CN108517035A - Have both fluorine-containing PI films and the application of high transparency and mechanical property - Google Patents
Have both fluorine-containing PI films and the application of high transparency and mechanical property Download PDFInfo
- Publication number
- CN108517035A CN108517035A CN201810576656.6A CN201810576656A CN108517035A CN 108517035 A CN108517035 A CN 108517035A CN 201810576656 A CN201810576656 A CN 201810576656A CN 108517035 A CN108517035 A CN 108517035A
- Authority
- CN
- China
- Prior art keywords
- dicarboxylic anhydride
- tetrabasic carboxylic
- acid
- carboxylic acid
- fluorinated polyimide
- 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.)
- Granted
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000011737 fluorine Substances 0.000 title claims abstract description 15
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 108
- -1 diamine compound Chemical class 0.000 claims abstract description 66
- 229920001721 polyimide Polymers 0.000 claims abstract description 43
- 239000004642 Polyimide Substances 0.000 claims abstract description 40
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 33
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 230000005693 optoelectronics Effects 0.000 claims abstract 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 27
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 24
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 19
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 3
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical class C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 claims description 3
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical class 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
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 34
- 230000000694 effects Effects 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
- 230000035699 permeability Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
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- 239000002904 solvent Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 235000019441 ethanol Nutrition 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
- 239000007787 solid Substances 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
- 238000006722 reduction reaction Methods 0.000 description 5
- 125000005591 trimellitate group Chemical group 0.000 description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- 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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical class [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- 239000004519 grease Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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
- 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 229920000642 polymer Polymers 0.000 description 2
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- 150000003254 radicals Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
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- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
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- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
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- 239000012141 concentrate Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 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
- 230000007812 deficiency Effects 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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 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
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000003863 metallic catalyst Substances 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
- DKJCSMHIPYRALV-UHFFFAOYSA-N methoxymethyl propanoate Chemical compound CCC(=O)OCOC DKJCSMHIPYRALV-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-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
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-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
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 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
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- WGRQANOPCQRCME-PMACEKPBSA-N teneligliptin Chemical compound O=C([C@H]1NC[C@H](C1)N1CCN(CC1)C1=CC(=NN1C=1C=CC=CC=1)C)N1CCSC1 WGRQANOPCQRCME-PMACEKPBSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Disclose a kind of fluorine-containing PI films having both high transparency and mechanical property, the film contains obtains fluorinated polyimide by polyamic acid dehydration closed-loop, wherein, polyamic acid is obtained with tetrabasic carboxylic acid dicarboxylic anhydride by polycondensation reaction by the diamine compound of formula (I).In addition the application of above-mentioned fluorine-containing PI films in the opto-electronic device is also disclosed.It is preferable in the permeability of far ultraviolet and near infrared region light in conjunction with fluorine-containing bridged bond when introducing hexafluoro naphthalene structure in polyimide molecule.Above structure further increases the interaction between polyimide molecule main chain, to while keeping compared with high transparency, have both excellent mechanical property；It is preferable with the compatibility of other matrixes simultaneously.Further, it is balanced by the specific selection of tetrabasic carboxylic acid dicarboxylic anhydride so that the counterbalance effect of the transparency and mechanical property is more preferably.
Description
Technical field
The invention belongs to optical material fields；It is related to a kind of Kapton and its application more particularly to one kind has both
The fluorine-containing PI films and application of high transparency and mechanical property.
Background technology
Polyimides (PI) is that molecular structure contains the pentacyclic a kind of high molecular material of acid imide, mainly passes through aromatic series
Dianhydride compound is made with diamine compound by polycondensation method.This kind of compound is since it is with excellent thermal stability, machine
Tool intensity, dielectric properties, insulation characterisitic, and have the characteristics that toughness and flexibility outstanding, gradually it is applied to many fields,
Especially develop faster Flexible Displays industry in recent years.
With industrial expansions such as aerospace, solar energy, microelectronics, constantly to the heat resistance of polyimide material,
Dielectric properties, mechanical property and the transparency propose further requirement.Due to the height of traditional polyimide molecule main chain
Transferance is complexed in charge in aromatic conjugated property and strand, and Kapton usually has color, while photopermeability is poor,
It is almost opaque in visible light region.
To improve the use characteristic of Kapton in these areas, researcher has been carried out a series of exploration work
Make, part research work also achieves some effects.For example, Chinese patent application CN101674923A disclose it is a kind of colourless
The preparation method and preparation facilities of bright Kapton, this method use 1,2,4,5- hexamethylene tetracid of alicyclic dianhydride compound
Dianhydride is made with diamine compound polymerization technique, and transparent polyimide film, thickness obtained are directly prepared using the solution
Degree is that the light transmittance of 200 μm of films is 89.8%.It is poly- that Chinese patent application CN102634022 A disclose a kind of colourless high transparency
Imide membrane and the preparation method and application thereof polymerize to obtain transparent polyamides well sub- using fatty dianhydride and different diamines
Amine film.However, the heat resistance of above-mentioned Kapton is unsatisfactory.
On this basis, Chinese patent application CN106674027 A disclose a kind of using strong and fluorine-containing with fluorine-containing bridge
The fluorinated polyimide film that the diamines of benzene is prepared with dianhydride.The Kapton is in heat resistance, dissolubility and transparency etc.
Aspect all has more excellent performance.However, while bringing high transparency, fluorine-containing bridge is strong and the introducing containing fluorobenzene causes
The mechanical property of the Kapton reduces, and can not be satisfactory with the compatibility of other matrixes.
Invention content
According to background above, technical problem solved by the invention is how preferably to make Kapton with height
Excellent mechanical property is had both while transparent；It is preferable with the compatibility of other matrixes simultaneously.
Based on this, one of the object of the invention is to overcome the deficiencies of the prior art and provide a kind of fluorinated polyimide, described to contain
Fluorine polyimides is obtained by polyamic acid dehydration closed-loop；It is characterized in that, diamine compound of the polyamic acid by formula (I)
It is obtained by polycondensation reaction with tetrabasic carboxylic acid dicarboxylic anhydride.
Fluorinated polyimide according to the present invention, wherein the tetrabasic carboxylic acid dicarboxylic anhydride is selected from aromatic tetracarboxylic acid two
Acid anhydrides and/or Alicyclic tetracarboxylic acid dicarboxylic anhydride.
In one preferred embodiment, the tetrabasic carboxylic acid dicarboxylic anhydride is selected from aromatic tetracarboxylic acid's dicarboxylic anhydride.
As aromatic tetracarboxylic acid's dicarboxylic anhydride that the present invention uses, including but not limited to, pyromellitic acid dianhydride, 3,3 ', 4,
4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydrides, 1,4,5,8- naphthalene tetracarboxylic acids dicarboxylic anhydride,
2,3,6,7- naphthalene tetracarboxylic acids dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-dimethyl diphenyls
Silane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetrabasic carboxylic acid dicarboxylic anhydrides, 1,2,3,4- furans tetrabasic carboxylic acids dicarboxylic anhydride, 4,
4 '-two (3,4- di carboxyl phenyloxies) diphenylsulfide dicarboxylic anhydrides, 4,4 '-two (3,4- di carboxyl phenyloxies) diphenyl sulfone diacid
Acid anhydride, 4,4 '-two (3,4- di carboxyl phenyloxies) diphenyl propane dicarboxylic anhydrides, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalandione two
Acid anhydride, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydrides, two (phthalandione) phosphniline oxide dicarboxylic anhydrides, (the triphenyl phthalein of p-phenylene-two
Acid) dianhydride,-phenylene-two (triphenyl phthalandione) dianhydride, two (triphenyl phthalandione) -4,4 '-diphenyl ether dianhydrides, two (triphenyls
Phthalandione) -4,4 '-diphenyl methane dianhydrides, ethylene glycol-two (dehydration trimellitate), (the dehydration trimellitic acid of propylene glycol-two
Ester), 1,4- butanediols-two (dehydration trimellitate), 1,6-HD-two (dehydration trimellitate), 1,8- ethohexadiols-two
(dehydration trimellitate), 2,2- bis- (4- hydroxyphenyls) propane-two (dehydration trimellitate).
Preferably, aromatic tetracarboxylic acid's dicarboxylic anhydride is selected from 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydrides, 4,4 '-
Two (3,4- di carboxyl phenyloxies) diphenylsulfide dicarboxylic anhydrides, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydrides, 1,4,5,8-
Naphthalene tetracarboxylic acid dicarboxylic anhydride, 2,3,6,7- naphthalene tetracarboxylic acids dicarboxylic anhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalandione dianhydride, 3,3 ',
It is one or more in 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydrides.
It is highly preferred that aromatic tetracarboxylic acid's dicarboxylic anhydride is selected from 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydrides, 3,
It is one or more in 3 ', 4,4 '-perfluor isopropylidene, two phthalandione dianhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydrides.
Most preferably, aromatic tetracarboxylic acid's dicarboxylic anhydride is selected from 3,3 ', 4,4 '-perfluor isopropylidene, two phthalandione dianhydride,
Its structural formula is as described below：
In one preferred embodiment, the tetrabasic carboxylic acid dicarboxylic anhydride is selected from aromatic tetracarboxylic acid's dicarboxylic anhydride and alicyclic
The combination of tetrabasic carboxylic acid dicarboxylic anhydride.
As aromatic tetracarboxylic acid's dicarboxylic anhydride preferred, more preferred and most preferred in the embodiment, as described above.
In addition, as the Alicyclic tetracarboxylic acid dicarboxylic anhydride that the present invention uses, including but not limited to, butane tetracarboxylic acid diacid
Acid anhydride, 1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, 1,2- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, 1,3- diformazans
Base -1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, bis- chloro- 1,2,3,4- cyclobutane tetrabasic carboxylic acid dicarboxylic anhydrides of 1,3-, 1,2,3,4- tetra-
Methyl-1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, 1,2,3,4- pentamethylene tetrabasic carboxylic acids dicarboxylic anhydride, 1,2,4,5- hexamethylene tetracarboxylic acids
Acid diacid acid anhydride, 1,2,4,5- norbornane tetrabasic carboxylic acids dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydrides, 2,3,5- tri-
Carboxyl cyclopenta acetic acid dianhydride, tri- carboxyl norbornane -2- acetic acid dianhydrides of 3,5,6-, 2,3,4,5- tetrahydrofuran tetracarboxylic acid acid diacids
Acid anhydride, 1,3,3a, 4,5,9b- hexahydros -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furans -1,3- diketone, 1,
3,3a, 4,5,9b- hexahydro -5- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furans -1,3- diketone,
1,3,3a, 4,5,9b- hexahydro -5- ethyls -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furans -1,3- two
Ketone, 1,3,3a, 4,5,9b- hexahydro -7- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furans -1,3-
Diketone, 1,3,3a, 4,5,9b- hexahydro -7- ethyls -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furans -1,
3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furans -
1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- ethyls -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,2-c]-furan
Mutter -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -5,8- dimethyl -5- (tetrahydrochysene -2,5- dioxo -3- furyls)-naphthalene [1,
2-c]-furans -1,3- diketone, 5- (2,5- dioxotetrahydros fural) -3- methyl -3- cyclohexene -1,2- dicarboxylic acids two
Acid anhydride, bicyclic [2,2,2]-octyl- 7- alkene -2,3,5,6- tetrabasic carboxylic acids dicarboxylic anhydride, 3- oxabicyclos [3.2.1] octane -2,4- diketone -6-
Spiral shell -3 '-(tetrahydrofuran -2 ', 5 '-diketone).
Preferably, the Alicyclic tetracarboxylic acid dicarboxylic anhydride is selected from 1,2,3,4- cyclobutane tetrabasic carboxylic acid dicarboxylic anhydrides, 1,2- diformazans
Base -1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, 1,2,3,4-
Tetramethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, 1,2,3,4- pentamethylene tetrabasic carboxylic acids dicarboxylic anhydride, 1,2,4,5- hexamethylenes four
It is one or more in carboxylic diacid acid anhydride, 1,2,4,5- norbornane tetrabasic carboxylic acid dicarboxylic anhydrides.
It is highly preferred that the Alicyclic tetracarboxylic acid dicarboxylic anhydride is selected from 1,2,3,4- cyclobutane tetrabasic carboxylic acid dicarboxylic anhydrides, 1,2,3,
4- pentamethylene tetrabasic carboxylic acids dicarboxylic anhydride, 1,2,4,5- cyclopentanetetracarboxylics dicarboxylic anhydride, 1,2,4,5- norbornane tetrabasic carboxylic acid dicarboxylic anhydrides
In it is one or more.
Most preferably, the Alicyclic tetracarboxylic acid dicarboxylic anhydride is selected from 1,2,3,4- cyclobutane tetrabasic carboxylic acid dicarboxylic anhydride (cyclobutane
Tetracarboxylic acid dianhydride), it is one or more in 1,2,3,4- pentamethylene tetrabasic carboxylic acid dicarboxylic anhydrides.The structural formula of the two distinguishes following institute
It states：
Fluorinated polyimide according to the present invention, wherein when the tetrabasic carboxylic acid dicarboxylic anhydride is selected from aromatic tetracarboxylic acid
When the combination of dicarboxylic anhydride and Alicyclic tetracarboxylic acid dicarboxylic anhydride, aromatic tetracarboxylic acid's dicarboxylic anhydride and the Alicyclic tetracarboxylic acid two
The molar ratio of acid anhydrides is 0.75~0.99；Preferably, the molar ratio of the two is 0.78~0.95；It is highly preferred that mole of the two
Than being 0.80~0.90.
In a specific embodiment, aromatic tetracarboxylic acid's dicarboxylic anhydride and the Alicyclic tetracarboxylic acid dicarboxylic anhydride
Molar ratio be 0.85.
In one more specifically embodiment, it is different that aromatic tetracarboxylic acid's dicarboxylic anhydride is selected from 3,3 ', 4,4 '-perfluors
Two phthalandione dianhydride of propylidene；The Alicyclic tetracarboxylic acid dicarboxylic anhydride is selected from 1,2,3,4- cyclobutane tetrabasic carboxylic acid dicarboxylic anhydrides；The two
Molar ratio is 0.85.
In other more specifically embodiment, above-mentioned molar ratio can be all specific of special value range
Value.For example, when using the term of " 0.80~0.90 ", be equal to 0.80,0.81,0.82,0.83,0.84,0.85,0.86,
0.87,0.88,0.89 or 0.90.The meaning that other numberical ranges indicate is similar, repeats no more.
Fluorinated polyimide according to the present invention, wherein shown in the structural formula of the polyamic acid such as formula (II)：
Wherein, R is originated from the quadrivalent organic radical of tetrabasic carboxylic acid dicarboxylic anhydride；Polymerization degree n is in 5 to 500 ranges.
Further, it is preferable to, more preferable and most preferred aromatic tetracarboxylic acid's dicarboxylic anhydride, as described above.
Further, it is preferable to, more preferable and most preferred Alicyclic tetracarboxylic acid dicarboxylic anhydride, as described above.
In a specific embodiment, R is originated from the quadrivalent organic radical of aromatic tetracarboxylic acid's dicarboxylic anhydride.
In one more specifically embodiment, R is originated from the four of 3,3 ', 4,4 '-perfluor isopropylidene, two phthalandione dianhydride
Valence organic group.
In another particular embodiment of the invention, R is originated from aromatic tetracarboxylic acid's dicarboxylic anhydride and Alicyclic tetracarboxylic acid dicarboxylic anhydride
Combination.Wherein, aromatic tetracarboxylic acid's dicarboxylic anhydride is selected from 3,3 ', 4,4 '-perfluor isopropylidene, two phthalandione dianhydride；The fat
Ring race tetrabasic carboxylic acid dicarboxylic anhydride is selected from 1,2,3,4- cyclobutane tetrabasic carboxylic acid dicarboxylic anhydrides；The molar ratio of the two is 0.85.
Preferably, the polymerization degree n of the polyamic acid is in 8 to 300 ranges；It is highly preferred that the polyamic acid is poly-
Right n is in 10 to 200 ranges；And further, the polymerization degree n of the polyamic acid is in 15 to 150 ranges.It is optimal
Selection of land, the polymerization degree n of the polyamic acid is in 20 to 120 ranges.
In a specific embodiment, the polymerization degree n of the polyamic acid is 100.
Fluorinated polyimide according to the present invention, wherein the number-average molecular weight Mn of the polyamic acid 2.0~15.0 ×
104In the range of dalton.Preferably, the number-average molecular weight Mn of the polyamic acid is 4.0~13.0 × 104The model of dalton
In enclosing；It is highly preferred that the number-average molecular weight Mn of the polyamic acid is 6.0~12.0 × 104In the range of dalton；And
Most preferably, the number-average molecular weight Mn of the polyamic acid is 7.0~11.0 × 104In the range of dalton.
In a specific embodiment, the number-average molecular weight Mn of the polyamic acid is 9.2 × 104Dalton.
Fluorinated polyimide according to the present invention, wherein the diamine compound of formula (I) is prepared in following manner：(1) make
The compound of formula (III)
Reaction generates the dinitro compound of formula (IV)；
(2) so that the dinitro compound of formula (IV) is restored, obtain the diamine compound of formula (I).
In the present invention, the compound of formula (III-1) is known compound, and No. CAS is 76238-88-5P；System is according to document
(Selivanov, B.A. etc., Zhurnal Organicheskoi Khimii (1980), 16 (9), 1910-1924) is synthesized
It arrives, is directly used in work of the present invention.
In specific preparation method, the compound of formula (III) first reacts the compound lithium for generating formula (III) with butyl lithium
Salt, then the compound lithium salts of formula (III) react the step of forming intermediate with halogenated alkane；The intermediate is with substitution or not
Substituted nitrophenol reaction generates the compound of formula (IV).
In a specific embodiment, the halogenated alkane is difluorodibromomethane.The compound lithium salts of formula (III)
It further reacts to form intermediate with difluorodibromomethane.The intermediate is reacted with p-nitrophenol.
In specific preparation method, solvent can be used as needed.As above-mentioned solvent, as long as specific two can be made
Amine compounds dissolve, and will not interfere reaction, it is not particularly limited.It can enumerate aromatic hydrocarbon such as benzene, toluene；
The ethers such as ether, tetrahydrofuran, dioxane；The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；And dimethyl is sub-
Sulfone, dimethylformamide, dimethylacetylamide etc..
In specific preparation method, the use of the compound and substituted or unsubstituted compounds p-nitrophenol of formula (III)
Ratio, relative to the compound of 1 mole of formula (III), the latter is preferably 2~20 moles.Further, it is preferable to be 2~10 moles；
More preferably 2~5 moles；And most preferably 2~3 moles.
When the reduction of the dinitro compound of formula (IV), the reducing agents such as hydrogen, hydrazine, hydrochloric acid can be used in known catalyst
In the presence of carry out.
As above-mentioned catalyst, can enumerate for example with group VIII metal, i.e. iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, indium, platinum
Equal metals, which are the metallic catalyst of active main body, specifically can enumerate Metal Supported in supported catalyst, above-mentioned metal
Complex catalyst.Above-mentioned reduction reaction can be that homogeneous system can also be heterogeneous system.
In a specific embodiment, catalyst is selected from palladium, and load is on the activated carbon.
The dosage of catalyst can use ratio appropriate.Such as when catalyst is using above-mentioned group VIII metal as active main body
When, relative to 100 parts by weight dinitro compounds, it is preferable to use 0.0001~100 parts by weight, particularly preferably use 0.001~
20 parts by weight.In addition, as above-mentioned reduction reaction, zinc also can be used, tin, carbonization tin (II), vulcanized sodium, sodium bisulfide, connect two
The method of sodium sulfite, ammonium sulfide as reducing agent.Relative to the nitro of 1 mole of dinitro compound, reducing agent it is preferable to use
0.001~10 mole.
As the solvent used in above-mentioned reduction reaction, it is preferably able to dissolve dinitro compound and two amine compounds simultaneously
Object, and will not be rotten because of reduction reaction solvent, the alcohols such as methanol, ethyl alcohol, propyl alcohol, butanol can be enumerated；Ether, 1,
The ethers such as 2- dimethoxy-ethanes, tetrahydrofuran, dioxane, anisole.
In a specific embodiment, when preparing the diamine compound of formula (I), preparation method is as follows：
(1) using tetrahydrofuran as solvent under the compound low temperature of formula (III), by reacting synthesis formula (III) with butyl lithium
The lithium reagent of compound；
(2) difluorodibromomethane of 2~3 equivalents is added under low temperature to above-mentioned reaction solution, is quenched after completion of the reaction with dilute hydrochloric acid
It goes out reaction, the concentrate of oily is obtained after processing；
(3) p-nitrophenol, room is added in the presence of non-protonic solvent, inorganic base in the grease that above step obtains
By series of processes after temperature reaction, yellow solid is obtained；
(4) above-mentioned solid is dissolved in toluene, ethyl alcohol or tetrahydrofuran, at Pd/C and hydrogen effect, is reduced to
Diamine compound.
Fluorinated polyimide according to the present invention, wherein the polyamic acid is by making diamine compound and tetrabasic carboxylic acid two
Anhydride reaction is made.Wherein, the usage rate of tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound, preferably with respect to 1 equivalent, two amine compounds
Amino contained in object, it is the ratio of 0.2~2 equivalent, more preferably 0.3~1.2 equivalent to make the anhydride group of tetrabasic carboxylic acid dicarboxylic anhydride
Ratio；Further, it is preferable to for the ratio of 0.8~1.2 equivalent.The most preferably ratio of 0.9~1.1 equivalent.
Fluorinated polyimide according to the present invention, wherein the synthetic reaction of polyamic acid, in organic solvent in 100~
250 DEG C, be preferable over 150~220 DEG C, more preferably carry out under 170~200 DEG C of temperature condition.
As organic solvent, as long as the polyamic acid of synthesis can be dissolved or be disperseed, it is not particularly limited.It can be with
Illustrate such as n-methyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), γ-fourth
The aprotic polar solvents such as lactone, tetramethylurea, hexamethyl phosphorous acid triamide；Between sylvan, dimethlbenzene, phenol, halogenated
The phenol solvents such as phenol.
In addition, in the range of not making the polyamic acid of generation be precipitated, can also be used in combination in above-mentioned organic solvent poly-
Amic acid poor solvent alcohols, ketone, esters, ethers, halogenated hydrocarbon, hydro carbons etc..As the specific example of this poor solvent,
Such as methanol, ethyl alcohol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4- butanediols, triethylene glycol, ethylene glycol list can be enumerated
Methyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, methyl acetate, ethyl acetate,
Butyl acetate, methoxy methyl propionate, ethoxyl ethyl propionate, diethy-aceto oxalate, diethyl malonate, ether, ethylene glycol first
Ether, ethylene glycol ethyl ether, ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ethers
Ether acetic acid ester, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid
Ester, diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran, dichloromethane, 1,2- dichloroethanes, 1,4- dichloroetane, trichloroethanes, chlorine
Benzene, o-dichlorohenzene, hexane, heptane, octane, benzene,toluene,xylene etc..
As described above, obtaining the reaction solution of dissolving polyamic acid.Then, which is distributed to a large amount of bad molten
In agent, precipitate is obtained.Then, precipitate is filtered, washed, dried, obtain polyamic acid.
Fluorinated polyimide according to the present invention, wherein the dehydration closed-loop step is：Polyamic acid is dissolved in organic
In solvent, the film on cleaning substrate, then gradually drying, is finally dried, cooling, obtains polyimides.
In a specific embodiment, preparation method is as follows：
(1) diamines of equivalent and dianhydride are added in metacresol solvent, are heated up under nitrogen or argon gas protection
It to 170~200 DEG C, heats 8~15 hours, then cools to room temperature, disperseed with methanol solvate, filter, wash, it is dry,
Obtain polyamic acid (performed polymer)；
(2) polyamic acid is dissolved in organic solvent, then the film on clean substrate, then gradually drying, finally
It is dried 120 minutes at 200~300 DEG C, it is cooling, obtain Kapton.
On the other hand, the present invention provides a kind of fluorine-containing PI films having both high transparency and mechanical property, contain this hair
Bright fluorinated polyimide above-mentioned.
The Kapton of the present invention can be used for a variety of photoelectric devices in the market, include, but are not limited to photoelectron device
Part, solar cell device, flexible display device (such as OLED and LCD), e-book, electronic tag or photoelectric sensor.It is excellent
Selection of land, the photoelectric device are selected from solar cell device, flexible display device (such as OLED and LCD).This part phototube
Part is to the transparency and mechanical property requirements higher, it is necessary to while having both the balance of two kinds of performances.
It is not intended to limited to any theory, inventor has found, total with the height fragrance of traditional polyimide molecule main chain
In yoke and strand charge complexing transferance normally result in the transparency reduce it is different, when being introduced in polyimide molecule
When hexafluoro naphthalene structure, in conjunction with fluorine-containing bridged bond (OCF2And CF2O), preferable in the permeability of far ultraviolet and near infrared region light.With it is existing
Technology is compared, and the transparency is substantially in same level.At the same time, above structure further increases between polyimide molecule main chain
Interaction, to keep compared with high transparency while, have both excellent mechanical property；It is affine with other matrixes simultaneously
Property is preferable.With it is generally desirable to it is consistent, naphthalene ring causes polyimide molecule conjugate unit slightly to increase, inevitably
The transparency is caused to be slightly below full-fluorinated benzene ring structure；But this is balanced further through the specific selection of tetrabasic carboxylic acid dicarboxylic anhydride so that
The counterbalance effect of the transparency and mechanical property is more preferably.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after having read present disclosure, those skilled in the art
The present invention can be made various changes or modifications, such equivalent forms are equally fallen within defined by the application the appended claims
Range.
It will be helpful to understand the present invention by following embodiments, but cannot limit the scope of the invention.
Embodiment 1：Prepare the compound of formula (II)
(1) formula (III-1) compound of 35.4g (0.15mol) is added in 1L there-necked flasks, 500ml tetrahydrofurans install
Stirring, cryostat, dropwise addition and nitrogen protection device start stirring, are cooled to -80 DEG C under nitrogen protection, and 150ml butyl is added dropwise
Lithium solution (0.35mol) after being added dropwise, keeps -70 DEG C of 1h stirred below, then proceedes to that difluorodibromomethane solution is added dropwise
(containing 0.40mol difluorodibromomethanes) is kept for -70 DEG C hereinafter, be added dropwise, continues to stir 1h, then with 10% dilute salt
Acid is hydrolyzed, and then post-processes, and obtains sepia grease 45g, yield 61% is not required to be further processed, directly carry out down
Single step reaction.
(2) grease 40g, 500ml dimethylformamide made from addition step (1) in 1L there-necked flasks, 1g potassium iodide,
22.5g p-nitrophenols are heated to 105 DEG C, after reacting 4 hours, stop heating and ice water is added into reaction system after cooling,
It is precipitated to product, filtering after washing, is crystallized with ethyl alcohol, obtains yellow solid 24.2g, yield 48%, purity 98%.1H
NMR(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 value:C 47.23%, F
31.13%, N 4.59%, O 15.73%, measured value：C 47.56%, F 30.89%, N 4.52%, O 15.34%.
(3) step dinitro compound obtained, 150ml toluene, 100ml ethyl alcohol, 1g 5% on 20g are added in 1L autoclaves
Pd/C, normal temperature and pressure adds hydrogen 8 hours, by gas-chromatography monitor reaction it is qualified after, carry out the processing of next step, filter, it is dense
Contracting is used in combination 120ml isopropanols to crystallize, and obtains pink solid powder, 16.5g, gas chromatographic purity 99%, yield are obtained after dry
91%.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 value:C 52.38%, F 34.52%, N 5.06%, O 5.81%, measured value：C 52.47%, F
34.39%, N 5.15%, O 5.64%.
Embodiment 2：Prepare polyamic acid
In 500mL there-necked flasks, 3,3 ', 4, the 4 '-perfluors that the diamine compound 8g and 6.4g of embodiment 1 is added are different
Two phthalandione dianhydride of propylidene,
300g metacresols are heated to 190 DEG C, after reacting 8 hours, are cooled to 60 DEG C or so, reaction solution is divided under stiring
It is scattered in methanol, suction strainer after cooling is used in combination methanol to wash.It is dry, obtain 12.8g stringy solids.Number-average molecular weight Mn=10.5
×104, index=2.12 molecular weight distribution PDI.Molecular weight and molecular weight distribution are examined on PE Series 200GPC instrument
It surveys, polystyrene is standard specimen.
Embodiment 3：Prepare polyamic acid
It is identical according to mole dosage conversion with embodiment 2, but by 3,3 ', 4,4 '-perfluor isopropylidene, two phthalandione dianhydride
The 90%3,3 ' of molal quantity, 4,4 '-perfluor isopropylidene, two phthalandione dianhydride：The mixture of 10% cyclobutanetetracarboxylic dianhydride.Number
Average molecular weight Mn=9.7 × 104, index=2.05 molecular weight distribution PDI.
Embodiment 4：Prepare polyamic acid
It is identical according to mole dosage conversion with embodiment 2, but by 3,3 ', 4,4 '-perfluor isopropylidene, two phthalandione dianhydride
The 80%3,3 ' of molal quantity, 4,4 '-perfluor isopropylidene, two phthalandione dianhydride：The mixture of 20% cyclobutanetetracarboxylic dianhydride.Number
Average molecular weight Mn=9.4 × 104, index=1.99 molecular weight distribution PDI.
Embodiment 5：Prepare polyamic acid
It is identical according to mole dosage conversion with embodiment 2, but by 3,3 ', 4,4 '-perfluor isopropylidene, two phthalandione dianhydride
The 70%3,3 ' of molal quantity, 4,4 '-perfluor isopropylidene, two phthalandione dianhydride：The mixture of 30% cyclobutanetetracarboxylic dianhydride.Number
Average molecular weight Mn=8.1 × 104, index=2.36 molecular weight distribution PDI.
Application Example：Kapton and its performance
Stringy solids made from embodiment 2-5 are dissolved in 5% N-Methyl pyrrolidone, 5% solution is made into, are used
0.45 μm of filter membrane is filtered, to remove mechanical admixture.Then polymer solution is coated on clean glass substrate, 50 DEG C
Drying 1 hour, 100 DEG C 1 hour, it is last 200 DEG C dry 2 hours, be cooled to room temperature, demoulding, respectively be made thickness be about 20 μm
Transparent polyimide film, as the present invention apply
Embodiment 1-4.
Wherein, the optical transparence of above-mentioned Kapton and thermal stability respectively in UV- visible spectrophotometers and
It is measured on TGA/DSC synchronous solvings；The mechanical property of Kapton is tested on CMT-4104 type universal testing machines,
Sample is prepared according to above-mentioned same procedure, and size is 60 × 10 × 0.045mm3, test initial force is 5Kg, and rate of extension is
2mm/min, test result take 3 average values.
Using comparative example：Using comparative example：Respectively by the polyimides of Chinese patent application CN106674027A embodiments 3
Film carries out above-mentioned test according to the identical method of the present invention, respectively as using comparative example 1.
As a result referring to table 1.
Table 1
As can be seen from Table 1, when introducing hexafluoro naphthalene structure in polyimide molecule, in conjunction with fluorine-containing bridged bond, remote purple
Outer and near infrared region light permeability is preferable.Compared with application comparative example 1, the transparency is substantially in same level.At the same time, on
It states structure and further increases interaction between polyimide molecule main chain, it is simultaneous to while keeping compared with high transparency
Have excellent tensile strength and elongation at break；It is preferable with the compatibility of other matrixes simultaneously.In addition, passing through tetrabasic carboxylic acid dicarboxylic anhydride
Specific selection so that the transparency and mechanical property counterbalance effect more preferably.As use (80-90) %3,3 ', 4,4 '-perfluors are different
The mixture of two phthalandione dianhydride of propylidene and (20-10) % cyclobutanetetracarboxylic dianhydrides, 450nm transmitances reach 87% or more,
The requirement that most transparent membranes in the market can preferably be met, in addition, mechanical property can also obtain preferable balance.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., be all included in the scope of protection of the present invention.
Claims (10)
1. a kind of fluorinated polyimide, the fluorinated polyimide is obtained by polyamic acid dehydration closed-loop；It is characterized in that, described
Polyamic acid by formula (I) diamine compound
It is obtained by polycondensation reaction with tetrabasic carboxylic acid dicarboxylic anhydride.
2. fluorinated polyimide according to claim 1, wherein the tetrabasic carboxylic acid dicarboxylic anhydride is selected from aromatic tetracarboxylic acid two
Acid anhydrides；Or the combination selected from aromatic tetracarboxylic acid's dicarboxylic anhydride and Alicyclic tetracarboxylic acid dicarboxylic anhydride.
3. fluorinated polyimide according to claim 1, wherein aromatic tetracarboxylic acid's dicarboxylic anhydride is selected from 3,3 ', 4,
4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydrides, 4,4 '-two (3,4- di carboxyl phenyloxies) diphenylsulfide dicarboxylic anhydrides, 3,3 ', 4,4 '-
Diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8- naphthalene tetracarboxylic acids dicarboxylic anhydride, 2,3,6,7- naphthalene tetracarboxylic acids dicarboxylic anhydride, 3,3 ', 4,4 '-
It is one or more in two phthalandione dianhydride of perfluor isopropylidene, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydrides；
The Alicyclic tetracarboxylic acid dicarboxylic anhydride is selected from 1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, 1,2- dimethyl -1,2,3,4-
Cyclobutane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, tetramethyl -1,2 1,2,3,4-,
3,4- cyclobutane tetrabasic carboxylic acids dicarboxylic anhydride, 1,2,3,4- pentamethylene tetrabasic carboxylic acids dicarboxylic anhydride, 1,2,4,5- cyclopentanetetracarboxylics dicarboxylic anhydride,
It is one or more in 1,2,4,5- norbornane tetrabasic carboxylic acid dicarboxylic anhydrides.
4. fluorinated polyimide according to claim 2 or 3, wherein aromatic tetracarboxylic acid's dicarboxylic anhydride is selected from 3,3 ',
4,4 '-perfluor isopropylidene, two phthalandione dianhydride；The Alicyclic tetracarboxylic acid dicarboxylic anhydride is selected from 1,2,3,4- cyclobutane tetrabasic carboxylic acid two
It is one or more in acid anhydrides, 1,2,3,4- pentamethylene tetrabasic carboxylic acid dicarboxylic anhydrides.
5. fluorinated polyimide according to claim 4, wherein aromatic tetracarboxylic acid's dicarboxylic anhydride with it is described alicyclic
The molar ratio of tetrabasic carboxylic acid dicarboxylic anhydride is 0.75~0.99；Preferably 0.78~0.95；More preferably 0.80~0.90.
6. fluorinated polyimide according to claim 1, wherein shown in the structural formula of the polyamic acid such as formula (II)：
Wherein, R is originated from the quadrivalent organic radical of the tetrabasic carboxylic acid dicarboxylic anhydride；Polymerization degree n 5 to 500, preferably 8 to 300, more preferably
10 to 200, in the range of further 15 to 150, most preferably 20 to 120.
7. fluorinated polyimide according to claim 6, wherein the number-average molecular weight Mn of the polyamic acid 2.0~
15.0×104, preferably 4.0~13.0 × 104, more preferable 6.0~12.0 × 104, most preferably, 7.0~11.0 × 104Dalton
In the range of.
8. fluorinated polyimide according to claim 1, wherein the dehydration closed-loop step is：Polyamic acid is dissolved
In organic solvent, the film on cleaning substrate, then gradually drying, is finally dried, cooling, obtains polyimides.
9. a kind of fluorine-containing PI films having both high transparency and mechanical property, which is characterized in that contain any one of claim 1-8
The fluorinated polyimide.
10. the application of fluorine-containing PI films in the opto-electronic device described in claim 9；Preferably, the photoelectric device is selected from too
Positive energy battery device, flexible display device.
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| CN111808284A (en) * | 2020-07-03 | 2020-10-23 | 株洲时代新材料科技股份有限公司 | Polyamide acid, polyamide acid resin, heat-resistant transparent polyimide and preparation method |
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