomer II is (1-5): 1;
preferably, in step (2), the molar ratio of the solid product obtained in step (1) to hydrazine hydrate is 1 (15 to 50).
Preferably, in the step (1) and the step (2), the organic solvent is one or two or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) and N-methylpyrrolidone (NMP).
Preferably, in step (2), the catalyst is Pd/C, raney-Nickel/H 2 、SnCl 2 HCl or Fe/HCl; the catalyst is used in the following amount: 20mg to 80mg of catalyst is added per 1mmol of the solid product obtained in the step (1).
Preferably, in the step (2), the filtrate is concentrated to 0.1 to 0.8 times the original volume of the filtrate.
A polyimide obtained by polymerizing a diamine containing a intramolecular imide ring and an aliphatic alkyl group with a carboxylic anhydride to obtain a polyamic acid, and subjecting the polyamic acid to thermal imidization or chemical imidization; wherein the carboxylic anhydride is tetracarboxylic dianhydride or hexa-acid dianhydride.
Preferably, the carboxylic anhydride is 1,2,4, 5-pyromellitic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic anhydride, 4' - (hexafluoro-isopropenyl) isophthalic anhydride, tetrahydronaphthalene dianhydride, cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-butanetetracarboxylic acid 1,2,3, 4-dianhydride, cis-1, 2,3, 4-cyclopentane tetracarboxylic dianhydride, 2, 3',4' -diphenylether tetracarboxylic dianhydride, 1,2,3, 4-cyclopentatetracarboxylic dianhydride, 1,6,7, 12-tetrachloro-3, 4,9, 10-perylene tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 1,6,7, 12-tetra-tert-butylphenoxy perylene-3, 4,9, 10-tetracarboxylic dianhydride, bicyclo (2.2.2) oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,2, 4-benzene tricarboxylic acid 1, 2-anhydride ethylene ester, ethylenediamine tetraacetic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 3',4' -diphenyl sulfone tetracarboxylic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, p-phenyl bis (trimellitate) dianhydride, azo phthalic anhydride, 4' - (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride), mellitic dianhydride, 5- (2, 5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, or 3,4,9, 10-perylene tetracarboxylic anhydride.
A polyimide film prepared from the polyimide described above.
The specific steps of one preparation method (thermal imidization method) of the polyimide film are as follows:
1) Adding diamine and carboxylic anhydride containing molecular imide ring and fatty alkyl with the molar ratio of (1-1.2) 1 into an organic solvent, and carrying out polycondensation reaction to obtain a polyamic acid solution with the solid content of 10-25 wt%; wherein the reaction temperature of the polycondensation reaction is-10 ℃ to 100 ℃ and the reaction time is 4 hours to 24 hours;
2) Coating the polyamic acid solution on a glass plate by adopting a scraping method, and vacuum drying at 80-120 ℃ for 1-2 h to remove the solvent; then placing the mixture into a muffle furnace in nitrogen atmosphere, gradually raising the temperature to 280-350 ℃ at the heating rate of 2-5 ℃/min, and continuing to react for 1-1.5 h at the constant temperature of 350 ℃; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The other preparation method (chemical imidization method) of the polyimide film comprises the following specific steps:
1) 1, diamine and carboxylic anhydride containing a molecular imide ring and fatty alkyl are added into an organic solvent according to the molar ratio of (1-1.2), and a polyamide acid solution with the solid content of 10-25 wt.% is prepared through polycondensation reaction; wherein the reaction temperature of the polycondensation reaction is-10 ℃ to 100 ℃ and the reaction time is 4 hours to 24 hours;
2) Mixing 1-10 times of acetic anhydride containing the mole of the diamine of the intramolecular imide ring and the aliphatic alkyl and 1-12 times of triethylamine containing the mole of the diamine of the intramolecular imide ring and the aliphatic alkyl, slowly dripping the mixture into a polyamide acid solution, and stirring the mixture at 20 ℃ for reaction for 12 hours; coating the reaction product liquid on a glass plate by adopting a scraping method, and removing the solvent after vacuum drying at 80 ℃ for 2 hours; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 200 ℃ at a heating rate of 5 ℃/min, and continuing to react at the constant temperature of 200 ℃ for 1h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to chemical imidization.
An optical material comprising the aforementioned polyimide or polyimide film.
An image display device comprising the aforementioned polyimide or polyimide film.
An electronic device comprising the aforementioned polyimide or polyimide film.
Compared with the prior art, the diamine containing the intramolecular imide ring and the fatty alkyl is a novel monomer for synthesizing polyimide, the fatty alkyl and the imide ring structure are introduced through the condensation reaction of the nitroanhydride and the diamine containing the fatty alkyl, and then the nitro at two ends of the molecule is reduced to prepare the aromatic diamine containing the imide ring and the fatty alkyl; the alkalinity of diamine monomer amino can be effectively weakened when polyimide is polymerized by monomer, and the phenomenon that the polymerization is difficult due to the formation of precipitation caused by salification in the polymerization process is avoided, so that the polymerization degree is improved, the molecular weight of polyimide is improved, and the mechanical property of polyimide film is improved; in addition, the introduction of R groups into the diamine monomer can interrupt the conjugated structure on the polyimide molecular chain, inhibit the formation of a complex for charge transfer between a diamine electron donor and a dianhydride electron acceptor, and improve the optical transparency of the polyimide film; experiments prove that the glass transition temperature Tg and the tensile strength Ts of the polyimide film prepared from the diamine containing the molecular maleimide ring and the aliphatic alkyl are obviously superior to those of the traditional polyimide film, the polyimide film has higher optical transparency, and has good application and popularization prospects in the fields of electronic products such as flexible electronic display devices, flexible circuit board matrix materials and the like.
Drawings
FIG. 1 is an infrared ray diagram of a polyimide film prepared in example 9 of the present invention;
FIG. 2 (a) is a physical view of a polyimide film prepared in example 9 of the present invention;
FIG. 2 (b) is a physical view of the polyimide film prepared in comparative example 1 of the present invention;
FIG. 2 (c) is a physical view of the polyimide film prepared in comparative example 2 of the present invention;
FIG. 2 (d) is a physical view of the polyimide film prepared in comparative example 3 of the present invention;
FIG. 3 (a) is a sectional Scanning Electron Microscope (SEM) of a polyimide film prepared in example 9 of the present invention;
FIG. 3 (b) is a scanning electron microscope image of the polyimide film surface prepared in example 9 of the present invention;
fig. 4 is an XRD pattern of the polyimide film prepared in example 9 of the present invention.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and specific examples, which are in no way limiting.
Example 1
A diamine containing a molecular imide ring and an aliphatic alkyl group, which is prepared by the following method:
s1, dissolving 3.86g of 4-nitroanhydride in 30mL of NMP solution to obtain 4-nitroanhydride solution;
s2, under the protection of nitrogen atmosphere and stirring, adding 9.1g of trans-1, 4-cyclohexanediamine into 50mL of NMP, slowly dropwise adding the 4-nitroaniline solution prepared in the step S1, placing the obtained mixed reaction solution at room temperature for reaction for 12 hours, and heating to 150 ℃ for reflux reaction for 18 hours, thus finishing the reaction;
S3, naturally cooling the reaction generating solution prepared in the step S2 until solid is separated out, filtering, washing the filtered precipitate with dilute hydrochloric acid and distilled water to be neutral in sequence, and washing with methanol twice to obtain a crude product 1;
s4, recrystallizing the crude product 1 by utilizing DMF, and drying the obtained solid in vacuum at 50 ℃ to obtain 3.6g of solid product 1, wherein the yield is 78%;
s5, taking 0.93g of solid product 1, dissolving the solid product 1 in 15mL of DMF, adding 85mg of catalyst Pd/C, dropwise adding 3.12g of hydrazine hydrate under ice-water bath, and after the dropwise adding is finished, placing the mixed reaction solution at 60 ℃ for continuous reaction for 6 hours to obtain reaction product liquid;
s6, filtering the reaction product liquid obtained in the step S5 while the reaction product liquid is hot, concentrating the filtrate to 0.2 times of the original volume, and separating out solids from the obtained concentrated solution, namely a crude product 2;
s7, recrystallizing the crude product 2 by utilizing DMF, and drying the obtained solid in vacuum at 20 ℃ to finally obtain 0.79g of white solid powdery diamine monomer, wherein the yield is 98%.
The chemical formula of the product obtained in this example 1 is:
example 2
A diamine containing a molecular imide ring and an aliphatic alkyl group, which is prepared by the following method:
s1, dissolving 3.86g of 4-nitroanhydride in 30mL of DMF (dimethyl formamide) solution to obtain a 4-nitroanhydride solution;
S2, under the protection of nitrogen atmosphere and stirring, adding 6g of ethylenediamine into 50mL of DMF, slowly dropwise adding the 4-nitroaniline solution prepared in the step S1, reacting the obtained mixed reaction solution at room temperature for 11h, heating to 155 ℃ and carrying out reflux reaction for 12h, and finishing the reaction;
s3, naturally cooling the reaction generating solution prepared in the step S2 until solid is separated out, filtering, washing the filtered precipitate with dilute hydrochloric acid and distilled water to be neutral in sequence, and washing with methanol twice to obtain a crude product 1;
s4, recrystallizing the crude product 1 by utilizing DMF, and drying the obtained solid in vacuum at 80 ℃ to obtain 2.87g of solid product 1 with the yield of 70%;
s5, taking 0.82g of solid product 1, dissolving the solid product 1 in 15mL of DMF, adding 40mg of catalyst Pd/C, dropwise adding 1.87g of hydrazine hydrate under ice-water bath, and after the dropwise adding is finished, placing the mixed reaction solution at 20 ℃ for continuous reaction for 5 hours to obtain reaction product liquid;
s6, filtering the reaction product liquid obtained in the step S5 while the reaction product liquid is hot, concentrating the filtrate to 0.1 time of the original volume, and separating out solids from the obtained concentrated solution, namely a crude product 2;
s7, recrystallizing the crude product 2 by utilizing DMF, and drying the obtained solid in vacuum at 30 ℃ to finally obtain 0.67g of white solid powdery diamine monomer, wherein the yield is 95%.
The chemical formula of the product obtained in this example 2 is:
example 3
A diamine containing a molecular imide ring and an aliphatic alkyl group, which is prepared by the following method:
s1, dissolving 3.86g of 4-nitroanhydride in 30mL of DMAc solution to obtain a 4-nitroanhydride solution;
s2, under the protection of nitrogen atmosphere and stirring, adding 6.8g of 1, 3-bis (2-aminoethyl) cyclohexane into 50mL of DMAc, slowly dropwise adding the 4-nitroanhydride solution prepared in the step S1, reacting the obtained mixed reaction solution at room temperature for 10 hours, and heating to 180 ℃ for reflux reaction for 16 hours, thereby finishing the reaction;
s3, naturally cooling the reaction generating solution prepared in the step S2 until solid is separated out, filtering, washing the filtered precipitate with dilute hydrochloric acid and distilled water to be neutral in sequence, and washing with methanol for three times to obtain a crude product 1;
s4, recrystallizing the crude product 1 by utilizing DMF, and drying the obtained solid in vacuum at 90 ℃ to obtain 3.54g of solid product 1, wherein the yield is 68%;
s5, taking 1.04g of solid product 1, dissolving the solid product 1 in 15mL of NMP, adding 60mg of catalyst Pd/C, placing the mixture in an ice-water bath, dropwise adding 2.5g of hydrazine hydrate, and placing the mixed reaction solution at 30 ℃ for continuous reaction for 7 hours after the dropwise addition is finished to obtain reaction product liquid;
S6, filtering the reaction product liquid obtained in the step S5 while the reaction product liquid is hot, concentrating the filtrate to be 0.3 times of the original volume, and separating out solids from the obtained concentrated solution, namely a crude product 2;
s7, recrystallizing the crude product 2 by utilizing DMF, and drying the obtained solid in vacuum at 30 ℃ to finally obtain 0.84g of white solid powdery diamine monomer, wherein the yield is 92%.
The chemical formula of the product obtained in this example 3 is:
example 4
A diamine containing a molecular imide ring and an aliphatic alkyl group, which is prepared by the following method:
s1, dissolving 4.86g of 6-nitronaphthalene anhydride in 30mL of NMP solution to obtain 6-nitronaphthalene anhydride solution;
s2, under the protection of nitrogen atmosphere and stirring, adding 6.8g of 1, 3-diaminocyclohexane into 50mL of NMP, slowly dropwise adding the 6-nitronaphthalene anhydride solution prepared in the step S1, placing the obtained mixed reaction solution at room temperature for reaction for 9 hours, and heating to 220 ℃ for reflux reaction for 20 hours, thus finishing the reaction;
s3, naturally cooling the reaction generating solution prepared in the step S2 until solid is separated out, filtering, washing the filtered precipitate with dilute hydrochloric acid and distilled water to be neutral in sequence, and washing with methanol for three times to obtain a crude product 1;
s4, recrystallizing the crude product 1 by utilizing DMF, and drying the obtained solid in vacuum at 100 ℃ to obtain 4.23g of solid product 1, wherein the yield is 75%;
S5, taking 1.13g of solid product 1, dissolving the solid product 1 in 15mL of DMSO, adding 80mg of catalyst Pd/C, placing the mixture in an ice water bath, dropwise adding 3.74g of hydrazine hydrate, and placing the mixed reaction solution at 40 ℃ for continuous reaction for 9 hours after the dropwise addition is finished to obtain reaction generating solution;
s6, filtering the reaction product liquid obtained in the step S5 while the reaction product liquid is hot, concentrating the filtrate to be 0.4 times of the original volume, and separating out solids from the obtained concentrated solution, namely a crude product 2;
s7, recrystallizing the crude product 2 by utilizing DMF, and drying the obtained solid in vacuum at 50 ℃ to finally obtain 0.9g of white solid powdery diamine monomer, wherein the yield is 90%.
The chemical formula of the product obtained in this example 4 is:
example 5
A diamine containing a molecular imide ring and an aliphatic alkyl group, which is prepared by the following method:
s1, dissolving 4.86g of 6-nitronaphthalene anhydride in 30mL of DMSO solution to obtain a 6-nitronaphthalene anhydride solution;
s2, under the protection of nitrogen atmosphere and stirring, adding 6.25g of bis (aminomethyl) ether into 50mL of DMSO, slowly dropwise adding the 6-nitronaphthalene anhydride solution prepared in the step S1, placing the obtained mixed reaction solution at room temperature for reaction for 8 hours, and heating to 200 ℃ for reflux reaction for 22 hours, wherein the reaction is completed;
S3, naturally cooling the reaction generating solution prepared in the step S2 until solid is separated out, filtering, washing the filtered precipitate with dilute hydrochloric acid and distilled water to be neutral in sequence, and washing with methanol four times to obtain a crude product 1;
s4, recrystallizing the crude product 1 by utilizing DMF, and drying the obtained solid in vacuum at 70 ℃ to obtain 4.27g of solid product 1, wherein the yield is 77%;
s5, taking 1.1g of solid product 1, dissolving the solid product 1 in 15mL of DMAc, adding 100mg of catalyst Pd/C, dropwise adding 5g of hydrazine hydrate under an ice water bath, and after the dropwise adding is finished, placing the mixed reaction solution at 50 ℃ for continuous reaction for 8 hours to obtain reaction generating solution;
s6, filtering the reaction product liquid obtained in the step S5 while the reaction product liquid is hot, concentrating the filtrate to 0.5 times of the original volume, and separating out solids from the obtained concentrated solution, namely a crude product 2;
s7, recrystallizing the crude product 2 by utilizing DMF, and drying the obtained solid in vacuum at 10 ℃ to finally obtain 0.87g of white solid powdery diamine monomer, wherein the yield is 88%.
The chemical formula of the product obtained in this example 5 is:
example 6
A diamine containing a molecular imide ring and an aliphatic alkyl group, which is prepared by the following method:
s1, dissolving 3.86g of 4-nitroanhydride in 30mL of NMP solution to obtain 4-nitroanhydride solution;
S2, under the protection of nitrogen atmosphere and stirring, adding 4.2g of bis (4-aminocyclohexyl) methane into 50mL of NMP, slowly dropwise adding the 4-nitroanhydride solution prepared in the step S1, placing the obtained mixed reaction solution at room temperature for reaction for 9 hours, and heating to 220 ℃ for reflux reaction for 24 hours, thus finishing the reaction;
s3, naturally cooling the reaction generating solution prepared in the step S2 until solid is separated out, filtering, washing the filtered precipitate with dilute hydrochloric acid and distilled water to be neutral in sequence, and washing with methanol four times to obtain a crude product 1;
s4, recrystallizing the crude product 1 by utilizing DMF, and drying the obtained solid in vacuum at 100 ℃ to obtain 4.1g of solid product 1, wherein the yield is 73%;
s5, taking 1.12g of solid product 1, dissolving the solid product 1 in 15mL of DMSO, adding 120mg of catalyst Pd/C, dropwise adding 4.24g of hydrazine hydrate under ice-water bath, and after the dropwise adding is finished, placing the mixed reaction solution at 60 ℃ for continuous reaction for 12 hours to obtain reaction generating solution;
s6, filtering the reaction product liquid obtained in the step S5 while the reaction product liquid is hot, concentrating the filtrate to be 0.6 times of the original volume, and separating out solids from the obtained concentrated solution, namely a crude product 2;
s7, recrystallizing the crude product 2 by utilizing DMF, and drying the obtained solid in vacuum at 0 ℃ to finally obtain 0.84g of white solid powdery diamine monomer, wherein the yield is 84%.
The chemical formula of the product obtained in this example 6 is:
example 7
A diamine containing a molecular imide ring and an aliphatic alkyl group, which is prepared by the following method:
s1, dissolving 3.86g of 4-nitroanhydride in 30mL of DMF (dimethyl formamide) solution to obtain a 4-nitroanhydride solution;
s2, under the protection of nitrogen atmosphere and stirring, adding 9.6g of 1, 2-bis (aminomethoxy) ethane into 50mL of DMF, slowly dropwise adding the 4-nitroanhydride solution prepared in the step S1, placing the obtained mixed reaction solution at room temperature for reaction for 10 hours, and heating to 160 ℃ for reflux reaction for 17 hours, wherein the reaction is finished;
s3, naturally cooling the reaction generating solution prepared in the step S2 until solid is separated out, filtering, washing the filtered precipitate with dilute hydrochloric acid and distilled water to be neutral in sequence, and washing with methanol for five times to obtain a crude product 1;
s4, recrystallizing the crude product 1 by utilizing DMF, and drying the obtained solid in vacuum at 60 ℃ to obtain 3.2g of solid product 1, wherein the yield is 69%;
s5, taking 0.94g of solid product 1, dissolving the solid product 1 in 15mL of NMP, adding 140mg of catalyst Pd/C, dropwise adding 4.4g of hydrazine hydrate under an ice-water bath, and after the dropwise adding is finished, placing the mixed reaction solution at 70 ℃ for continuous reaction for 10 hours to obtain reaction product liquid;
S6, filtering the reaction product liquid obtained in the step S5 while the reaction product liquid is hot, concentrating the filtrate to be 0.7 times of the original volume, and separating out solids from the obtained concentrated solution, namely a crude product 2;
s7, recrystallizing the crude product 2 by utilizing DMF, and drying the obtained solid in vacuum at 25 ℃ to finally obtain 0.68g of white solid powdery diamine monomer, wherein the yield is 83%.
The chemical formula of the product obtained in this example 7 is:
example 8
A diamine containing a molecular imide ring and an aliphatic alkyl group, which is prepared by the following method:
s1, dissolving 3.86g of 4-nitroanhydride in 30mL of DMF (dimethyl formamide) solution to obtain a 4-nitroanhydride solution;
s2, under the protection of nitrogen atmosphere and stirring, adding 6.2g of 2, 6-bis (aminomethyl) bicyclo [2.2.1] heptane into 50mL of DMF, slowly dropwise adding the 4-nitroaniline solution prepared in the step S1, placing the obtained mixed reaction solution at room temperature for reaction for 12 hours, and heating to 180 ℃ for reflux reaction for 19 hours, thus finishing the reaction;
s3, naturally cooling the reaction generating solution prepared in the step S2 until solid is separated out, filtering, washing the filtered precipitate with dilute hydrochloric acid and distilled water to be neutral in sequence, and washing with methanol for five times to obtain a crude product 1;
S4, recrystallizing the crude product 1 by utilizing DMF, and drying the obtained solid in vacuum at 70 ℃ to obtain 3.63g of solid product 1, wherein the yield is 72%;
s5, taking 1.09g of solid product 1, dissolving the solid product 1 in 15mL of DMAc, adding 160mg of catalyst Pd/C, dropwise adding 3.12g of hydrazine hydrate under an ice water bath, and after the dropwise adding is finished, placing the mixed reaction solution at 90 ℃ for continuous reaction for 11 hours to obtain reaction product liquid;
s6, filtering the reaction product liquid obtained in the step S5 while the reaction product liquid is hot, concentrating the filtrate to 0.8 times of the original volume, and separating out solids from the obtained concentrated solution, namely a crude product 2;
s7, recrystallizing the crude product 2 by utilizing DMF, and drying the obtained solid in vacuum at 35 ℃ to finally obtain 0.68g of white solid powdery diamine monomer with 77% yield.
The chemical formula of the product obtained in this example 8 is:
example 9
4g of the diamine monomer prepared in example 1 was dissolved in 19.6mL of DMF, and 2.2g of pyromellitic dianhydride was further added thereto at 0℃to allow the diamine monomer and pyromellitic dianhydride to undergo polycondensation reaction under stirring for 20 hours, to obtain a polyamic acid solution having a solid content of 25 wt.%;
coating the polyamic acid solution on a glass plate by a scraping method, and vacuum-drying at 80 ℃ for 2 hours to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually heating to 280 ℃ at a heating rate of 5 ℃/min, and continuing to react at the constant temperature of 280 ℃ for 1h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
example 10
3.5g of the diamine monomer prepared in example 2 was dissolved in 47.8mL of NMP, and 1.96g of cyclobutane tetracarboxylic dianhydride was further added thereto at-10℃to allow the diamine monomer and cyclobutane tetracarboxylic dianhydride to undergo polycondensation reaction under stirring for 24 hours, to obtain a polyamic acid solution having a solid content of 10 wt.%;
coating the polyamic acid solution on a glass plate by a scraping method, and vacuum drying at 100 ℃ for 1h to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually heating to 290 ℃ at a heating rate of 4 ℃/min, and continuing to react for 1.5h at the constant temperature of 290 ℃; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
example 11
4.6g of the diamine monomer prepared in example 3 was dissolved in 33.5mL of DMSO, and 1.98g of 1,2,3, 4-butanetetracarboxylic acid-1, 2,3, 4-dianhydride was further added thereto at 20℃to cause polycondensation of the diamine monomer and 1,2,3, 4-butanetetracarboxylic acid-1, 2,3, 4-dianhydride with stirring for 4 hours, to obtain a polyamic acid solution having a solid content of 15 wt.%;
Coating the polyamic acid solution on a glass plate by a scraping method, and vacuum drying at 120 ℃ for 1.5 hours to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually heating to 300 ℃ at a heating rate of 3 ℃/min, and continuing to react for 2 hours at the constant temperature of 300 ℃; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
example 12
5.04g of the diamine monomer prepared in example 4 was dissolved in 30.8mL of DMAc, and 2.2g of pyromellitic dianhydride was further added thereto at 30℃to allow the diamine monomer and pyromellitic dianhydride to undergo polycondensation reaction under stirring for 8 hours, to obtain a polyamic acid solution having a solid content of 20 wt.%;
coating the polyamic acid solution on a glass plate by a scraping method, and vacuum drying at 100 ℃ for 2 hours to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually heating to 310 ℃ at a heating rate of 2 ℃/min, and continuing to react at the constant temperature of 310 ℃ for 2.5 hours; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
Example 13
4.94g of the diamine monomer prepared in example 5 was dissolved in 66.8mL of DMF, and 2.1g of 1,2,3, 4-cyclopentanetetracarboxylic acid dianhydride was further added thereto at 50℃to allow the diamine monomer and 1,2,3, 4-cyclopentanetetracarboxylic acid dianhydride to undergo polycondensation reaction under stirring for 12 hours to obtain a polyamic acid solution having a solid content of 10 wt.%;
coating the polyamic acid solution on a glass plate by a scraping method, and vacuum drying at 120 ℃ for 1h to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually heating to 320 ℃ at a heating rate of 1 ℃/min, and continuing to react at the constant temperature of 320 ℃ for 2 hours; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
example 14
5g of the diamine monomer prepared in example 6 was dissolved in 31.5mL of NMP, and 3.1g of 2, 3',4' -diphenylether tetracarboxylic dianhydride was further added thereto at 80℃to allow the diamine monomer and 2, 3',4' -diphenylether tetracarboxylic dianhydride to undergo polycondensation reaction under stirring for 14 hours, thereby obtaining a polyamic acid solution having a solid content of 20 wt.%;
Coating the polyamic acid solution on a glass plate by a scraping method, and vacuum-drying at 110 ℃ for 2.5 hours to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 330 ℃ at the heating rate of 2 ℃/min, and continuing to react at the constant temperature of 330 ℃ for 1.5h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
example 15
4.1g of the diamine monomer prepared in example 7 was dissolved in 17.2mL of DMSO, and 2.2g of pyromellitic dianhydride was further added thereto at 70℃to allow the diamine monomer and pyromellitic dianhydride to undergo polycondensation reaction under stirring for 16 hours, to obtain a polyamic acid solution having a solid content of 25 wt.%;
coating the polyamic acid solution on a glass plate by a scraping method, and vacuum-drying at 90 ℃ for 2.5 hours to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 340 ℃ at the heating rate of 3 ℃/min, and continuing to react at the constant temperature of 340 ℃ for 1h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
Example 16
4.45g of the diamine monomer prepared in example 8 was dissolved in 25.7mL of DMAc, 3.58g of 3,3', 4' -diphenylsulfone tetracarboxylic dianhydride was further added thereto at 100℃to allow the diamine monomer and 3,3', 4' -diphenylsulfone tetracarboxylic dianhydride to undergo polycondensation reaction under stirring for 20 hours, to obtain a polyamic acid solution having a solid content of 25 wt.%;
coating the polyamic acid solution on a glass plate by a scraping method, and vacuum-drying at 85 ℃ for 1.5 hours to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 350 ℃ at a heating rate of 5 ℃/min, and continuing to react for 1.5 hours at the constant temperature of 350 ℃; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
example 17
4.1g of the diamine monomer prepared in example 7 was dissolved in 26.6mL of DMF, and 2.24g of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride was further added thereto at 0℃to allow the diamine monomer and 1,2,4, 5-cyclohexane tetracarboxylic dianhydride to undergo polycondensation reaction under stirring for 20 hours, to obtain a polyamic acid solution having a solid content of 25 wt.%;
9.4mL of acetic anhydride and 13.9mL of triethylamine are mixed and slowly added into the polyamic acid solution in a dropwise manner, and the mixture is stirred at 20 ℃ for reaction for 12 hours; coating the reaction product liquid on a glass plate by adopting a scraping method, and removing the solvent after vacuum drying at 80 ℃ for 2 hours; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 200 ℃ at a heating rate of 5 ℃/min, and continuing to react at the constant temperature of 200 ℃ for 1h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to chemical imidization.
The chemical structural formula of the polyimide film is as follows:
example 18
4.04g of the diamine monomer prepared in example 1 was dissolved in 69.7mL of NMP, 3.92g of 3,4,9, 10-perylenetetracarboxylic anhydride was further added thereto at 20℃to allow the diamine monomer and 3,4,9, 10-perylenetetracarboxylic anhydride to undergo polycondensation reaction under stirring for 18 hours, to obtain a polyamic acid solution having a solid content of 10 wt.%;
9.4mL of acetic anhydride and 13.9mL of triethylamine are mixed and slowly added into the polyamic acid solution in a dropwise manner, and the mixture is stirred at 20 ℃ for reaction for 12 hours; coating the reaction product liquid on a glass plate by adopting a scraping method, and removing the solvent after vacuum drying at 80 ℃ for 2 hours; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 200 ℃ at a heating rate of 5 ℃/min, and continuing to react at the constant temperature of 200 ℃ for 1h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to chemical imidization.
The chemical structural formula of the polyimide film is as follows:
example 19
3.5g of the diamine monomer prepared in example 2 was dissolved in 28.7mL of DMAc, and 3.22g of 3,3', 4' -benzophenone tetracarboxylic dianhydride was further added thereto at 50℃to allow the diamine monomer and 3,3', 4' -benzophenone tetracarboxylic dianhydride to undergo polycondensation reaction under stirring for 14 hours, to obtain a polyamic acid solution having a solid content of 20 wt.%;
9.4mL of acetic anhydride and 13.9mL of triethylamine are mixed and slowly added into the polyamic acid solution in a dropwise manner, and the mixture is stirred at 20 ℃ for reaction for 12 hours; coating the reaction product liquid on a glass plate by adopting a scraping method, and removing the solvent after vacuum drying at 80 ℃ for 2 hours; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 200 ℃ at a heating rate of 5 ℃/min, and continuing to react at the constant temperature of 200 ℃ for 1h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to chemical imidization.
The chemical structural formula of the polyimide film is as follows:
example 20
4.6g of the diamine monomer prepared in example 3 was dissolved in 20.6mL of DMSO, and 2.94g of 3,3', 4' -biphenyltetracarboxylic dianhydride was further added thereto at 20℃to allow the diamine monomer and 3,3', 4' -biphenyltetracarboxylic dianhydride to undergo polycondensation reaction under stirring for 10 hours, thereby obtaining a polyamic acid solution having a solid content of 25 wt.%;
9.4mL of acetic anhydride and 13.9mL of triethylamine are mixed and slowly added into the polyamic acid solution in a dropwise manner, and the mixture is stirred at 20 ℃ for reaction for 12 hours; coating the reaction product liquid on a glass plate by adopting a scraping method, and removing the solvent after vacuum drying at 80 ℃ for 2 hours; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 200 ℃ at a heating rate of 5 ℃/min, and continuing to react at the constant temperature of 200 ℃ for 1h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to chemical imidization.
The chemical structural formula of the polyimide film is as follows:
comparative example 1
2g of 4,4' -diaminodiphenyl ether is dissolved in 11.45mL of DMSO, and 2.2g of pyromellitic dianhydride is added into the DMSO at 20 ℃ to cause the diamine monomer and the pyromellitic dianhydride to undergo polycondensation reaction under stirring for 20 hours, so as to obtain a polyamide acid solution with 25wt.% of solid content;
coating the polyamic acid solution on a glass plate by a scraping method, and vacuum-drying at 90 ℃ for 2.5 hours to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 300 ℃ at a heating rate of 3 ℃/min, and continuing to react at the constant temperature of 300 ℃ for 1h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
comparative example 2
2g of 4,4' -diaminodiphenyl ether is dissolved in 11.8mL of DMSO, and 2.24g of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride is added into the solution at 25 ℃ to carry out polycondensation reaction on diamine monomer and 1,2,4, 5-cyclohexane tetracarboxylic dianhydride under the stirring condition, wherein the reaction time is 18 hours, so as to obtain a polyamide acid solution with 25wt.% of solid content;
coating the polyamic acid solution on a glass plate by a scraping method, and vacuum drying at 120 ℃ for 2 hours to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 300 ℃ at a heating rate of 3 ℃/min, and continuing to react at the constant temperature of 300 ℃ for 1h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
comparative example 3
2.92g of 1, 4-bis (4-aminophenoxy) benzene was dissolved in 11.8mL of DMSO, and 2.94g of 3,3', 4' -biphenyltetracarboxylic dianhydride was further added thereto at 20℃to allow the diamine monomer and 3,3', 4' -biphenyltetracarboxylic dianhydride to undergo polycondensation reaction under stirring for 16 hours, to obtain a polyamic acid solution having a solid content of 25 wt%;
Coating the polyamic acid solution on a glass plate by a scraping method, and vacuum-drying at 80 ℃ for 2 hours to remove the solvent; then placing the mixture in a muffle furnace in nitrogen atmosphere, gradually increasing the temperature to 200 ℃ at a heating rate of 5 ℃/min, and continuing to react at the constant temperature of 200 ℃ for 1h; and after natural cooling, removing the film from the glass plate to obtain the polyimide film subjected to thermal imidization.
The chemical structural formula of the polyimide film is as follows:
performance test:
molecular weight test of polyimide film:
among the above examples, examples 1 to 8 are examples of the preparation of diamines containing a intramolecular imide ring and an aliphatic alkyl group; examples 9 to 16 are examples of polyimide film preparation using thermal imidization to achieve the present application; examples 17 to 20 are examples of polyimide film preparation using chemical imidization to achieve the present application; comparative examples 1 to 3 are examples for realizing the preparation of a conventional polyimide film by using a thermal imidization method. Among them, the weight average molecular weights of the polyimide films prepared in examples 9 to 20 and comparative examples 1 to 3 and the phenomena occurring during the preparation are shown in the following table 1.
Table 1:
based on the analysis of the results in Table 1, it is found that in comparative examples 1 to 3, since diamine in the polycondensation polymerization is strongly basic, a partial salt formation phenomenon occurs in the polymerization process, and the polymerization reaction is inhibited, the molecular weight of polyimide synthesized by polycondensation is lower than that of polyimide prepared by using the diamine monomer of the present application.
(II) characterization of the infrared structure of polyimide films:
FIG. 1 is an infrared chart of the polyimide film prepared in example 9; as can be seen from the figure, the characteristic absorption peaks of the amide at wavelengths 3300-3500cm-1 (N-H) and 1660cm-1 (C=O) disappeared. Characteristic absorption peaks of imine rings appear at 1780cm-1 (C=O asymmetric extension), 1720cm-1 (C=O symmetric extension) and 1360cm-1 (C-N extension) 720cm-1 (C=O), which prove that polyimide polymers are successfully synthesized. Accordingly, the infrared spectrograms of the polyimide films prepared in examples 10 to 20 have the same characteristic features of functional groups as in example 9.
Macroscopic and microscopic characterization of polyimide films:
FIG. 2 (a) is a schematic diagram showing a polyimide film prepared in example 9; as can be seen from the figure, example 9 successfully prepared a polyimide film, and the resulting film was a dense, defect-free transparent film material; correspondingly, the polyimide films prepared in examples 10 to 20 are all the same as those prepared in example 9 in terms of physical appearance, and are compact and defect-free transparent films.
As shown in fig. 2 (b), 2 (c) and 2 (d), which are physical drawings of the polyimide films prepared in comparative examples 1 to 3, respectively, it can be seen from the drawings that the polyimide film prepared in comparative example 1 has a dark brown color, the polyimide film prepared in comparative example 2 has a yellow color, the polyimide film prepared in comparative example 3 has a dark yellow color, and the transparency is worse than those of the polyimide films of comparative examples 1 and 2; compared with the polyimide films prepared in comparative examples 1 to 3, the polyimide films prepared in the examples of the application have significantly lighter color than the conventional polyimide films.
FIG. 3 (a) is a cross-sectional Scanning Electron Microscope (SEM) image of the polyimide film prepared in example 9; FIG. 3 (b) is a surface scanning electron microscope image of the polyimide film prepared in example 9; the graph shows that the section and the surface of the obtained polyimide film are flawless, and the polyimide compact film is successfully prepared. Accordingly, the sem images of the polyimide films prepared in examples 10 to 20 also had the same microstructure characteristics as those of example 9.
An XRD pattern of the polyimide film prepared in example 9 is shown in fig. 4; the XRD pattern has only one large broad peak characteristic of the polymer, i.e., it is confirmed that the polyimide polymer was successfully synthesized. Accordingly, the XRD patterns of the polyimide films prepared in examples 10 to 20 were also the same as those of the characterization result in example 9, i.e., each had only one large broad peak characteristic of the polymer.
(IV) mechanical optical characterization of polyimide film:
the mechanical properties and optical properties of the imide films prepared in examples 9 to 20 and comparative examples 1 to 3 were measured, and the specific test results are shown in Table 2 below.
Table 2:
as is apparent from the mechanical test results of table 2, based on the analysis of the molecular weight test results of the polyimide films described above, the polyimide films of comparative examples 1 to 3 did exhibit mechanical properties (glass transition temperature Tg and tensile strength Ts) significantly lower than those of the polyimide films prepared in examples 9 to 20, respectively; specifically, the glass transition temperature of the polyimide film ranges from 332 ℃ to 367 ℃, the highest tensile strength can reach 180MPa, and the excellent glass transition temperature and the tensile strength can enable the polyimide film to become the first-choice polymer material for improving the reliability of a flexible circuit, so that the polyimide film prepared from the diamine monomer containing the imide ring and the aliphatic alkyl structure has great potential for flexible electronic display devices.
As is apparent from the optical test results of Table 1, since the conjugation of the conventional imine molecular chain is strong and the complex of charge transfer between diamine and dianhydride is significantly increased, the polyimide films prepared in comparative examples 1 to 3 are significantly too deep in color and have low optical transparency, compared to the polyimide films prepared from the diamine monomers containing an imide ring and an aliphatic alkyl structure of the present application in examples 9 to 20. Specifically, the polyimide films prepared in examples 9 to 20 all have a transmittance of higher than 82% at a wavelength of 450nm and a transmittance of 95.9% at a wavelength of 500 nm; meanwhile, the chromaticity index of the polyimide film in the aspects of brightness parameters L, red and green parameters a and yellow Lan Canshu b is obviously better than that of the polyimide films prepared in examples 9-20, and further shows that the film has higher optical transparency, namely the polyimide film optical performance can be obviously improved by adopting the diamine monomer containing the imide ring and the aliphatic alkyl structure. The excellent optical transparency of the polyimide film becomes an alternative substrate material for the flexible circuit board, and along with the advent of novel electronic products such as foldable mobile phones and the like and the increasing of demands for high-quality flexible circuit boards, the polyimide film also has higher requirements on the light transmittance of polyimide serving as the substrate material, so that the polyimide film with excellent optical performance prepared from the diamine monomer containing the imide ring and the aliphatic alkyl structure has good prospect in the field of electronic products such as the flexible circuit boards and the like.
Claims (10)
1. A diamine containing a intramolecular imide ring and an aliphatic alkyl group, characterized by having the chemical structural formula:
wherein Ar is a benzene ring or a naphthalene ring; r is one of the formulas (1) to (10);
formula (1):
wherein m is an integer, and the value range of m is 2-7;
formula (2):
wherein m and n are integers, the value range of m is 1-4, and the value range of n is 1-4;
formula (3):
wherein m is an integer, and the value range of m is 2-6;
formula (4):
wherein m is an integer, and the value range of m is 1-5;
formula (5):
formula (6):
wherein m and n are integers, the value range of m is 1-3, and the value range of n is 1-3;
formula (7):
wherein m and n are integers, the value range of m is 1-5, and the value range of n is 1-5;
formula (8):
wherein m, n and o are integers, and the value range of m is 1 to the whole range3, the value range of n is 2-3, and the value range of o is 1-3;
formula (9):
wherein m, n, o, p is an integer, m is 1-3, n is 2-3, o is 2-3, and p is 1-3;
formula (10):
wherein m, n, o, p, q is an integer, m is 1-3, n is 2-3, o is 2-3, p is 2-3, and q is 1-3.
2. A process for the preparation of a diamine containing a intramolecular imide ring and an aliphatic alkyl group according to claim 1, characterized by the following steps:
(1) Under the protection of inert gas, adding the monomer I and the monomer II into an organic solvent, mixing and stirring uniformly, reacting for 8-12 hours at room temperature, and then heating to 150-220 ℃ for reflux for 12-24 hours; naturally cooling the reaction product liquid until solid is separated out, filtering, washing the filtered precipitate with dilute hydrochloric acid and distilled water to neutrality, and washing with methanol for 2-5 times to obtain coarse product; recrystallizing the crude product by utilizing DMF, and vacuum drying the obtained solid at 50-100 ℃ to obtain a solid product; wherein, monomer I is
The monomer II is 4-nitroanhydride or 6-nitronaphthalene anhydride, and the molar ratio of the two is (1-5) 1;
(2) Dissolving the solid product obtained in the step (1) in an organic solvent, adding a catalyst, dropwise adding hydrazine hydrate into the solution under an ice water bath, and after the dropwise adding is finished, placing the mixed reaction solution at 20-90 ℃ for continuous reaction for 5-12 h to obtain a reaction product solution; filtering the obtained reaction product liquid while the reaction product liquid is hot, and concentrating the filtrate to separate out solids to obtain a crude product; recrystallizing the crude product by utilizing DMF, and vacuum drying the obtained solid at 0-50 ℃ to obtain diamine monomer; wherein the molar ratio of the solid product obtained in the step (1) to the hydrazine hydrate is 1 (15-50).
3. The method for producing a diamine containing an intramolecular imide ring and an aliphatic alkyl group according to claim 2, wherein in the step (1) and the step (2), the organic solvent is N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), or N-methylpyrrolidone (NMP).
4. The diamine containing a intramolecular imide ring and an aliphatic alkyl group according to claim 1, wherein in the step (2), the catalyst is Pd/C, raney-Nickel/H 2 、SnCl 2 HCl or Fe/HCl; the catalyst is used in the following amount: 20mg to 80mg of catalyst is added per 1mmol of the solid product obtained in the step (1).
5. A polyimide obtained by polymerizing the diamine containing a intramolecular imide ring and an aliphatic alkyl group according to claim 1 with a carboxylic anhydride to obtain a polyamic acid, and subjecting the polyamic acid to thermal imidization or chemical imidization; wherein the carboxylic anhydride is tetracarboxylic dianhydride or hexa-acid dianhydride.
6. The polyimide according to claim 5, wherein the carboxylic anhydride is 1,2,4, 5-pyromellitic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic anhydride, 4' - (hexafluoro-isopropenyl) isophthalic anhydride, tetrahydronaphthalene dianhydride, cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-butanetetracarboxylic acid 1,2,3, 4-dianhydride, cis-1, 2,3, 4-cyclopentane tetracarboxylic dianhydride, 2, 3',4' -diphenylether tetracarboxylic dianhydride, 1,2,3, 4-cyclopentatetracarboxylic dianhydride, 1,6,7, 12-tetrachloro-3, 4,9, 10-perylene tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 1,6,7, 12-tetra-tert-butylphenoxy perylene-3, 4,9, 10-tetracarboxylic dianhydride, bicyclo (2.2.2) oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,2, 4-benzene tricarboxylic acid 1, 2-anhydride ethylene ester, ethylenediamine tetraacetic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 3',4' -diphenyl sulfone tetracarboxylic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, p-phenyl bis (trimellitate) dianhydride, azo phthalic anhydride, 4' - (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride), mellitic dianhydride, 5- (2, 5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, or 3,4,9, 10-perylene tetracarboxylic anhydride.
7. A polyimide film prepared from the polyimide of claim 5 or 6.
8. An optical material comprising the polyimide of claim 5 or 6, or the polyimide film of claim 7.
9. An image display device comprising the polyimide according to claim 5 or 6, or the polyimide film according to claim 7.
10. An electronic device comprising the polyimide of claim 5 or 6, or the polyimide film of claim 7.
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| JPS4419858Y1 (en) * | 1966-11-30 | 1969-08-26 | ||
| JPS50135076A (en) * | 1974-04-16 | 1975-10-25 | ||
| US5212277A (en) * | 1990-05-15 | 1993-05-18 | Korea Research Institute Of Chemical Technology | Polyetherimideimides and a method for manufacturing them |
| JP2000230048A (en) * | 1999-02-12 | 2000-08-22 | Ube Ind Ltd | Soluble polyimide and its production |
| CN102911359A (en) * | 2012-10-19 | 2013-02-06 | 中国科学院宁波材料技术与工程研究所 | Transparent polyimide and preparation method thereof |
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2023
- 2023-03-17 CN CN202310259608.5A patent/CN116354864A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4419858Y1 (en) * | 1966-11-30 | 1969-08-26 | ||
| JPS50135076A (en) * | 1974-04-16 | 1975-10-25 | ||
| US5212277A (en) * | 1990-05-15 | 1993-05-18 | Korea Research Institute Of Chemical Technology | Polyetherimideimides and a method for manufacturing them |
| JP2000230048A (en) * | 1999-02-12 | 2000-08-22 | Ube Ind Ltd | Soluble polyimide and its production |
| CN102911359A (en) * | 2012-10-19 | 2013-02-06 | 中国科学院宁波材料技术与工程研究所 | Transparent polyimide and preparation method thereof |
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