CN115232309B - Polyimide, preparation method thereof, polyimide film and application - Google Patents
Polyimide, preparation method thereof, polyimide film and application Download PDFInfo
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- CN115232309B CN115232309B CN202210920113.8A CN202210920113A CN115232309B CN 115232309 B CN115232309 B CN 115232309B CN 202210920113 A CN202210920113 A CN 202210920113A CN 115232309 B CN115232309 B CN 115232309B
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- polyimide
- dianhydride
- compound
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- conh
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 152
- 239000004642 Polyimide Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000000758 substrate Substances 0.000 claims abstract description 16
- -1 diamine compound Chemical class 0.000 claims description 110
- 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 34
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 30
- 150000004985 diamines Chemical class 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 20
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 11
- 125000000732 arylene group Chemical group 0.000 claims description 10
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 125000006763 (C3-C9) cycloalkyl group Chemical group 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 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
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 125000006159 dianhydride group Chemical group 0.000 claims description 3
- 125000001475 halogen functional group Chemical group 0.000 claims 2
- 238000002834 transmittance Methods 0.000 abstract description 8
- 239000002346 layers by function Substances 0.000 abstract description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 125000000753 cycloalkyl group Chemical group 0.000 description 20
- 239000011521 glass Substances 0.000 description 18
- 229920005575 poly(amic acid) Polymers 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 230000009477 glass transition Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000010408 film Substances 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 9
- 239000009719 polyimide resin Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 125000004979 cyclopentylene group Chemical group 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 2
- 239000012024 dehydrating agents Substances 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
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- XLOGCGOPKPCECW-UHFFFAOYSA-N 1719-83-1 Chemical compound C1=CC2C3C(=O)OC(=O)C3C1C1C(=O)OC(=O)C21 XLOGCGOPKPCECW-UHFFFAOYSA-N 0.000 description 1
- 229940075142 2,5-diaminotoluene Drugs 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- MSDFJCWRZDPWQP-UHFFFAOYSA-N 2-[methyl(phenyl)silyl]propanedioic acid Chemical compound C(=O)(O)C([SiH](C)C1=CC=CC=C1)C(=O)O MSDFJCWRZDPWQP-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 description 1
- AASJYPLKPXYUJL-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenoxy)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=CC=CC=2)OC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O AASJYPLKPXYUJL-UHFFFAOYSA-N 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 1
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 1
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 108010053481 Antifreeze Proteins Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004976 cyclobutylene group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004977 cycloheptylene group Chemical group 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000005725 cyclohexenylene group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 125000004431 deuterium atom Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005067 haloformyl group Chemical group 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000005560 phenanthrenylene group Chemical group 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 125000006684 polyhaloalkyl group Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 125000004385 trihaloalkyl group Chemical group 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention relates to a polyimide comprising structural unitsSelected from the group consisting ofR 1 is-CONH-, R 2 And R is 3 At least one of them is-CONH-, R 4 、R 5 And R is 6 At least one of them is-CONH-. Y is Y 2 Selected from any one of the formulas (I), (II) and (III). The invention also relates to a polyimide film which has high light transmittance, good heat resistance, low thermal expansion coefficient, higher strength and difficult breakage, and can be used for preparing a functional layer of a flexible display screen or a substrate independently used as the functional layer.
Description
Technical Field
The invention relates to the field of polymer synthesis, in particular to polyimide, a preparation method thereof, a polyimide film and application.
Background
With the rapid development of OLED display technology, polymer films have gradually become substrates in OLED devices instead of hard glass. Currently, there are three main light emitting modes of OLED, including top emission, bottom emission and double-sided emission, in which for a bottom emission (bottom-emission) OLED device, the substrate must be a colorless transparent polymer film to ensure light to exit from the TFT array substrate side of the anode, so it is important to ensure good optical transparency of the substrate.
Polyimide (PI) is widely used as a flexible substrate in the field of optoelectronics due to its excellent heat resistance, and currently, a method of improving its optical transparency includes: (1) introducing an alicyclic structure; (2) introducing a pendent group with a large steric hindrance effect; (3) introducing a flexible linking group. Most polyimide films prepared based on the above method can improve optical transmittance, but can result in lower glass transition temperature (lower than 350 ℃), higher CTE value (such as higher than 30ppm K-1), unsuitable for thermal processing, weaker substrate strength, chipping, curling or peeling due to mismatch of CTE values between PI and inorganic or metal layers during high temperature processing, and volatile substances generated by thermal decomposition of PI substrate at high temperature pollute OLED device, thereby affecting service life.
Based on this, it is necessary to provide a polyimide film having a low thermal expansion coefficient, high strength and sufficient optical transparency.
Disclosure of Invention
The object of the present invention is to provide a polyimide which can produce a polyimide film having a low thermal expansion coefficient, a high strength and a high optical transparency.
A first aspect of the present invention provides a polyimide comprising structural units
wherein ,
selected from any one of the following structures:
R 1 is-CONH-;
R 2 、R 3 、R 4 、R 5 and R6 Each independently selected from: single bond, -O-, -S-, -SO 2 -, -CONH-, -COO-or-Si (CH) 3 ) 2 OSi(CH 3 ) 2 -, and R 2 and R3 At least one of them is-CONH-, R 4 、R 5 and R6 At least one of them is-CONH-;
R 11 、R 12 、R 13 、R 14 、R 15 and R16 Each independently selected from: H. halo, ester, C1-C9 alkyl, C1-C9 haloalkyl or C3-C9 cycloalkyl;
A 1 、A 2 and A3 Each independently selected from: a substituted or unsubstituted C6-C10 arylene group, or a substituted or unsubstituted C1-C5 cycloalkylene group;
*-Y 2 any one selected from the structures shown in the following general formula:
R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 、R 31 、R 32 、R 41 and R42 Each independently selected from: H. halo, ester, C1-C9 alkyl, C1-C9 fluoroalkyl or C3-C9 cycloalkyl;
R 7 、R 8 、R 9 and R10 Independently selected from: -O-, -SO 2 -、-COO-、-CONH-、-C(CH 3 ) 2 -、-C(CF 3 ) 2 -、-Si(CH 3 ) 2 -or-Si (CH) 3 ) 2 OSi(CH 3 ) 2 -；
-X-is selected from-O-, -S-.
In some embodiments of the invention, in the polyimide, R 25 、R 26 、R 31 and R32 Each independently is a C1-C9 fluoroalkyl group.
In some embodiments of the invention, in the polyimide, R 2 、R 3 、R 4 、R 5 and R6 Each independently is-CONH-.
In some embodiments of the invention, X is selected from-O-or-S-.
In some embodiments of the invention, in the polyimide, R 11 、R 12 、R 13 、R 14 、R 15 and R16 Each independently is H.
In some embodiments of the invention, in the polyimide, a 1 、A 2 and A3 Each independently selected from: phenylene or cyclopentylene.
In some embodiments of the invention, the polyimide has the formula in each moleculeThe number of the structural units is 3-3000.
The second aspect of the present invention provides a method for producing polyimide, comprising the steps of: adding a diamine compound I and a dianhydride compound I, optionally adding a dianhydride compound II, optionally adding a diamine compound II into an organic solvent I, mixing, and carrying out polymerization reaction to obtain polyamide acid I;
carrying out dehydration reaction on the polyamide acid I to obtain polyimide I;
wherein the polyimide i is as defined in the first aspect of the invention.
In some embodiments of the present invention, in the method for preparing polyimide, the organic solvent i is one or more selected from N-methylpyrrolidone, dimethylacetamide and N-methyl-2-pyrrolidone; and/or the number of the groups of groups,
the structure of the diamine compound II comprises one or more of the following: -O-, -SO 2 -, fluoro, trifluoromethyl, cycloalkyl.
In some embodiments of the present invention, in the method for producing polyimide, the molar ratio of the diamine compound i to the diamine compound ii is 10: (0-50);
The molar ratio of the dianhydride compound I to the dianhydride compound II is 10: (0-50).
A third aspect of the invention provides a polyimide composition comprising a filler and a polyimide, the polyimide being as defined in the first aspect of the invention.
A fourth aspect of the present invention provides a polyimide film comprising the polyimide of the first aspect of the present invention, or the polyimide produced by the production process of the second aspect of the present invention, or a polyimide composition comprising the third aspect of the present invention; preferably, the polyimide film has a thickness of 10 to 250 μm.
In a fifth aspect of the present invention, there is provided an application of the polyimide film of the fourth aspect of the present invention in preparing an OLED substrate, a cover plate or a touch pad.
Polyimide has high light transmittance but is limited by its own structure, and is generally very dark in color, and thus is not suitable for the photoelectric field. The current method for obtaining colorless polyimide mainly comprises the steps of improving the structure of polyimide, reducing charge transfer in molecules or among molecules, and preparing colorless transparent polyimide (CPI) with low yellow index, but the glass transition temperature performance is weakened, so that the polyimide is not suitable for thermal processing, the thermal expansion coefficient is higher, cracking, curling or stripping are generated due to mismatch of CTE values between PI and an inorganic or metal layer during high-temperature processing, and volatile substances generated by thermal decomposition of a PI substrate at high temperature pollute OLED (organic light emitting diode) devices, so that the service life is influenced.
The polyimide molecule of the application contains-CONH-and Cardo fluorenyl structures, and the amide bond can lead the molecular chains to form hydrogen bonds, thereby forming a hydrogen bond cross-linked network, promoting the in-plane orientation of the molecular chains and enhancing the interaction force between the molecular chains, thereby reducing the thermal expansion coefficient, improving the glass transition temperature and simultaneously retaining the transparency of the polyimide; the Cardo fluorenyl with large steric hindrance effect can increase the rotational kinetic energy of polyimide molecular chains, limit chain segment movement, greatly improve the glass transition temperature and simultaneously maintain the transparency of polyimide.
The polyimide film prepared by the polyimide has high optical transparency, excellent heat resistance, low thermal expansion coefficient and high glass transition temperature, and also has certain flexibility, strength and bending resistance, and can be used for preparing the substrate of the OLED display screen.
Detailed Description
The application is further illustrated below in conjunction with the embodiments and examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it is to be understood that various changes and modifications may be made by one skilled in the art after reading the teachings of the application, and such equivalents are intended to fall within the scope of the appended claims.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
the term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other. It should be noted that, when at least three items are connected by at least two conjunctions selected from the group consisting of "and/or", "and/or", it is to be understood that, in the present application, the technical solutions certainly include technical solutions that all use "logical and" connection, and also certainly include technical solutions that all use "logical or" connection. For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
Herein, "preferred", "better", etc. are merely embodiments or examples that describe better results, and it should be understood that they do not limit the scope of the invention.
In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.
In the present invention, the terms "first", "second", "third", "fourth", "fifth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of the indicated technical features. Also, "first," "second," "third," "fourth," "fifth," etc. are for non-exhaustive list of descriptive purposes only and are not to be construed as limiting the number of closed forms.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, a numerical range (i.e., a numerical range) is referred to, and optional numerical distributions are considered to be continuous within the numerical range and include two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range and each numerical value between the two numerical endpoints unless otherwise specified. When a numerical range merely points to integers within the numerical range, both end integers of the numerical range are included, as well as each integer between the two ends, unless expressly stated otherwise. Further, when a plurality of range description features or characteristics are provided, these ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
In the present invention, the number of atoms described by a numerical range includes both the end points of the numerical range and also includes each integer of the two end points. For example, "C1-C9 alkyl" means an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, or 9 carbon atoms.
In the present invention, "×" indicates a ligation site.
Herein, cardo fluorenyl structure refers toThe fused structures shown include derivatives having the same parent nucleus, such as analogs having one or more substituents on the aromatic ring a or B or C or D. The A and B rings may also be further condensed, such as by a single bond or a divalent bond such as-O-, -S-or the like.
In the present invention, -CONH-, andhas the same meaning and can be used interchangeably; -SO 2- and />Has the same meaning and can be used interchangeably; ester bond, -COO-and->Has the same meaning and can be used interchangeably；-Si(CH 3 ) 2 OSi(CH 3 ) 2- and />Has the same meaning and can be used interchangeably.
Herein, "halogen" or "halo" refers to F, cl, br or I.
Herein, the term "alkyl" refers to a monovalent residue of a saturated hydrocarbon containing a primary (positive) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof, losing one hydrogen atom. Phrases containing this term, e.g., "C 1 ～ 9 Alkyl "means an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be, independently of the other, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, C 7 Alkyl, C 8 Alkyl or C 9 An alkyl group. Suitable examples include, but are not limited to: methyl (Me, -CH) 3 ) Ethyl (Et, -CH) 2 CH 3 ) 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH 3 ) 2-propyl (i-Pr, i-propyl, -CH (CH) 3 ) 2 ) 1-butyl (n-Bu, n-butyl, -CH) 2 CH 2 CH 2 CH 3 ) 2-methyl-1-propyl (i-Bu, i-butyl, -CH) 2 CH(CH 3 ) 2 ) 2-butyl (s-Bu, s-butyl, -CH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH) 3 ) 3 ) 1-pentyl (n-pentyl, -CH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH 3) CH2CH2CH 3), 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) 1-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-hexyl (-CH (CH) 3 )CH 2 CH 2 CH 2 CH 3 ) 3-hexyl (-CH (CH) 2 CH 3 )(CH 2 CH 2 CH 3 ) 2-methyl-2-pentyl (-C (CH) 3 ) 2 CH 2 CH 2 CH 3 ) 3-methyl-2-pentyl (-CH (CH) 3 )CH(CH 3 )CH 2 CH 3 ) 4-methyl-2-pentyl (-CH (CH) 3 )CH 2 CH(CH 3 ) 2 ) 3-methyl-3-pentyl (-C (CH) 3 )(CH 2 CH 3 ) 2 ) 2-methyl-3-pentyl (-CH (CH) 2 CH 3 )CH(CH 3 ) 2 ) 2, 3-dimethyl-2-butyl (-C (CH) 3 ) 2 CH(CH 3 ) 2 ) 3, 3-dimethyl-2-butyl (-CH (CH) 3 )C(CH 3 ) 3 And octyl (- (CH) 2 ) 7 CH 3 )。
Herein, "haloalkyl" refers to an alkyl group substituted with one or more halogen (chlorine, fluorine, bromine, or iodine) atoms. Polyhaloalkyl groups have the same or mixed types of halogen atoms. "perhaloalkyl" means that each hydrogen atom in the alkyl group is replaced with a halogen atom. A haloalkyl group "fully halogenated" with respect to a particular carbon atom means that all of the hydrogen atoms attached to that carbon atom are replaced with halogen atoms. Representative mono-, di-and tri-haloalkyl groups include: chloromethyl, chloroethyl, bromomethyl, bromoethyl, iodomethyl, iodoethyl, chloropropyl, bromopropyl, iodopropyl, 1-dichloromethyl, 1-dibromomethyl, 1-dichloropropyl, 1, 2-dibromopropyl, 2, 3-dibromopropyl, 1-chloro-2-bromoethyl, 2-chloro-3-bromopropyl, trifluoromethyl, trichloromethyl, and the like.
As used herein, "cycloalkyl" refers to a non-aromatic hydrocarbon containing ring carbon atoms, which may be a monocycloalkyl, or spirocycloalkyl, or bridged cycloalkyl. The phrase containing the term, for example, "C3-C9 cycloalkyl" refers to cycloalkyl groups containing 3 to 9 carbon atoms, which at each occurrence may be, independently of one another, C3 cycloalkyl, C4 cycloalkyl, C5 cycloalkyl, C6 cycloalkyl, C7 cycloalkyl, C8 cycloalkyl or C9 cycloalkyl. Suitable examples include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. In addition, "cycloalkyl" may also contain one or more double bonds, and representative examples of cycloalkyl groups containing a double bond include cyclopentenyl, cyclohexenyl, cyclohexadienyl, and cyclobutenyl.
As used herein, the term "arylene" refers to an aromatic hydrocarbon radical derived from the removal of two hydrogen atoms on the basis of an aromatic ring compound, which may be a monocyclic arylene radical, or a fused-ring arylene radical, or a polycyclic arylene radical, at least one of which is an aromatic ring system for a polycyclic species. For example, "C 6 ～C 10 Arylene "means arylene groups containing 6 to 10 carbon atoms, each occurrence of which may be independently of one another C 6 Arylene group, C 7 Arylene group, C 8 Arylene group, C 9 Arylene or C 10 Arylene groups. Suitable examples include, but are not limited to: phenylene, biphenylene, naphthylene, anthracenylene, phenanthrenylene, perylene, triphenylene and derivatives thereof.
Herein, the term "cycloalkylene" refers to a hydrocarbon group derived by removing two hydrogen atoms on the basis of a cycloalkyl group to form a center having two monovalent groups, which may be a monocycloalkylene group, or a spirocycloalkylene group, or a bridged cycloalkyl group. For example, "C3-C9 cycloalkylene" refers to cycloalkylene groups containing 3-9 carbon atoms, and each occurrence may be, independently of the other, C3 cycloalkylene, C4 cycloalkylene, C5 cycloalkylene, C6 cycloalkylene, C7 cycloalkylene, C8 cycloalkylene, or C9 cycloalkylene. Suitable examples include, but are not limited to: cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene and cycloheptylene. In addition, the "cycloalkylene group" may also contain one or more double bonds, and representative examples of the cycloalkylene group containing double bonds include cyclopentylene group, cyclohexenylene group, cyclohexadienylene group, and cyclobutenylene group.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood that the defined group may be substituted with one or more substituents R selected from, but not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 9C atoms, cycloalkyl containing 3 to 9C atoms, -NR' R ", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, and which may be further substituted with substituents acceptable in the art; it is understood that R 'and R "in-NR' R" are each independently selected from, but not limited to: H. deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 9C atoms, cycloalkyl groups containing 3 to 9C atoms.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
In the present invention, the weight may be a mass unit known in the chemical industry field such as mu g, mg, g, kg.
Substrates for optoelectronic devices often need to have colorless transparent properties, and, to accommodate production processing temperatures, the polymeric material needs to have high heat resistance (T g >380 c) and also has excellent thermal dimensional stability (CTE) in order to prevent the device from peeling, warping, and even chipping due to thermal stress generated at the interface of the thin film and the inorganic material at high temperature<15ppm K -1 @50-300 ℃). The substrate prepared from polyimide has better transparency and is widely applied, but polyimide is limited by the structural characteristics of polyimide, a colored film is often formed to limit the application, and the partially improved polyimide has the problem that the glass transition temperature and the thermal expansion coefficient cannot be combined.
The inventors speculate that this is mainly the current contradiction to polyimide improvement:
For example, a method for increasing the glass transition temperature (Tg) of polyimide mainly includes: (1) Rigid aromatic heterocycle (imidazole, oxazole, pyridine, thiazole and the like) or side group with large steric hindrance effect (spiro, fluorenyl Cardo structure and the like) is introduced into the molecular chain; (2) A group capable of constructing hydrogen bonds, such as imidazole, amide and the like, is introduced into the molecular chain; (3) introducing a crosslinked structure into the molecular chain. PI films obtained based on the above method have excellent heat resistance, but these films tend to have extremely dark colors.
The structural unit of the polyimide molecular chain is regulated and controlled to reduce the absorption of the PI film to the blue-violet light in the visible light region, so that colorless transparent polyimide (CPI) with high light transmittance and low yellow index is prepared, but the action force among polyimide molecular chains is weakened, the glass transition performance is reduced, and the thermal expansion coefficient is obviously increased.
The introduction of rigid rod-like structures in the molecular chains or hydrogen bonding between the molecular chains can reduce the Coefficient of Thermal Expansion (CTE), but tends to cause the CPI film to lose optical transparency.
Thus, the current preparation of colorless transparent, high heat resistant (Tg >380 ℃) polyimide films with low coefficients of thermal expansion (CTE <15 ppmK-1) remains a technical difficulty.
The polyimide disclosed by the invention has the advantages of good heat resistance, low thermal expansion coefficient, high glass transition temperature, no color and transparency, capability of preparing a colorless polyamide film with high optical transparency, proper flexibility and strength, and capability of being used for preparing a flexible display screen of an OLED (organic light emitting diode).
A first aspect of the present invention provides a polyimide comprising structural units
In some embodiments, the polyimide comprises 3 to 3000 formulasThe structural units shown.
In some preferred embodiments, the polyimide molecules comprise formula (I)The number of structural units shown can be selected from 3 to 200, 200 to 800, 500 to 1000, 800 to 2000, 1500 to 3000, 2000 to 3000 or 2000 to 3000.
In some embodiments, the polyimide has a viscosity of 10000 to 50000CPs, and in some embodiments, the polyimide is a viscous colorless transparent liquid with good flowability.
In some embodiments of the present invention, in some embodiments,selected from any one of the following structures:
preferably, the method comprises the steps of,selected from->
In some embodiments, R 1 is-CONH-.
In some embodiments, R 2 、R 3 、R 4 、R 5 and R6 Each independently selected from: single bond, -O-, -S-, -SO 2 -, -CONH-, -COO-or-Si (CH) 3 ) 2 OSi(CH 3 ) 2 -, and R 2 and R3 At least one of them is-CONH-, R 4 、R 5 and R6 At least one of them is-CONH-.
In some embodiments, R 2 、R 3 、R 4 、R 5 and R6 Each independently is-CONH-.
In some embodiments, R 11 、R 12 、R 13 、R 14 、R 15 and R16 Each independently selected from: -H, halo, ester, C1-C9 alkyl, C1-C9 haloalkyl or C3-C9 cycloalkyl.
In some embodiments, a 1 、A 2 and A3 Each independently selected from: a substituted or unsubstituted C6-C10 arylene group, or a substituted or unsubstituted C3-C9 cycloalkylene group.
In some embodiments of the invention, A 1 、A 2 and A3 Each independently selected from: phenylene or cyclopentylene.
In some embodiments of the present invention, in some embodiments,selected from->Further, is selected from the following structures
In some embodiments of the present invention, in some embodiments,selected from->Further, any one selected from the following structures:
in some embodiments, -Y 2 -any one selected from the following structures:
in some embodiments, R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 、R 28 、R 29 、R 30 、R 31 、R 32 、R 41 and R42 Each independently selected from: -H, halo, ester, C1-to-upC9 alkyl, C1-C9 fluoroalkyl or C3-C9 cycloalkyl.
In some embodiments, R 25 、R 26 、R 31 and R32 Each independently is a C1-C9 fluoroalkyl group. Preferably, it is-CF 3 。
In some embodiments, R 7 、R 8 、R 9 and R10 Independently selected from: -O-, -SO 2 -、-COO-、-CONH-、-C(CH 3 ) 2 -、-C(CF 3 ) 2 -、-Si(CH 3 ) 2 -or-Si (CH) 3 ) 2 OSi(CH 3 ) 2 -。
In some embodiments, X is selected from the group consisting of-O-, -S-, -CH 2 -an alike group.
In some embodiments, X is selected from-O-or-S-. preferably-O-.
In some embodiments, -Y 2 Selected fromFurther, is selected from-> Further preferred R 41 and R42 Each independently selected from H or halogen.
In some embodiments, -Y 2 Selected fromFurther, is selected from->
In some embodiments, R 21 and R22 Independently selected from C1-C9 fluoroalkyl groups, further selected from-CF 3 。
In some embodiments, R 23 and R24 Each independently selected from H.
In some embodiments, R 25 and R26 Each independently selected from H.
In some embodiments, X is-O-.
In some embodiments, -Y 2 Selected fromFurther, is selected from->
In some embodiments, R 27 and R28 Independently selected from C1-C9 fluoroalkyl groups, further selected from-CF 3 。
In some embodiments, R 29 and R30 Independently selected from H or C1-C9 fluoroalkyl, further from H or-CF 3 。
In some embodiments, R 31 and R32 Each independently selected from H.
Second aspect of the invention
In a second aspect, the present invention provides a method for producing a polyimide. The raw dianhydride and raw diamine of the polyimide of the present invention include-CONH-and Cardo fluorenyl structures. The introduction of the-CONH-can lead the molecular chains to form hydrogen bonds, so as to form a hydrogen bond cross-linked network, promote the in-plane orientation of the molecular chains and enhance the interaction force between the molecular chains, thereby reducing the thermal expansion coefficient, improving the glass transition temperature and simultaneously keeping the transparency of polyimide; the introduction of the Cardo fluorenyl structure with large steric hindrance effect is beneficial to increasing the rotation function of polyimide molecular chains, limiting chain segment movement, greatly improving the glass transition temperature and simultaneously retaining the transparency of polyimide.
In some embodiments of the present invention, a method for preparing polyimide comprises the following preparation steps:
s100: adding monomer diamine and monomer dianhydride into organic solvent, mixing and polymerizing to obtain polyamic acid.
S200: and (3) carrying out dehydration reaction on the polyamide acid to obtain polyimide.
S100: preparation of Polyamic acid
S100: adding monomer diamine (diamine compound I) and monomer dianhydride (dianhydride compound I) into an organic solvent (organic solvent I), mixing and carrying out polymerization reaction to obtain polyamide acid I.
In some embodiments, diamine compound i has a Cardo fluorenyl structure.
In some embodiments, diamine compound i is selected from any one of the following structures:
/>
in some embodiments, dianhydride compound I has a-CONH-structure.
In some embodiments, dianhydride compound i is selected from any of the following structures:
in some embodiments, the organic solvent i is selected from one or more of N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, m-cresol, N-methylcaprolactam, sulfolane, dimethylsulfoxide (DMSO), cyclohexanone, hexamethylphosphoramide, and gamma-butyrolactone. In addition, even a solvent in which polyamic acid is not dissolved may be added to the above solvent within the range where a homogeneous solution is obtained. In some embodiments, the organic solvent I is selected from one or more of N-methylpyrrolidone, dimethylacetamide and N-methyl-2-pyrrolidone.
In some embodiments, after the diamine compound I and the dianhydride compound I are added to the organic solvent (organic solvent I), another dianhydride compound (dianhydride compound II) may be optionally added.
In some embodiments, dianhydride compound ii is selected from any one of (4-phthalic anhydride) formyloxy-4-phthalate, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, hexafluorodianhydride, and biphenyl dianhydride. In some preferred embodiments, dianhydride compound II is selected from hexafluorodianhydride or phthalic anhydride.
In some embodiments, dianhydride compound ii is selected from any of the following structures:
in some embodiments, the molar ratio of dianhydride compound i to dianhydride compound ii is 10: (0 to 50) to obtain a high transparency, a high glass transition temperature and a low thermal expansion coefficient, and more preferably, 10: (2-40).
In some embodiments, after the diamine compound I and the dianhydride compound I are added to the organic solvent (organic solvent I), another diamine compound (diamine compound II) may be optionally added.
In some embodiments, the structure of diamine compound ii comprises one or more of the following: -O-, -SO 2 -, fluoro, trifluoromethyl, cycloalkyl. In the invention, cycloalkyl in the diamine compound II refers to a carbocycle substituent group formed by connecting 3 or more carbon atoms, wherein a single bond, a double bond or a triple bond can be arranged between two adjacent carbon atoms in a ring, and the number of the rings can be one or more. Preferably, C3-C9 saturated carbocycles are meant. Cycloalkyl groups may be monosubstituted, for example:etc., and may also be a linker, two or more attachment sites being drawn from the same or different rings, such as, for example:
in some embodiments, diamine compound ii is selected from any one of the following structures:
in some embodiments, the molar ratio of dianhydride compound i to dianhydride compound ii is 10: (0 to 50) to obtain a high transparency, a high glass transition temperature and a low thermal expansion coefficient, and more preferably, 10: (2-40).
In some embodiments, the dianhydride compound II, and optionally a third dianhydride (dianhydride compound III) may be added after the diamine compound I and dianhydride compound I are added to the organic solvent (organic solvent I). In some embodiments, dianhydride compound III is added in an amount of no more than 10% of the total dianhydride molar amount.
In some embodiments, after the diamine compound I and the dianhydride compound I are added to the organic solvent (organic solvent I), the diamine compound II, optionally, a third diamine (diamine compound III) may be added to further improve heat resistance. In some embodiments, diamine compound III is added in an amount of no more than 10% of the total diamine molar amount.
In some embodiments, dianhydride compound III is selected from any of 4- (2, 5-dioxatetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid dianhydride, bis (dicarboxyphenyl dimethyl) silane dianhydride, bis (dicarboxybenzoic acid) hydroquinone ester dianhydride, bis (dicarboxyphenoxy) benzene dianhydride, bis (dicarboxyphenoxy diphenyl) sulfide dianhydride, isopropylidene diphenoxy diphthalic anhydride, bicyclo [2.2.2] -7-octene-2, 3,5, 6-tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, and cyclohexane tetracarboxylic dianhydride.
In some embodiments of the present invention, in some embodiments, the diamine compound III is selected from p-phenylenediamine, m-phenylenediamine, 2, 5-diaminotoluene, 2, 6-diaminotoluene, 4-aminobenzoic acid (4-aminophenol) ester, 1, 3-bis (4, 4 '-aminophenoxy) benzene, 4' -diamino-1, 5-phenoxypentane 3,3 '-dimethyl-4, 4' -benzidine, 3 '-dimethoxy-4, 4' -benzidine, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenyl methane, 2' -diaminodiphenyl propane, bis (3, 5-diethyl-4-aminophenyl) methane, and one of 4,4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) diphenyl sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2' -diaminodiphenyl propane, 1, 4-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-cyclohexanediamine, 4 '-diaminodicyclohexylmethane and 4,4' -methylenebis (2-methylcyclohexylamine).
The method for producing the polyamic acid of the present invention is not particularly limited, and can be referred to methods conventionally used in the art. For example, a conventional polyimide is known from the conventional method for producing a polyimide by solution polymerization of a monomer dianhydride (dianhydride compound I, dianhydride compound II, dianhydride compound III) and a monomer diamine (such as diamine compound I, diamine compound II, diamine compound III). The method of mixing the monomeric dianhydride with the monomeric diamine in the organic solvent and reacting the mixture may be easily carried out. For example, a diamine may be prepared by dissolving or dispersing a diamine in an organic solvent in a slurry form to prepare a diamine solution, and adding a dianhydride to the diamine solution. The tetracarboxylic dianhydride may be added in a solid state or may be dissolved or dispersed in an organic solvent in a slurry state.
In the present invention, in the step of preparing the polyamic acid (in step S100), the temperature of the polymerization reaction is not particularly limited. The reaction temperature is preferably 80℃or less from the viewpoint of suppressing the decrease in molecular weight of the polyamic acid due to depolymerization. The reaction temperature is more preferably 0 to 50℃from the viewpoint of properly conducting the polymerization reaction. The reaction time may be arbitrarily set within a range of 10 minutes to 30 hours.
In the present invention, the molecular weight of the polyamic acid can be controlled by changing the molar ratio of the sum of all dianhydrides to the sum of all diamines in the polymerized monomer in the reaction, such as a usual polycondensation reaction, and the ratio of the sum of all dianhydrides to the sum of all diamines in the polymerized monomer is 100 (95 to 105), preferably the molar ratio is close to 100:100, and the molecular weight of the polyamic acid obtained becomes larger.
S200: preparation of polyimide
In some embodiments, polyamic acid I (produced in step S100) is subjected to a dehydration reaction to produce polyimide I.
In some embodiments, polyimide i of step S200 is as defined in the first aspect of the invention.
In some embodiments, the manner in which the dehydration reaction is performed is not particularly limited, and may be, for example, a heating method or a chemical method. In some embodiments, the heating process to effect dehydration reaction comprises the steps of: the polyamic acid was gradually heated from 80℃to 400℃and the polyamic acid was intramolecular dehydrated and cyclized to form a polyimide.
In some embodiments, chemically performing the dehydration reaction comprises the steps of: and adding a chemical dehydrating agent to dehydrate the polyamide acid. In some embodiments, the dehydrating agent may be selected from acetic anhydride. The dehydration reaction by the chemical method may be performed in the presence of a catalyst. In some embodiments, the catalyst may be selected from organic bases such as pyridine or triethylamine. In some embodiments, the step of chemically conducting the dehydration reaction may be at a reaction temperature selected from any of-20 ℃ to 200 ℃.
In some embodiments, in step S200, the polyamic acid i is subjected to a dehydration reaction, and the polymerization solution of the polyamic acid may be used without change, or may be diluted. The polyimide-containing solution thus obtained may be used, or may be used by: the polymer is precipitated using a solvent such as methanol or ethanol and then isolated in the form of a powder, or the resulting powder is redissolved in a suitable solvent prior to use. The solvent for redissolving is not particularly limited as long as the resulting polymer can be dissolved, and examples thereof may include m-cresol, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, cyclohexanone and γ -butyrolactone.
Third aspect of the invention
In a third aspect of the present invention, there is provided a polyimide composition, wherein the amide group of the polyimide of the present invention can form a hydrogen bond with a group containing an active hydrogen (hydroxyl group, amino group, carboxyl group, etc.) in the filler, thereby enhancing the compatibility of the polyimide with the filler and improving the film properties (e.g., heat resistance, mechanical properties, etc.).
In some embodiments, the polyimide composition includes a filler. In some embodiments, the filler may be selected from one or more of silica, tetraalkoxysilane, polysiloxane, silicone surfactant, silicone coupling agent.
In some embodiments, the filler may be selected from one or more of nanosilica, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, polyether siloxane, and polyphenyl silsesquioxane.
In some embodiments, the filler is present in an amount of 0.01 to 30 parts by weight, preferably 0.1 to 15 parts by weight, per 100 parts by weight of the polyamic acid.
Fourth aspect of the invention
The fourth aspect of the invention provides a polyimide film which is colorless, high in light transmittance, excellent in heat resistance, flexible, not easy to break, and capable of directly forming a functional layer necessary for flexible display, for example, being used for preparing an OLED display screen; depending on the thickness, it is also possible to form self-supporting film materials of different strength (relative to the type of film material depending on the support) and to display the necessary functional layers in terms of surface-processing flexibility.
In some embodiments, the polyimide film comprises a polyamic acid according to the first aspect of the invention, or comprises a polyamic acid prepared by the method of preparation according to the second aspect of the invention, or comprises a polyamic acid composition according to the third aspect of the invention.
In some embodiments, the polyimide film is prepared by the steps comprising: the polyamic acid is cast on a support and then subjected to a dehydration reaction to produce a polyimide film.
In some embodiments, the polyimide film is further heat treated to remove thermal hysteresis and residual stress from the film, thereby ensuring higher thermal stability and lower coefficient of thermal expansion.
The thickness of the polyimide film of the present application is not particularly limited. In some embodiments, the polyimide film has a thickness of 10 to 250 μm, and further may be 10 to 100 μm.
Fifth aspect of the application
In a fifth aspect of the present application, there is provided the use of a polyimide film according to the fourth aspect of the present application for the preparation of an OLED substrate, cover plate or touch pad. The polyimide film has low thermal expansion coefficient, high strength and enough optical transparency, can be used for preparing an OLED device substrate cover plate or a touch control plate, and has the advantages of strong heat resistance, strong mechanical property and long service life.
The following are some specific examples.
The experimental parameters not specified in the following specific examples are preferentially referred to the guidelines given in the present document, and may also be referred to the experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer.
The starting materials and reagents referred to in the following specific examples may be obtained commercially or may be prepared by known means by those skilled in the art.
(1) Coefficient of Thermal Expansion (CTE): a static thermo-mechanical analyzer (TMA) model TMA Q400 is used for representing the thermal dimensional change behavior of the polyimide film, the polyimide film is tested under the nitrogen atmosphere, the temperature interval is 50-300 ℃, the fixed load is 0.05N, the heating rate is 5 ℃/min, and the sample is heated to 300 ℃ to eliminate residual stress before the test.
(2) Optical transmittance: the average light transmittance of the Shimadzu UV-2550 ultraviolet visible spectrum tester at the wavelength of 380-780 nm.
(3) Glass transition temperature (T) g ): the glass transition behavior of the polyimide film is characterized by adopting TA DMA Q800, the test frequency is 1Hz, and the heating rate is 10 ℃/min.
Raw materials:
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example 1
5.0422g of the diamine compound (5), 3.2023g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 50g N-methylpyrrolidone were added to the reaction vessel, and dissolved by stirring at 20 ℃. 3.3724g of dianhydride compound (1) and 2.9422g of biphenyl dianhydride were added in this order and polymerized for 24 hours.
6.12g of acetic anhydride and 3.03g of triethylamine were added to the polymerization system, and the reaction was continued for 2 hours. The reaction mixture was slowly poured into ethanol. A white fine-wire-like precipitate precipitated. Filtering out filiform deposit and drying. A transparent polyimide resin was obtained. The resin was dissolved in N-methylpyrrolidone to form a 20% mass fraction solution, coated on the front and back surfaces of a glass plate, and heated to 200℃in an oven to form a transparent polyimide film.
Example 2
Into the reaction vessel were charged 2.5211g of the diamine compound (5), 1.6011g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 80.0g of dimethylacetamide, and the mixture was dissolved by stirring at 20 ℃. 4.5636g of the dianhydride compound (2) was added in this order, and the polymerization was carried out for 24 hours. 5.10g of acetic anhydride and 2.525g of triethylamine were added to the polymerization system, and the reaction was continued for 8 hours. The reaction mixture was slowly poured into ethanol. A white fine-wire-like precipitate precipitated. Filtering out filiform deposit and drying. A transparent polyimide resin was obtained. The resin was dissolved in N-methylpyrrolidone to form a 20% mass fraction solution, coated on the front and back surfaces of a glass plate, and heated to 200℃in an oven to form a transparent polyimide film.
Example 3
6.8261g of the diamine compound (6), 3.2023g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 89g N-methylpyrrolidone were charged into a reaction vessel and dissolved by stirring at 15 ℃. 4.5636g of dianhydride compound (3) and 2.1812g of pyromellitic dianhydride were added in this order and polymerized for 12 hours. And (3) coating the reaction mixture and the surface of a glass plate, and placing the glass plate in a vacuum oven, and heating to 300 ℃ in a gradient way to form the transparent polyimide film.
Example 4
6.6863g of the diamine compound (7), 3.3426g of 2, 2-bis (4-aminophenyl) hexafluoropropane and 120g N-methylpyrrolidone were charged into a reaction vessel and dissolved by stirring at 0 ℃. 4.6241g of dianhydride compound (4) and 3.3822g of (4-phthalic anhydride) formyloxy-4-phthalate were added in this order and polymerized for 48 hours. 20.4g of acetic anhydride and 10.2g of triethylamine were added to the polymerization system, and the reaction was continued for 5 hours. The reaction mixture was slowly poured into ethanol. A white fine-wire-like precipitate precipitated. Filtering out filiform deposit and drying. A transparent polyimide resin was obtained. The resin was dissolved in N-methylpyrrolidone to form a 20% mass fraction solution, coated on the front and back surfaces of a glass plate, and heated to 200℃in an oven to form a transparent polyimide film.
Example 5
6.8261g of the diamine compound (6) and 3.2023g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl were added to the reaction vessel, and the mixture was dissolved by stirring at a temperature of 10 to 20 ℃. 4.5636g of the dianhydride compound (2) and 2.2417g of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride were successively added and polymerized under a nitrogen atmosphere for 24 hours to form a precursor solution of transparent polyimide. 7.14g acetic anhydride and 5.54g pyridine were added to the polymerization system and the reaction was continued for 5 hours. The reaction mixture was slowly poured into methanol. A white fine-wire-like precipitate precipitated. Filtering out filiform deposit and drying. A transparent polyimide resin was obtained. The resin is dissolved in gamma-butyrolactone to form a solution with the mass fraction of 20%, the solution is coated on the surface and the inside of a glass plate, and the glass plate is placed in an oven to be heated to 150 ℃ to form a transparent polyimide film.
Example 6
7.3666g of diamine compound (8), 3.3426g of 2, 2-bis (4-aminophenyl) hexafluoropropane, 0.10g of nano silicon dioxide and 46.62g of dimethylacetamide are added into a reaction vessel, and the mixture is stirred and dissolved at a temperature of not more than 10 ℃. 4.5636g of the dianhydride compound (3) and 2.1812g of pyromellitic dianhydride were added in portions and polymerized under a nitrogen atmosphere for 24 hours to form a precursor solution of transparent polyimide. The polymerization solution is coated on the surface and the inside of a glass plate, and is placed in an oven, and the temperature is gradually increased from 80 to 300 ℃ to form the transparent polyimide film.
Example 7
To the reaction vessel were added 7.2268g of diamine compound (9), 3.3426g of 2, 2-bis (4-aminophenyl) hexafluoropropane, 45.6g N-methyl-2-pyrrolidone, and 3.3724g of dianhydride compound (1), 1.9611g of cyclobutane tetracarboxylic dianhydride, and the mixture was polymerized under nitrogen atmosphere for 12 hours to form a precursor solution of transparent polyimide. The polymerization solution is coated on the surface and the inside of a glass plate, and is placed in an oven, and the temperature is heated from 80 ℃ to 280 ℃ in a gradient way, so that the transparent polyimide film is formed.
Example 8
7.3666g of the diamine compound (8), 3.2023g of 2,2' -bis (trifluoromethyl) diaminobiphenyl, 44g of dimethylacetamide and an ice water bath were added to the reaction vessel, and the mixture was dissolved by stirring. 4.5636g of the dianhydride compound (1) and 4.4424g of hexafluorodianhydride were added in this order, and polymerization was carried out for 10 hours to form a precursor solution of transparent polyimide. 4.08g acetic anhydride and 5.17g isoquinoline were added to the polymerization system and the reaction was continued for 2 hours. The reaction mixture was slowly poured into ethanol. A white fine-wire-like precipitate precipitated. Filtering out filiform deposit and drying. A transparent polyimide resin was obtained. The resin was dissolved in N-methylpyrrolidone to form a 20% mass fraction solution, coated on the front and back surfaces of a glass plate, and heated to 200℃in an oven to form a transparent polyimide film.
Example 9
7.3666g of the diamine compound (8), 3.2023g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 80g of dimethylacetamide were charged into a reaction vessel, and dissolved by stirring at 20 ℃. 6.7448g of the dianhydride compound (1) was added in this order, and the polymerization was carried out for 12 hours. 12.24g acetic anhydride and 6.06g triethylamine were added to the polymerization system and the reaction was continued for 6 hours. The reaction mixture was slowly poured into ethanol. A white fine-wire-like precipitate precipitated. Filtering out filiform deposit and drying. A transparent polyimide resin was obtained. The resin was dissolved in N-methylpyrrolidone to form a 20% mass fraction solution, coated on the front and back surfaces of a glass plate, and heated to 250℃in an oven to form a transparent polyimide film.
Example 10
To the reaction vessel were added 7.2268g of diamine compound (9), 3.3426g of 2, 2-bis (4-aminophenyl) hexafluoropropane, 45.6g N-methyl-2-pyrrolidone, and 4.5636g of dianhydride compound (3), 2.9422g of biphenyl dianhydride, and the mixture was polymerized under nitrogen atmosphere for 15 hours to form a precursor solution of transparent polyimide, after the solids were completely dissolved. The polymerization solution is coated on the surface and the inside of a glass plate, and is placed in an oven, and the temperature is heated from 50 ℃ to 280 ℃ in a gradient way, so that the transparent polyimide film is formed.
Example 11
7.2268g of a diamine compound (9), 3.3426g of 2, 2-bis (4-aminophenyl) hexafluoropropane, 80g of dimethylacetamide, and 5.4846g of a dianhydride compound (12), 1.9611g of cyclobutane tetracarboxylic dianhydride were added in portions until all the solids were dissolved, and polymerized under a nitrogen atmosphere for 18 hours to form a precursor solution of transparent polyimide. The polymerization solution is coated on the surface and the inside of a glass plate, and is placed in an oven, and the temperature is heated from 50 ℃ to 300 ℃ in a gradient way, so that the transparent polyimide film is formed.
Example 12
6.8261g of the diamine compound (6) and 3.2023g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl were added to the reaction vessel, and the mixture was dissolved by stirring at a temperature of 0 to 20 ℃. 4.5735g of the dianhydride compound (13) and 2.2417g of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride were successively added and polymerized under a nitrogen atmosphere for 12 hours to form a precursor solution of transparent polyimide. 14.3g of acetic anhydride and 11.08g of pyridine were added to the polymerization system, and the reaction was continued for 24 hours. The reaction mixture was slowly poured into methanol. A white fine-wire-like precipitate precipitated. Filtering out filiform deposit and drying. A transparent polyimide resin was obtained. The resin was dissolved in dimethylacetamide to form a 20% mass fraction solution, which was coated on the surface and inside of a glass plate, and heated to 200 ℃ in an oven to form a transparent polyimide film.
Comparative example 1
3.4844g of the diamine compound (10), 3.2023g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, and 80.0g of dimethylacetamide were charged into a reaction vessel, and dissolved by stirring at 20 ℃. 3.3724g of dianhydride compound (1) and 2.1812g of pyromellitic dianhydride were added in this order and polymerized for 24 hours. 10.209g of acetic anhydride and 5.05g of triethylamine were added to the polymerization system, and the reaction was continued for 2 hours. The reaction mixture was slowly poured into ethanol. A white fine-wire-like precipitate precipitated. Filtering out filiform deposit and drying. A transparent polyimide resin was obtained. The resin was dissolved in N-methylpyrrolidone to form a 20% mass fraction solution, coated on the front and back surfaces of a glass plate, and heated to 200℃in an oven to form a transparent polyimide film.
Comparative example 2
6.3663g of the diamine compound (11), 3.2023g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 60g N-methylpyrrolidone were added to the reaction vessel, and the mixture was dissolved by stirring at 20 ℃. 4.5636g of dianhydride compound (2) and 2.1812g of pyromellitic dianhydride were added in this order and polymerized for 24 hours. 20.4g of acetic anhydride and 5.05g of triethylamine were added to the polymerization system, and the reaction was continued for 5 hours. The reaction mixture was slowly poured into ethanol. A white fine-wire-like precipitate precipitated. Filtering out filiform deposit and drying. A transparent polyimide resin was obtained. The resin was dissolved in N-methylpyrrolidone to form a 20% mass fraction solution, coated on the front and back surfaces of a glass plate, and heated to 200℃in an oven to form a transparent polyimide film.
Comparative example 3
To the reaction vessel were added 7.2268g of diamine compound (9), 3.3426g of 2, 2-bis (4-aminophenyl) hexafluoropropane, 45.6g N-methyl-2-pyrrolidone, and 7.3863g of dianhydride compound (14), 2.9422g of biphenyl dianhydride, and the mixture was polymerized under nitrogen atmosphere for 20 hours to form a precursor solution of transparent polyimide. The polymerization solution is coated on the surface and the inside of a glass plate, and is placed in an oven, and the temperature is heated from 70 ℃ to 300 ℃ in a gradient way, so that the transparent polyimide film is formed.
Performance test:
the polyimide films of the examples and comparative examples were tested using the test methods commonly used in the art, and the test items and test results are shown in the following table (table 1).
TABLE 1 Performance test results of transparent polyimide films
As can be seen from table 1, when the Cardo structure containing ether bond or halogen in the diamine component, the thermal dimensional stability of the transparent polyimide film is significantly improved, i.e., CTE is reduced. In addition, the glass transition temperature of the film is increased, the heat resistance of the transparent polyimide film is improved, and meanwhile, the good light transmittance and excellent mechanical properties of the film are maintained.
All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Unless otherwise indicated to the contrary by the intent and/or technical aspects of the present application, all references to which this application pertains are incorporated by reference in their entirety for all purposes. When reference is made to a cited document in the present application, the definitions of the relevant technical features, terms, nouns, phrases, etc. in the cited document are also incorporated. In the case of the cited documents, examples and preferred modes of the cited relevant technical features are also incorporated into the present application by reference, but are not limited to being able to implement the present application. It should be understood that when a reference is made to the description of the application in conflict with the description, the application is modified in light of or adaptive to the description of the application.
The technical features of the above-described embodiments and examples may be combined in any suitable manner, and for brevity of description, all of the possible combinations of the technical features of the above-described embodiments and examples are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered to be within the scope described in the present specification.
The above examples merely represent a few embodiments of the present invention and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Further, it is understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the above teachings, and equivalents thereof are intended to fall within the scope of the present invention. It should also be understood that, based on the technical solutions provided by the present invention, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the invention should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.
Claims (12)
1. A polyimide comprising a structural unit
wherein ,
selected from->
R 2 and R3 Each independently selected from: single bond, -CONH-, or-COO-, and R 2 and R3 At least one of them is-CONH-;
R 13 and R14 Each independently selected from: H. halo, ester, C1-C9 alkyl, C1-C9 haloalkyl or C3-C9 cycloalkyl;
A 1 selected from substituted or unsubstituted C6-C10 arylene or cycloalkylene;
*-Y 2 one selected from the following structures:
R 21 、R 22 、R 27 and R28 Selected from C1-C9 fluoroalkyl groups;
R 23 、R 24 、R 25 、R 26 、R 29 、R 30 、R 31 and R32 Each independently selected from: H. halo, ester, C1-C9 alkyl, C1-C9 fluoroalkyl or C3-C9 cycloalkyl;
R 7 、R 8 、R 9 and R10 Independently selected from: -O-or-CONH-;
x is selected from-O-or-S-.
2. The polyimide according to claim 1, wherein R 2 and R3 Each independently is-CONH-.
3. The polyimide according to claim 1, wherein X is selected from the group consisting of-O-.
4. The polyimide according to claim 1, wherein R 13 and R14 Each independently is H.
5. The polyimide according to claim 1, wherein A 1 Is phenylene.
6. The polyimide according to claim 1,characterized by the formula in each moleculeThe number of the structural units is 3-3000.
7. The preparation method of polyimide is characterized by comprising the following preparation steps: adding a diamine compound I and a dianhydride compound I, optionally adding a dianhydride compound II, optionally adding a diamine compound II into an organic solvent I, mixing, and carrying out polymerization reaction to obtain polyamide acid I;
carrying out dehydration reaction on the polyamide acid I to obtain polyimide I;
wherein the polyimide i is as defined in any one of claims 1 to 6;
the dianhydride compound I is selected fromCorresponding dianhydrides;
the diamine compound I is selected from the group consisting of 2 -a diamine selected from the group consisting of the corresponding structure of formula I or formula II;
the dianhydride compound II is selected from any one of (4-phthalic anhydride) formyloxy-4-phthalic ester, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, hexafluorodianhydride and biphenyl dianhydride;
the diamine compound II is selected from any one of the following structures:
8. the method for producing a polyimide according to claim 7, wherein the organic solvent I is one or more selected from the group consisting of N-methylpyrrolidone, dimethylacetamide and N-methyl-2-pyrrolidone.
9. The method for producing polyimide according to claim 8, wherein the molar ratio of the diamine compound i to the diamine compound ii is 10: (0-50);
the molar ratio of the dianhydride compound I to the dianhydride compound II is 10: (0-50).
10. A polyimide composition comprising a filler and a polyimide as defined in any one of claims 1 to 6.
11. A polyimide film comprising the polyimide of any one of claims 1 to 6, or comprising the polyimide produced by the production method of any one of claims 7 to 9, or comprising the polyimide composition of claim 10;
the thickness of the polyimide film is 10-250 mu m.
12. The use of the polyimide film of claim 11 for the preparation of an OLED substrate, cover plate or touch panel.
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