CN108517035B - Fluorine-containing PI film with high transparency and mechanical property and application thereof - Google Patents
Fluorine-containing PI film with high transparency and mechanical property and application thereof Download PDFInfo
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- CN108517035B CN108517035B CN201810576656.6A CN201810576656A CN108517035B CN 108517035 B CN108517035 B CN 108517035B CN 201810576656 A CN201810576656 A CN 201810576656A CN 108517035 B CN108517035 B CN 108517035B
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- China
- Prior art keywords
- tetracarboxylic dianhydride
- fluorine
- dianhydride
- containing polyimide
- polyimide according
- Prior art date
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000011737 fluorine Substances 0.000 title claims abstract description 46
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 46
- 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 95
- 229920001721 polyimide Polymers 0.000 claims abstract description 68
- 239000004642 Polyimide Substances 0.000 claims abstract description 48
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 47
- -1 diamine compound Chemical class 0.000 claims abstract description 35
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 33
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims description 18
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 claims description 15
- 125000002723 alicyclic group Chemical group 0.000 claims description 15
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 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 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000005693 optoelectronics Effects 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 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 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- MQQRFOXFIPBFOV-UHFFFAOYSA-N 1,2-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1(C)C(C(O)=O)C(C(O)=O)C1(C)C(O)=O MQQRFOXFIPBFOV-UHFFFAOYSA-N 0.000 claims description 3
- MRTAEHMRKDVKMS-UHFFFAOYSA-N 4-[4-[4-(3,4-dicarboxyphenoxy)phenyl]sulfanylphenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC(C=C1)=CC=C1SC(C=C1)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 MRTAEHMRKDVKMS-UHFFFAOYSA-N 0.000 claims description 3
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 claims description 3
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- SBHHKGFHJWTZJN-UHFFFAOYSA-N 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1(C)C(C(O)=O)C(C)(C(O)=O)C1C(O)=O SBHHKGFHJWTZJN-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
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 5
- AQHJZQNRAWNMKF-UHFFFAOYSA-N 1,2,3,4,5,6-hexafluoronaphthalene Chemical group FC1=C(F)C(F)=C(F)C2=C(F)C(F)=CC=C21 AQHJZQNRAWNMKF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical group FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-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
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
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- 230000000536 complexating effect Effects 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- NSZYKXMFFCRNJB-UHFFFAOYSA-N 1,2,3,4-tetramethylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1(C)C(C)(C(O)=O)C(C)(C(O)=O)C1(C)C(O)=O NSZYKXMFFCRNJB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
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- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
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- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- BKDVBBSUAGJUBA-UHFFFAOYSA-N bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Chemical compound C1=CC2C(C(O)=O)C(C(=O)O)C1C(C(O)=O)C2C(O)=O BKDVBBSUAGJUBA-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- UFOIOXZLTXNHQH-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1OC(C(O)=O)C(C(O)=O)C1C(O)=O UFOIOXZLTXNHQH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
Disclosed is a fluorine-containing PI film having high transparency and mechanical properties, which comprises a fluorine-containing polyimide obtained by dehydrating and ring-closing polyamic acid, wherein the polyamic acid is obtained by polycondensation reaction of a diamine compound of formula (I) and tetracarboxylic dianhydride. In addition, the application of the fluorine-containing PI film in photoelectric devices is also disclosed. When a hexafluoronaphthalene structure is introduced into a polyimide molecule, the fluorine-containing bridge bond is combined, so that the transmittance of light in far ultraviolet and near infrared regions is better. The structure further increases the interaction between the main chains of the polyimide molecules, thereby keeping higher transparency and having excellent mechanical properties; and meanwhile, the affinity with other matrixes is better. Furthermore, the balance effect of the transparency and the mechanical property is better by balancing the specific selection of the tetracarboxylic dianhydride.
Description
Technical Field
The invention belongs to the field of optical materials; relates to a polyimide film and application thereof, in particular to a fluorine-containing PI film with high transparency and mechanical property and application thereof.
Background
Polyimide (PI) is a high molecular material with a molecular structure containing an imide five-membered ring, and is mainly prepared by an aromatic dianhydride compound and a diamine compound through a polycondensation method. The compound has the characteristics of excellent thermal stability, mechanical strength, dielectric property, insulating property, outstanding toughness, flexibility and the like, and is gradually applied to a plurality of fields, particularly to the flexible display industry which develops rapidly in recent years.
With the development of aerospace, solar, microelectronic and other industries, further requirements on the heat resistance, dielectric property, mechanical property and transparency of polyimide materials are continuously provided. Due to the high aromatic conjugation of the main chain of the traditional polyimide molecule and the charge complexing transfer effect in the molecular chain, the polyimide film is usually colored, has poor light transmittance and is almost opaque in a visible light region.
In order to improve the use characteristics of polyimide films in these fields, researchers have conducted a series of research works, and some research works have achieved some effects. For example, chinese patent application CN101674923A discloses a method and an apparatus for preparing a colorless transparent polyimide film, wherein the method is prepared by a polymerization process of an alicyclic dianhydride compound 1,2,4, 5-cyclohexanetetracarboxylic dianhydride and a diamine compound, and the colorless transparent polyimide film is directly prepared from the solution, and the light transmittance of the prepared film with a thickness of 200 μm is 89.8%. Chinese patent application CN 102634022A discloses a colorless and highly transparent polyimide film, and a preparation method and application thereof, wherein a polyimide film with good transparency is obtained by polymerizing fatty dianhydride and different diamines. However, the heat resistance of the above polyimide film is not satisfactory.
On this basis, chinese patent application CN106674027A discloses a fluorine-containing polyimide film prepared using a fluorine-containing bridge and fluorine-containing diamine and dianhydride. The polyimide film has relatively excellent properties in heat resistance, solubility, transparency and the like. However, while bringing high transparency, the introduction of fluorine-containing bridges and fluorobenzene leads to a decrease in mechanical properties of the polyimide film, and the affinity with other substrates is not satisfactory.
Disclosure of Invention
According to the background, the technical problem solved by the invention is how to better enable the polyimide film to have high transparency and excellent mechanical properties; and meanwhile, the affinity with other matrixes is better.
Based on the above, one of the purposes of the present invention is to overcome the defects of the prior art and provide a fluorine-containing polyimide, wherein the fluorine-containing polyimide is obtained by dehydrating and ring-closing polyamic acid; characterized in that the polyamic acid is prepared from a diamine compound of formula (I)
And the tetracarboxylic dianhydride by a polycondensation reaction.
The fluorine-containing polyimide according to the present invention is a polyimide obtained by reacting a tetracarboxylic dianhydride with a fluorine-containing compound.
In a preferred embodiment, the tetracarboxylic dianhydride is selected from aromatic tetracarboxylic dianhydrides.
Aromatic tetracarboxylic acid dianhydrides to be used in the present invention include, but are not limited to, pyromellitic dianhydride, 3 ', 4, 4' -benzophenonetetracarboxylic acid dianhydride, 3 ', 4, 4' -diphenylsulfonetetracarboxylic acid dianhydride, 1,4,5, 8-naphthalenetetracarboxylic acid dianhydride, 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride, 3 ', 4, 4' -diphenylethertetracarboxylic acid dianhydride, 3 ', 4, 4' -dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3 ', 4, 4' -tetraphenylsilanetetracarboxylic acid dianhydride, 1,2,3, 4-furantetracarboxylic acid dianhydride, 4,4 '-bis (3, 4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4, 4' -bis (3, 4-dicarboxyphenoxy) diphenylsulfonedianhydride, dicarboxylic acid dianhydride, 4,4 ' -bis (3, 4-dicarboxyphenoxy) diphenylpropane dianhydride, 3 ', 4,4 ' -perfluoroisopropylidenediphthalic anhydride, 3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, bis (phthalic) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic) dianhydride, m-phenylene-bis (triphenylphthalic) dianhydride, bis (triphenylphthalic) -4,4 ' -diphenyl ether dianhydride, bis (triphenylphthalic) -4,4 ' -diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1, 4-butanediol-bis (anhydrotrimellitate), 1, 6-hexanediol-bis (anhydrotrimellitate), 1, 8-octanediol-bis (anhydrotrimellitate), 2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate).
Preferably, the aromatic tetracarboxylic dianhydride is selected from one or more of 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic dianhydride, 4,4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 3 ', 4,4 ' -perfluoroisopropylidene diphthalic dianhydride, and 3,3 ', 4,4 ' -biphenyl tetracarboxylic dianhydride.
More preferably, the aromatic tetracarboxylic dianhydride is selected from one or more of 3,3 ', 4, 4' -diphenylsulfone tetracarboxylic dianhydride, 3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride, and 3,3 ', 4, 4' -diphenyl ether tetracarboxylic dianhydride.
Most preferably, the aromatic tetracarboxylic dianhydride is selected from the group consisting of 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride, having the following structural formula:
in a preferred embodiment, the tetracarboxylic dianhydride is selected from the group consisting of aromatic tetracarboxylic dianhydrides and cycloaliphatic tetracarboxylic dianhydrides.
As preferred, more preferred and most preferred aromatic tetracarboxylic acid dianhydrides in this embodiment, as described above.
Further, as the alicyclic tetracarboxylic acid dianhydride used in the present invention, there are included, but not limited to, butanetetracarboxylic acid dianhydride, 1,2,3, 4-cyclobutanetetracarboxylic acid dianhydride, 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid dianhydride, 1, 3-dichloro-1, 2,3, 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic acid dianhydride, 1,2,4, 5-norbornane tetracarboxylic acid dianhydride, 3 ', 4, 4' -dicyclohexyltetracarboxylic acid dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid dianhydride, 3,5, 6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4, 5-tetrahydrofurantetracarboxylic acid dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalen [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-5-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalen [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-5-ethyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-7-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-7-ethyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-8-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-8-ethyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-5, 8-dimethyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphthalene [1,2-c ] -furan-1, 3-dione, 5- (2, 5-dioxotetrahydrofurylidene) -3-methyl-3-cyclohexene-1, 2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2, 4-dione-6-spiro-3 ' - (tetrahydrofuran-2 ', 5 ' -dione).
Preferably, the alicyclic tetracarboxylic dianhydride is selected from one or more of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 1,2,4, 5-norbornane-tetracarboxylic dianhydride.
More preferably, the alicyclic tetracarboxylic dianhydride is selected from one or more of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, and 1,2,4, 5-norbornanetetracarboxylic dianhydride.
Most preferably, the alicyclic tetracarboxylic dianhydride is selected from one or more of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (cyclobutanetetracarboxylic dianhydride), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride. The structural formulas of the two are respectively as follows:
the fluorine-containing polyimide is characterized in that when the tetracarboxylic dianhydride is selected from the combination of aromatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride, the molar ratio of the aromatic tetracarboxylic dianhydride to the alicyclic tetracarboxylic dianhydride is 0.75-0.99; preferably, the molar ratio of the two is 0.78-0.95; more preferably, the molar ratio of the two is 0.80 to 0.90.
In a particular embodiment, the molar ratio of the aromatic tetracarboxylic dianhydride to the cycloaliphatic tetracarboxylic dianhydride is 0.85.
In a more specific embodiment, the aromatic tetracarboxylic dianhydride is selected from the group consisting of 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride; the alicyclic tetracarboxylic dianhydride is selected from 1,2,3, 4-cyclobutane tetracarboxylic dianhydride; the molar ratio of the two was 0.85.
In other more particular embodiments, the above-described molar ratios may be all values specifically within a particular numerical range. For example, when the term "0.80 to 0.90" is used, it is equivalent to 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, or 0.90. Other numerical ranges have similar meanings and are not described in detail.
The fluorine-containing polyimide is characterized in that the structural formula of the polyamic acid is shown as the formula (II):
wherein R is derived from a tetravalent organic radical of a tetracarboxylic dianhydride; the degree of polymerization n is in the range of 5 to 500.
Further, preferred, more preferred and most preferred aromatic tetracarboxylic dianhydrides are as described above.
Further, preferred, more preferred and most preferred cycloaliphatic tetracarboxylic dianhydrides are as described above.
In a particular embodiment, R is derived from a tetravalent organic radical of an aromatic tetracarboxylic dianhydride.
In a more specific embodiment, R is derived from a tetravalent organic group of 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride.
In another specific embodiment, R is derived from a combination of an aromatic tetracarboxylic dianhydride and a cycloaliphatic tetracarboxylic dianhydride. Wherein the aromatic tetracarboxylic dianhydride is selected from 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride; the alicyclic tetracarboxylic dianhydride is selected from 1,2,3, 4-cyclobutane tetracarboxylic dianhydride; the molar ratio of the two was 0.85.
Preferably, the polymerization degree n of the polyamic acid is in the range of 8 to 300; more preferably, the polymerization degree n of the polyamic acid is in the range of 10 to 200; and, further, the polymerization degree n of the polyamic acid is in the range of 15 to 150. Most preferably, the polymerization degree n of the polyamic acid is in the range of 20 to 120.
In a specific embodiment, the polymerization degree n of the polyamic acid is 100.
The fluorine-containing polyimide of the present invention is characterized in that the polyamic acid has a number average molecular weight Mn of 2.0 to 15.0 x 104In daltons range. Preferably, the number average molecular weight Mn of the polyamic acid is 4.0-13.0 x 104(ii) in the daltons range; more preferably, the number average molecular weight Mn of the polyamic acid is 6.0 to 12.0 x 104(ii) in the daltons range; and, most preferably, the number average molecular weight Mn of the polyamic acid is 7.0 to 11.0 x 104In daltons range.
In a specific embodiment, the polyamic acid has a number average molecular weight Mn of 9.2X 104And D, dalton.
The fluorine-containing polyimide according to the present invention, wherein the diamine compound of formula (I) is prepared according to the following method: (1) reacting a compound of formula (III)
Reacting to produce a dinitro compound of formula (IV);
(2) the dinitro compound of formula (IV) is reduced to obtain the diamine compound of formula (I).
In the present invention, the compound of the formula (III-1) is a known compound having a CAS number of 76238-88-5P; are synthesized according to the literature (Selivanov, B.A., et al, Zhurnal organic heskoi Khimii (1980),16(9),1910-1924) and are directly used in the work of the present invention.
In a specific preparation method, firstly, reacting a compound of a formula (III) with butyl lithium to generate a compound lithium salt of the formula (III), and then reacting the compound lithium salt of the formula (III) with haloalkane to form an intermediate; the intermediate is reacted with a substituted or unsubstituted nitrophenol to produce a compound of formula (IV).
In a specific embodiment, the haloalkane is difluorodibromomethane. The lithium salt of the compound of formula (III) is further reacted with dibromodifluoromethane to form an intermediate. The intermediate is reacted with p-nitrophenol.
In a specific production method, a solvent may be used as needed. The solvent is not particularly limited as long as it can dissolve the specific diamine compound and does not interfere with the reaction. Examples thereof include aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and dimethyl sulfoxide, dimethylformamide, dimethylacetamide and the like.
In a specific production method, the compound of formula (III) and the substituted or unsubstituted nitrophenol compound are used in a ratio of preferably 2 to 20 moles with respect to 1 mole of the compound of formula (III). Further, it is preferably 2 to 10 moles; more preferably 2 to 5 mol; and most preferably 2 to 3 moles.
When the dinitro compound of the formula (IV) is reduced, it can be carried out with a reducing agent such as hydrogen, hydrazine, hydrochloric acid or the like in the presence of a known catalyst.
Examples of the catalyst include a metal catalyst mainly composed of a group VIII metal, i.e., a metal such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, indium, or platinum, and specifically, a catalyst in which a metal is supported on a carrier, and a complex catalyst of the above metals. The reduction reaction may be a homogeneous system or a heterogeneous system.
In a particular embodiment, the catalyst is selected from palladium, supported on activated carbon.
The amount of the catalyst may be used in an appropriate ratio. For example, when the catalyst mainly contains the above-mentioned group VIII metal as an active component, the amount of the catalyst is preferably 0.0001 to 100 parts by weight, particularly preferably 0.001 to 20 parts by weight, based on 100 parts by weight of the dinitro compound. In addition, as the reduction reaction, a method using zinc, tin (II) carbide, sodium sulfide, sodium hydrogen sulfide, sodium hydrosulfite, or ammonium sulfide as a reducing agent can be used. The reducing agent is preferably used in an amount of 0.001 to 10 moles per 1 mole of the nitro group of the dinitro compound.
The solvent used in the reduction reaction is preferably a solvent which can dissolve the dinitro compound and the diamine compound at the same time and does not change the quality by the reduction reaction, and examples thereof include alcohols such as methanol, ethanol, propanol, and butanol; ethers such as diethyl ether, 1, 2-dimethoxyethane, tetrahydrofuran, dioxane and anisole.
In a specific embodiment, when the diamine compound of formula (I) is prepared, the preparation method is as follows:
(1) synthesizing a lithium reagent of the compound of the formula (III) by reacting the compound of the formula (III) with butyl lithium at a low temperature by using tetrahydrofuran as a solvent;
(2) adding 2-3 equivalents of difluorodibromomethane into the reaction solution at low temperature, quenching the reaction with dilute hydrochloric acid after the reaction is finished, and treating to obtain an oily concentrate;
(3) adding p-nitrophenol into the oily substance obtained in the above steps in the presence of an aprotic solvent and an inorganic base, reacting at room temperature, and performing series treatment to obtain a yellow solid;
(4) the solid is dissolved in toluene, ethanol or tetrahydrofuran, and is reduced into diamine compound under the action of Pd/C and hydrogen.
The fluorine-containing polyimide according to the present invention, wherein the polyamic acid is prepared by reacting a diamine compound with a tetracarboxylic acid dianhydride. Wherein the ratio of the tetracarboxylic acid dianhydride to the diamine compound is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents, of the acid anhydride group of the tetracarboxylic acid dianhydride to 1 equivalent of the amino group contained in the diamine compound; further, the ratio is preferably 0.8 to 1.2 equivalents. Most preferably 0.9 to 1.1 equivalents.
The fluorine-containing polyimide according to the present invention is obtained by performing a synthesis reaction of a polyamic acid in an organic solvent at a temperature of 100 to 250 ℃, preferably 150 to 220 ℃, and more preferably 170 to 200 ℃.
The organic solvent is not particularly limited as long as it can dissolve or disperse the synthesized polyamic acid. Examples thereof include aprotic polar solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, tetramethylurea, hexamethylphosphorous triamide and the like; phenol solvents such as m-methylphenol, xylenol, phenol, and halogenated phenol.
In addition, the organic solvent may be used in combination with a polyamic acid poor solvent such as alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons, as long as the formed polyamic acid is not precipitated. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, methylene chloride, 1, 2-dichloroethane, 1, 4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol methyl lactate, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, 1, 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and the like.
As described above, a reaction solution in which the polyamic acid was dissolved was obtained. Then, the reaction solution was dispersed in a large amount of a poor solvent to obtain precipitates. Then, the precipitate was filtered, washed, and dried to obtain polyamic acid.
The fluorine-containing polyimide according to the present invention, wherein the dehydration ring-closing step is: dissolving polyamide acid in an organic solvent, coating a film on a clean substrate, then gradually drying, and finally drying and cooling to obtain the polyimide.
In one embodiment, the preparation method is as follows:
(1) adding equivalent amount of diamine and dianhydride into m-cresol solvent under the protection of nitrogen or argon, heating to 170-200 ℃, heating for 8-15 hours, cooling to room temperature, dispersing with methanol solvent, filtering, washing, and drying to obtain polyamide acid (prepolymer);
(2) dissolving polyamic acid in an organic solvent, coating on a clean substrate, gradually drying, finally drying at 200-300 ℃ for 120 minutes, and cooling to obtain the polyimide film.
On the other hand, the invention provides a fluorine-containing PI film with high transparency and mechanical property, which contains the fluorine-containing polyimide.
The polyimide film of the present invention may be used in a variety of optoelectronic devices on the market, including, but not limited to, optoelectronic devices, solar cell devices, flexible display devices (e.g., OLEDs and LCDs), electronic books, electronic tags, or photosensors. Preferably, the optoelectronic device is selected from the group consisting of a solar cell device, a flexible display device (e.g., OLED and LCD). The photoelectric device has higher requirements on transparency and mechanical property, and the two properties must be balanced at the same time.
Without wishing to be bound by any theory, the inventors found that, unlike the high aromatic conjugation property of the main chain of the conventional polyimide molecule and the charge complexing transfer effect in the molecular chain which generally cause a decrease in transparency, when a hexafluoronaphthalene structure is introduced into the polyimide molecule, a fluorine-containing bridge bond (OCF) is incorporated2And CF2O), light transmission in the far ultraviolet and near infrared regions is preferable. Compared with the prior art, the transparency is approximately at the same level. Meanwhile, the structure further increases the interaction between the main chains of the polyimide molecules, so that the polyimide film has excellent mechanical properties while keeping high transparency; and meanwhile, the affinity with other matrixes is better. In line with the general expectation, the naphthalene ring structure leads to a slight increase in the conjugated units of the polyimide molecule, inevitably resulting in slightly lower transparency than the perfluoro benzene ring structure; but this is balanced by the specific choice of tetracarboxylic dianhydride, so that the balance of transparency and mechanical properties is better。
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications can be made by those skilled in the art after reading the contents of the present invention, and those equivalents also fall within the scope of the invention defined by the appended claims.
The following examples will aid understanding of the present invention, but are not intended to limit the scope of the present invention.
Example 1: preparation of the Compound of formula (II)
(1) Adding 35.4g (0.15mol) of the compound shown in the formula (III-1) and 500ml of tetrahydrofuran into a 1L three-necked bottle, installing and stirring, cooling to-80 ℃ by a cold bath and a nitrogen protection device, starting stirring, cooling to-80 ℃ under the protection of nitrogen, dropwise adding 150ml of butyl lithium solution (0.35mol), keeping the temperature below-70 ℃ for stirring for 1h after the dropwise adding is finished, then continuously dropwise adding a difluorodibromomethane solution (containing 0.40mol of difluorodibromomethane), keeping the temperature below-70 ℃, continuing stirring for 1h after the dropwise adding is finished, then hydrolyzing by using 10% dilute hydrochloric acid, further performing post-treatment to obtain 45g of brown oily matter, wherein the yield is 61%, and the next-step reaction can be directly performed without further treatment.
(2) 40g of oily matter prepared in the step (1), 500ml of dimethylformamide, 1g of potassium iodide and 22.5g of p-nitrophenol are added into a 1L three-necked bottle, the temperature is increased to 105 ℃, after 4 hours of reaction, the heating is stopped, ice water is added into a reaction system after cooling, until products are separated out, the products are filtered and washed, and then the products are crystallized by ethanol, so that 24.2g of yellow solid is obtained, the yield is 48 percent, and the purity is 98 percent.1HNMR(δ,ppm,DMSO-d6):8.39(d,4H,ArH),8.27(d,4H,ArH)；FTIR(KBr,cm-1):1582,1343(-NO2) 1198(C-F),1165 (C-F); elemental analysis C24H8F10N2O6(610.31); theoretical C47.23%, F31.13%, N4.59%, O15.73%, found: 47.56% of C, 30.89% of F, 4.52% of N and 15.34% of O.
(3) 20g of the two obtained in the previous step were added to a 1L autoclaveThe nitro compound, 150ml of toluene, 100ml of ethanol, 1g of 5% Pd/C, hydrogenation for 8 hours at normal temperature and normal pressure, monitoring the qualified reaction through gas chromatography, carrying out the next step of treatment, filtering, concentrating, crystallizing with 120ml of isopropanol to obtain pink solid powder, and drying to obtain 16.5g of pink solid powder with 99% of gas chromatography purity and 91% of yield.1H NMR(δ,ppm,DMSO-d6):8.14(d,4H,ArH),7.82(d,4H,ArH),5.91(s,4H,NH2)；FTIR(KBr,cm-1):3418(-NH2),3367(-NH2) 1204(C-F),1132 (C-F); elemental analysis C24H12F10N2O2(550.35); theoretical values C52.38%, F34.52%, N5.06%, O5.81%, found values: c52.47%, F34.39%, N5.15%, O5.64%.
Example 2: preparation of Polyamic acid
Into a 500mL three-necked flask, 8g of the diamine compound of example 1 and 6.4g of 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride were charged,
300g of m-cresol, heated to 190 ℃, reacted for 8 hours, cooled to about 60 ℃, the reaction solution is dispersed into methanol under stirring, and after cooling, suction filtration and washing with methanol are carried out. Drying gave 12.8g of a filamentous solid. Number average molecular weight Mn 10.5X 104The molecular weight distribution PDI index is 2.12. The molecular weight and molecular weight distribution were measured on a PE Series 200GPC instrument using polystyrene as a standard.
Example 3: preparation of Polyamic acid
The same as example 2 except that the amount of 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride was 90% by mole of 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride: 10% of cyclobutanetetracarboxylic dianhydride. Number average molecular weight Mn 9.7X 104The molecular weight distribution PDI index is 2.05.
Example 4: preparation of Polyamic acid
The same as example 2, but using 3,3 ', 4, 4' -perfluoroisopropylidenediphthalic acidAnhydride was 80% of 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride in terms of molar amount by the same number: 20% of cyclobutanetetracarboxylic dianhydride. Number average molecular weight Mn 9.4X 104The molecular weight distribution PDI index is 1.99.
Example 5: preparation of Polyamic acid
The same as example 2 except that the amount of 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride was 70% by mole of 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride: a mixture of 30% cyclobutanetetracarboxylic dianhydride. Number average molecular weight Mn 8.1X 104The molecular weight distribution PDI index is 2.36.
The application example is as follows: polyimide film and properties thereof
The filamentous solid obtained in example 2 to 5 was dissolved in 5% N-methylpyrrolidone to prepare a 5% solution, which was then filtered through a 0.45 μm filter to remove mechanical impurities. Then coating the polymer solution on a clean glass substrate, drying for 1 hour at 50 ℃,1 hour at 100 ℃, finally drying for 2 hours at 200 ℃, cooling to room temperature, demoulding and respectively preparing a transparent polyimide film with the thickness of about 20 mu m as the application of the invention
Examples 1 to 4.
Wherein, the optical transparency and the thermal stability of the polyimide film are respectively measured on a UV-visible spectrophotometer and a TGA/DSC synchronous thermal analyzer; the mechanical properties of the polyimide film were measured in a CMT-4104 type universal tester, and test specimens prepared in the same manner as described above and having dimensions of 60X 10X 0.045mm3The initial force of the test is 5Kg, the stretching speed is 2mm/min, and the test result is taken as the average value of 3 times.
Application comparative example: application comparative example: the polyimide film of example 3 of chinese patent application CN106674027A was subjected to the above test according to the same method of the present invention, and used as comparative example 1.
See table 1 for results.
TABLE 1
As can be seen from table 1, when a hexafluoronaphthalene structure is introduced into a polyimide molecule, the transmittance of light in the far ultraviolet and near infrared regions is better in combination with a fluorine-containing bridge bond. The transparency was approximately the same level as that of comparative application example 1. Meanwhile, the structure further increases the interaction between the main chains of the polyimide molecules, so that the high transparency is maintained, and the excellent tensile strength and elongation at break are realized; and meanwhile, the affinity with other matrixes is better. In addition, the balance effect of the transparency and the mechanical property is better through the specific selection of the tetracarboxylic dianhydride. When the mixture of (80-90)% 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride and (20-10)% cyclobutane tetracarboxylic dianhydride is used, the 450nm transmittance reaches more than 87%, the requirements of most transparent films on the market can be better met, and in addition, the mechanical properties can also obtain better balance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (20)
1. The fluorine-containing polyimide is obtained by dehydrating and ring-closing polyamic acid; characterized in that the polyamic acid is prepared from a diamine compound of formula (I)
And the tetracarboxylic dianhydride by a polycondensation reaction.
2. The fluorine-containing polyimide according to claim 1, wherein the tetracarboxylic dianhydride is selected from aromatic tetracarboxylic dianhydrides; or a combination of aromatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride.
3. The fluorine-containing polyimide according to claim 2, wherein the aromatic tetracarboxylic dianhydride is selected from one or more of 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic dianhydride, 4,4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 3 ', 4,4 ' -perfluoroisopropylidene diphthalic dianhydride, 3 ', 4,4 ' -biphenyl tetracarboxylic dianhydride;
the alicyclic tetracarboxylic dianhydride is selected from one or more of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1, 2-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride, 1, 3-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride and 1,2,4, 5-norbornane tetracarboxylic dianhydride.
4. The fluorine-containing polyimide according to claim 2 or 3, wherein the aromatic tetracarboxylic dianhydride is selected from the group consisting of 3,3 ', 4, 4' -perfluoroisopropylidene diphthalic dianhydride; the alicyclic tetracarboxylic dianhydride is selected from one or more of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride and 1,2,3, 4-cyclopentane tetracarboxylic dianhydride.
5. The fluorine-containing polyimide according to claim 4, wherein the molar ratio of the aromatic tetracarboxylic dianhydride to the alicyclic tetracarboxylic dianhydride is 0.75 to 0.99.
6. The fluorine-containing polyimide according to claim 5, wherein the molar ratio of the aromatic tetracarboxylic dianhydride to the alicyclic tetracarboxylic dianhydride is 0.78 to 0.95.
7. The fluorine-containing polyimide according to claim 6, wherein the molar ratio of the aromatic tetracarboxylic dianhydride to the alicyclic tetracarboxylic dianhydride is 0.80 to 0.90.
8. The fluorine-containing polyimide according to claim 1, wherein the structural formula of the polyamic acid is represented by formula (II):
wherein R is derived from a tetravalent organic radical of said tetracarboxylic dianhydride; the degree of polymerization n is in the range of 5 to 500.
9. The fluorine-containing polyimide according to claim 8, wherein a degree of polymerization n is in a range of 8 to 300.
10. The fluorine-containing polyimide according to claim 9, wherein a degree of polymerization n is in a range of 10 to 200.
11. The fluorine-containing polyimide according to claim 10, wherein a degree of polymerization n is in a range of 15 to 150.
12. The fluorine-containing polyimide according to claim 11, wherein a degree of polymerization n is in a range of 20 to 120.
13. The fluorine-containing polyimide according to claim 8, wherein the polyamic acid has a number-average molecular weight Mn of 2.0 to 15.0 x 104In daltons range.
14. The fluorine-containing polyimide according to claim 13, wherein the polyamic acid has a number-average molecular weight Mn of 4.0 to 13.0 x 104In daltons range.
15. The fluorine-containing polyimide according to claim 14, wherein the polyamic acid has a number-average molecular weight Mn of 6.0 to 12.0 x 104In daltons range.
16. The fluorine-containing polyimide according to claim 15, wherein the polyamic acidThe number average molecular weight Mn of (A) is 7.0 to 11.0 x 104In daltons range.
17. The fluorine-containing polyimide according to claim 1, wherein the dehydration ring-closing step is: dissolving polyamide acid in an organic solvent, coating a film on a clean substrate, then gradually drying, and finally drying and cooling to obtain the polyimide.
18. A fluorine-containing PI film having both high transparency and mechanical properties, comprising the fluorine-containing polyimide according to any one of claims 1 to 17.
19. Use of a fluorine-containing PI film according to claim 18 in an optoelectronic device.
20. Use according to claim 19, the optoelectronic device being selected from the group consisting of solar cell devices, flexible display devices.
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| CN101456954A (en) * | 2008-12-23 | 2009-06-17 | 东华大学 | Method for preparing polyimide by diphthalazinone structure and trifluoromethyl substituted aromatic diamine monomer |
| CN102634022A (en) * | 2012-04-10 | 2012-08-15 | 中国科学院化学研究所 | Colorless highly-transparent polyimide film as well as preparation method and application thereof |
| CN102898644A (en) * | 2011-07-28 | 2013-01-30 | 苏州华辉材料科技有限公司 | Soluble fluorine-containing aromatic semi-alicyclic polyimide film material and preparation method thereof |
| CN104672901A (en) * | 2015-02-28 | 2015-06-03 | 重庆杰博科技有限公司 | Transparent polyimide film and preparation method thereof |
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| CN101456954A (en) * | 2008-12-23 | 2009-06-17 | 东华大学 | Method for preparing polyimide by diphthalazinone structure and trifluoromethyl substituted aromatic diamine monomer |
| CN102898644A (en) * | 2011-07-28 | 2013-01-30 | 苏州华辉材料科技有限公司 | Soluble fluorine-containing aromatic semi-alicyclic polyimide film material and preparation method thereof |
| CN102634022A (en) * | 2012-04-10 | 2012-08-15 | 中国科学院化学研究所 | Colorless highly-transparent polyimide film as well as preparation method and application thereof |
| CN104672901A (en) * | 2015-02-28 | 2015-06-03 | 重庆杰博科技有限公司 | Transparent polyimide film and preparation method thereof |
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Denomination of invention: Fluorine containing PI film with high transparency and mechanical properties and its application Effective date of registration: 20210305 Granted publication date: 20200424 Pledgee: Bank of China Limited Nanjing Jiangbei New Area Branch Pledgor: JIANGSU CREATIVE ELECTRONIC CHEMICALS Co.,Ltd. Registration number: Y2021980001484 |
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Denomination of invention: Fluorine containing PI film with high transparency and mechanical properties and its application Effective date of registration: 20220126 Granted publication date: 20200424 Pledgee: Bank of China Limited Nanjing Jiangbei New Area Branch Pledgor: JIANGSU CREATIVE ELECTRONIC CHEMICALS CO.,LTD. Registration number: Y2022980001141 |
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Date of cancellation: 20230601 Granted publication date: 20200424 Pledgee: Bank of China Limited Nanjing Jiangbei New Area Branch Pledgor: JIANGSU CREATIVE ELECTRONIC CHEMICALS CO.,LTD. Registration number: Y2022980001141 |