CN116574260A - Flexible transparent polyimide film precursor, film and preparation method thereof - Google Patents
Flexible transparent polyimide film precursor, film and preparation method thereof Download PDFInfo
- Publication number
- CN116574260A CN116574260A CN202310567332.7A CN202310567332A CN116574260A CN 116574260 A CN116574260 A CN 116574260A CN 202310567332 A CN202310567332 A CN 202310567332A CN 116574260 A CN116574260 A CN 116574260A
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- CN
- China
- Prior art keywords
- dianhydride
- diamine
- precursor solution
- film
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000002243 precursor Substances 0.000 title claims abstract description 57
- 229920001721 polyimide Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000004985 diamines Chemical class 0.000 claims abstract description 61
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 125000006159 dianhydride group Chemical group 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 49
- 239000002904 solvent Substances 0.000 claims description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004642 Polyimide Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 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 claims description 10
- -1 aliphatic diamine Chemical class 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- SBHHKGFHJWTZJN-UHFFFAOYSA-N 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1(C)C(C(O)=O)C(C)(C(O)=O)C1C(O)=O SBHHKGFHJWTZJN-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VBPWZDGHWDCOII-UHFFFAOYSA-N 4-n-(4-aminocyclohexyl)cyclohexane-1,4-diamine Chemical compound C1CC(N)CCC1NC1CCC(N)CC1 VBPWZDGHWDCOII-UHFFFAOYSA-N 0.000 claims description 5
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 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 3
- SZEWALYSKVMFAD-UHFFFAOYSA-N 4-(4-aminocyclohexyl)oxycyclohexan-1-amine Chemical compound C1CC(N)CCC1OC1CCC(N)CC1 SZEWALYSKVMFAD-UHFFFAOYSA-N 0.000 claims description 3
- HVSOOROWXIVZSH-UHFFFAOYSA-N 4-(9H-fluoren-1-yl)-2-fluoroaniline Chemical compound NC1=C(C=C(C=C1)C1=CC=CC=2C3=CC=CC=C3CC1=2)F HVSOOROWXIVZSH-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- SSDBTLHMCVFQMS-UHFFFAOYSA-N 4-[4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 SSDBTLHMCVFQMS-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- PMTMAFAPLCGXGK-JMTMCXQRSA-N (15Z)-12-oxophyto-10,15-dienoic acid Chemical compound CC\C=C/C[C@H]1[C@@H](CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-JMTMCXQRSA-N 0.000 claims description 2
- DOMPENMCTWZXEE-UHFFFAOYSA-N 1,2,3,4-tetramethylcyclobutane Chemical compound CC1C(C)C(C)C1C DOMPENMCTWZXEE-UHFFFAOYSA-N 0.000 claims description 2
- UVUCUHVQYAPMEU-UHFFFAOYSA-N 3-[2-(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound NC1=CC=CC(C(C=2C=C(N)C=CC=2)(C(F)(F)F)C(F)(F)F)=C1 UVUCUHVQYAPMEU-UHFFFAOYSA-N 0.000 claims description 2
- PMTMAFAPLCGXGK-UHFFFAOYSA-N OPDA Natural products CCC=CCC1C(CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-UHFFFAOYSA-N 0.000 claims description 2
- 101100028078 Oryza sativa subsp. japonica OPR1 gene Proteins 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 239000012784 inorganic fiber Substances 0.000 claims description 2
- 125000002183 isoquinolinyl group Chemical class C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 150000007660 quinolones Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 11
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000005622 photoelectricity Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 46
- 239000000203 mixture Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 229920005575 poly(amic acid) Polymers 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 238000005266 casting Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 6
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- OVASAEXSPYGGES-UHFFFAOYSA-N C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 Chemical compound C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 OVASAEXSPYGGES-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- GZDFHIJNHHMENY-UHFFFAOYSA-N Dimethyl dicarbonate Chemical compound COC(=O)OC(=O)OC GZDFHIJNHHMENY-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000010300 dimethyl dicarbonate Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DUTLDPJDAOIISX-UHFFFAOYSA-N 3-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=CC(C(C(F)(F)F)C(F)(F)F)=C1 DUTLDPJDAOIISX-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- LACZRKUWKHQVKS-UHFFFAOYSA-N 4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F LACZRKUWKHQVKS-UHFFFAOYSA-N 0.000 description 1
- RXNKCIBVUNMMAD-UHFFFAOYSA-N 4-[9-(4-amino-3-fluorophenyl)fluoren-9-yl]-2-fluoroaniline Chemical compound C1=C(F)C(N)=CC=C1C1(C=2C=C(F)C(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 RXNKCIBVUNMMAD-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
Classifications
-
- 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
- C08G73/1039—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
- C08G73/1042—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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention discloses a flexible transparent polyimide film precursor, a film and a preparation method thereof, belonging to the technical field of high polymer materials. The precursor solution is prepared by polymerization reaction of dianhydride and diamine; the film is prepared from a precursor solution. The precursor solution is prepared by mixing specific various diamines with specific various dianhydrides, and the polyimide film prepared by using the precursor solution is unexpectedly found to have good heat resistance and mechanical properties while maintaining good optical properties, and is suitable for the fields of flexible photoelectricity, aerospace and the like, particularly for flexible display and transparent display structural members or substrates.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a flexible transparent polyimide film precursor, a film and a preparation method thereof.
Background
Polyimide is a high-performance polymer material with wide application, and has unique imide ring and aromatic group in the main chain, excellent heat resistance, electrical property and mechanical property, and research on polyimide materials has become an important component for the development of the electronic industry.
In recent years, with the development of high and new technology industry, the flexibility and the transparency of photoelectric devices become a necessary development trend, and colorless transparent polyimide has the characteristics of transparency, light weight, impact resistance, excellent heat resistance and the like, and is receiving more and more attention in the fields of patterned display devices, liquid crystal orientation layers, optical films, organic photovoltaic solar panels, flexible printed circuit boards, touch panels and the like, so that in order to realize the real transparency and the flexibility of organic photoelectric devices represented by OLED, the polyimide film has excellent comprehensive mechanical properties besides the transparency and the heat resistance and is also an important influence factor applied as a flexible photoelectric material layer.
Conventional polyimide films are tan or yellow in color, and researchers have generally introduced special groups into the main chain structure of the molecule, such as large substituent side groups capable of imparting a large free volume, or asymmetric structures, in order to minimize intermolecular or intramolecular charge transfer interactions to produce colorless transparent polyimide, however, in most cases, the introduction of these functional groups sacrifices the flexibility of the film, so that conventional transparent polyimide materials have better optical properties, but the process is complicated, the product flexibility is insufficient, and the yield is low.
Chinese patent application 201810688078.5 discloses a wholly aromatic colorless transparent polyimide film and a preparation method thereof, wherein diamine monomer 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene with trifluoromethyl side group and intermediate ether bond is adopted as raw material, and is polymerized with 2, 3',4' -diphenyl ether tetracarboxylic dianhydride which contains ether bond in the middle and is isomerised, and then thermoplastic polyimide material is synthesized by adopting a chemical imidization method, and the polyimide film can be prepared by dissolving, coating and volatilizing solvent. The wholly aromatic colorless transparent polyimide film prepared by the method has high optical transparency and thermal stability, but the wholly aromatic CPI is generally formed by blocking intermolecular charge transfer complex by introducing fluorine atoms or fluorine-containing groups, but the wholly aromatic CPI has high cost, complex processing technology and poor surface cohesiveness of the transparent film, and limits industrialized popularization of the wholly aromatic CPI.
The invention discloses a cycloaliphatic dianhydride monomer and a high-transparency low-dielectric-constant polyimide film in the Chinese patent application 201910214276.2, which is characterized in that firstly diamine monomer is fully dissolved in aprotic polar solvent, then aprotic polar solution dissolved with the cycloaliphatic dianhydride monomer is added, and the mixture reacts for 0.5 to 6 hours at the temperature of-10 to 35 ℃ under the protection of nitrogen or inert gas to obtain cycloaliphatic polyimide precursor solution, then the cycloaliphatic polyimide precursor solution is coated on a substrate, and after imidization, stress is eliminated, thus obtaining the high-transparency low-dielectric-constant polyimide film. The film prepared by the invention has low dielectric constant and dielectric loss and excellent light transmittance, but the full aliphatic/alicyclic PI generally generates insoluble salt in the primary stage of PAA formation, so that polymerization is stopped, the synthesis process is complex, and even if the formation of the salt is avoided through complex process optimization in the synthesis stage, the complete PI film is prepared, and the film is poor in rigidity and heat resistance and lacks of practicability.
The transparent polyimide film with excellent heat resistance, optical performance, comprehensive mechanical property and easy processing is one of key materials which are urgently needed in the technical field of microelectronics and flexible display at present, and development of the material can meet the increasingly urgent technical requirements in the field of advanced electronics and flexible display. Therefore, the flexible and easy-to-process polyimide with excellent heat resistance, optical transparency and comprehensive mechanical properties is developed and has important significance.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide an easy-to-process flexible copolyimide film with excellent heat resistance, optical transparency and mechanical properties, and a preparation method and application thereof. The transparent polyimide has light transmittance of more than 88%, tg of more than 240 ℃ and CTE of less than 60 ppm/DEG C, and has better mechanical strength and elongation at break, thereby being beneficial to processing and forming.
The invention is realized by the following technical scheme:
in one aspect, the present invention provides a precursor solution for polyimide prepared by polymerizing dianhydride and diamine in a solvent.
The diamine comprises a first diamine and a second diamine; the first diamine is aliphatic diamine containing dicyclohexyl groups; the second dianhydride is a diamine other than the first diamine, preferably a fluorine-containing diamine.
The dianhydride comprises a first dianhydride and a second dianhydride; the first dianhydride is alicyclic dianhydride; the second dianhydride is a dianhydride other than the first dianhydride, preferably a fluorine-containing dianhydride or an aromatic dianhydride.
The addition amount of the first diamine is 10-90mol% of the total amount of diamine; the addition amount of the second diamine is 10-90mol% of the total amount of diamine;
the addition amount of the first dianhydride is 20-90mol% of the total amount of the dianhydride; the addition amount of the second dianhydride is 10-80 mol% of the total amount of the dianhydride;
the molar ratio of the total diamine to the total dianhydride is 1:0.9-1.1
The polymerization is carried out in the presence of at least one organic solvent.
As a preferable technical scheme, the first diamine has a structure shown in a general formula (1):
wherein R1 is selected from single bond, carbon atom, oxygen atom, amino group, C 1-6 One of alkyl or aryl;
r2 and R3 are each independently selected from the group consisting of a hydrogen atom, a methyl group, a halogen atom, a hydroxyl group, and C 1-4 One of alkyl or aryl;
further preferably, the first diamine is selected from one of 4,4' -diaminodicyclohexylmethane (HMDA), bis (4-aminocyclohexyl) ether (HEDA), N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine (HNDA) or 3,3' -dimethyl-4, 4' -diaminodicyclohexylmethane (DMDC).
The second diamine is selected from one of 4,4' -diamino-2, 2' -bistrifluoromethyl biphenyl (TFMB), 9' -bis (3-fluoro-4-aminophenyl) fluorene (FFDA), 2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether (6 FODA), 2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane (HFBAPP) or 2, 2-bis (3-aminophenyl) hexafluoropropane (APFP).
The first dianhydride is selected from one of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,3, 4-cyclopentane tetracarboxylic dianhydride (CPDA), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (H-PMDA), hydrogenated biphenyl tetracarboxylic dianhydride (H-BPDA), 1, 3-dimethyl-cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (DM-CBDA), 1,2,3, 4-tetramethyl cyclobutane, 1,2,3, 4-tetracarboxylic dianhydride (TM-CBDA) and norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5', 6' -tetracarboxylic dianhydride (CpODA).
The second dianhydride comprises one of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA), 3',4' -biphenyl tetracarboxylic dianhydride (BPDA), 2, 3',4' -biphenyl tetracarboxylic dianhydride (a-BPDA), diphenyl ether tetracarboxylic anhydride (OPDA), 3',4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) or 4,4' - (4, 4' -hexafluoroisopropyldiphenoxy) bis (phthalic anhydride) (6F-BPADA).
The organic solvent is selected from one or more of N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), r-butyrolactone (GBL), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), m-cresol, ethyl acetate and acetone.
The polymerization may be carried out in the presence of an auxiliary.
The auxiliary agent comprises a catalyst; the catalyst is selected from one or more of pyridine, isoquinoline compounds, quinolone compounds, imidazole compounds and benzimidazole compounds;
the molar ratio of the catalyst to the total amount of diamine is 1:0.005-0.03.
The auxiliary agent also comprises one or more of an antioxidant, a heat stabilizer, a color regulator, an antistatic agent and a tearing resistant agent;
the antioxidant, the heat stabilizer, the color regulator, the antistatic agent and the tearing-resistant agent are all conventional auxiliary agents in the field.
The auxiliary agent also comprises a filler, wherein the filler is selected from one or more of nano silicon dioxide, glass fiber, graphene, carbon nano tube, inorganic fiber, aluminum oxide and calcium carbonate.
The filler is added in an amount of 0.1-15%, preferably 5-15% of the solid content of the precursor mixed liquid.
In another aspect, the present invention provides the use of the above precursor solution for the preparation of polyimide films.
In yet another aspect, the present invention provides a polyimide film prepared from the precursor solution described above.
In still another aspect, the present invention also provides a method for preparing a polyimide film, comprising the steps of:
s1, mixing diamine and dianhydride, dissolving in a solvent, and stirring and mixing to obtain a mixed solution;
s2, adding a catalyst into the mixed solution, and stirring and mixing to obtain a precursor solution;
s3, pouring the precursor solution onto a substrate, drying, and removing part of the solvent to obtain a semi-dried film;
s4, placing the semi-dried film in an inert gas oven, and imidizing at a high temperature to obtain the film.
And (3) drying in the step (S3), wherein the temperature range is 50-180 ℃ and the drying time is 8-60min.
The high temperature imidization in the step S4 is performed at 200-300 ℃ for 5-60min.
The invention also provides application of the polyimide film in the flexible photoelectric field and the aerospace field, in particular application in preparing a structural member, a reinforcing layer or a base material of flexible transparent display.
Compared with the prior art, the invention has the beneficial effects that:
(1) The polyimide film disclosed by the invention has the advantages of simple preparation method, excellent performance, excellent heat resistance and good optical transmittance, the transmittance of the prepared polyimide film is more than 88%, the Tg is more than 250 ℃, the polyimide film has good mechanical properties, the polyimide film is favorable for processing and forming, can be used for flexible display in the fields of flexible photoelectricity and aerospace, and can be used as a structural member or a base material for transparent display, so that the market demand is met;
(2) According to the invention, a precursor solution is prepared by mixing specific various diamines with specific various dianhydrides and adding 0.1% -15% of filler, and the polyimide film prepared by using the precursor solution is unexpectedly found to have better heat resistance and mechanical strength while maintaining excellent optical performance.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. 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 invention belongs.
The invention does not limit the sources of the adopted raw materials, and if no special description exists, the adopted raw materials are all common commercial products in the technical field.
Example 1
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.08mol of 4,4' -diaminodicyclohexylmethane (HMDA) and 0.02mol of 2,2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether (6 FODA), stirred at room temperature to dissolve diamine and obtain a clear solution, followed by slow addition of 0.06mol of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA) and 0.04mol of 1, 3-dimethyl-cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (DM-CBDA) to react with diamine, and then stirring the mixture under nitrogen atmosphere for 36 hours to obtain a polyamic acid mixture having a viscosity of 1720 poise;
uniformly stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine to obtain a precursor solution; casting the obtained precursor liquid on a glass substrate and removing part of the solvent in an oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Example 2
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.06mol of 4,4' -diaminodicyclohexylmethane (HMDA) and 0.04mol of 4,4' -diamino-2, 2' -bistrifluoromethyl biphenyl (TFMB), stirred at room temperature to dissolve diamine and give a clear solution, followed by slowly adding 0.075mol of 2, 3',4' -biphenyltetracarboxylic dianhydride (a-BPDA) and 0.025mol of norbornane-2-spiro-alpha ' -spiro-2 ' -norbornane-5, 5', 6' -tetracarboxylic dianhydride (CpODA) to react with diamine, and stirring the mixture under nitrogen atmosphere for 36 hours to give a polyamic acid mixture having a viscosity of 1540 poise;
uniformly stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine to obtain a precursor solution; casting the obtained precursor liquid on a glass substrate and removing part of the solvent in an oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Example 3
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.05mol of bis (4-aminocyclohexyl) ether (HEDA) and 0.05mol of 2,2 '-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane (HFBAPP), stirred at room temperature to dissolve the diamine and give a clear solution, and then 0.06mol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA) and 0.04mol of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA) were slowly added to react with the diamine, and then the mixture was stirred under nitrogen atmosphere for 36 hours to give a polyamic acid mixture having a viscosity of 1920 poise;
uniformly stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine to obtain a precursor solution; casting the obtained precursor liquid on a glass substrate and removing part of the solvent in an oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Example 4
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.025 mole of 3,3' -dimethyl-4, 4' -diaminodicyclohexylmethane (DMDC) and 0.075 mole of 2,2' -bis (3-aminophenyl) hexafluoropropane (APFP), stirred at room temperature to dissolve diamine and obtain a clear solution, then 0.04 mole of diphenylether tetracarboxylic anhydride (ODPA) and 0.06 mole of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (H-PMDA) were slowly added to react with diamine, and then the mixture was stirred under nitrogen atmosphere for 36 hours to obtain a polyamic acid mixture having a viscosity of 1510 poise;
uniformly stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine to obtain a precursor solution; casting the obtained precursor liquid on a glass substrate and removing part of the solvent in an oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Example 5
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.04mol of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine (HNDA) and 0.06mol of 9,9 '-bis (3-fluoro-4-aminophenyl) fluorene (FFDA), stirred at room temperature to dissolve the diamine and give a clear solution, and then 0.025mol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA) and 0.075mol of hydrogenated biphenyltetracarboxylic dianhydride (H-BPDA) were slowly added to react with the diamine, and then the mixture was stirred under nitrogen atmosphere for 36 hours to give a polyamic acid mixture having a viscosity of 1920 poise.
Uniformly stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine to obtain a precursor solution; casting the obtained precursor liquid on a glass substrate and removing part of the solvent in an oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Example 6
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.08mol of 4,4' -diaminodicyclohexylmethane (HMDA) and 0.02mol of 4,4' -diamino-2, 2' -bistrifluoromethyl biphenyl (TFMB), stirred at room temperature to dissolve diamine and obtain a clear solution, and then 0.065mol of 2, 3',4' -biphenyltetracarboxylic dianhydride (a-BPDA) and 0.035mol of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA) were slowly added to react with diamine, and then the mixture was stirred under nitrogen atmosphere for 36 hours to obtain a polyamic acid mixture having a viscosity of 1920 poise;
uniformly stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine to obtain a precursor solution; casting the obtained precursor liquid on a glass substrate and removing part of the solvent in an oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Example 7
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.08mol of 4,4' -diaminodicyclohexylmethane (HMDA) and 0.02mol of 2,2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether (6 FODA), stirred at room temperature to dissolve diamine and obtain a clear solution, followed by slow addition of 0.06mol of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA) and 0.04mol of 1, 3-dimethyl-cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (DM-CBDA) to react with diamine, and then stirring the mixture under nitrogen atmosphere for 36 hours to obtain a polyamic acid mixture having a viscosity of 1720 poise;
stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine together to obtain a precursor solution; adding the nano silicon dioxide dispersion liquid into the mixed liquid according to the solid content of 7.5 percent, fully mixing until the mixture is uniformly stirred, and finally casting the obtained precursor liquid on a glass substrate and removing part of the solvent in a baking oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Example 8
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.08mol of 4,4' -diaminodicyclohexylmethane (HMDA) and 0.02mol of 2,2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether (6 FODA), stirred at room temperature to dissolve diamine and obtain a clear solution, followed by slow addition of 0.06mol of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA) and 0.04mol of 1, 3-dimethyl-cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (DM-CBDA) to react with diamine, and then stirring the mixture under nitrogen atmosphere for 36 hours to obtain a polyamic acid mixture having a viscosity of 1720 poise;
stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine together to obtain a precursor solution; adding the nano silicon dioxide dispersion liquid into the mixed liquid according to the solid content of 15%, fully mixing until the mixture is uniformly stirred, and finally casting the obtained precursor liquid on a glass substrate and removing part of the solvent in a baking oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Comparative example 1
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.1mol of 4,4 '-diamino-2, 2' -bistrifluoromethyl biphenyl (TFMB), stirred at room temperature to dissolve diamine and obtain a clear solution, followed by slowly adding 0.025mol of 2, 3',4' -biphenyltetracarboxylic dianhydride (a-BPDA) and 0.075mol of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA) to react with diamine, and then stirring the mixture under nitrogen atmosphere for 36 hours to obtain a polyamic acid mixture having a viscosity of 1920 poise;
uniformly stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine to obtain a precursor solution; casting the obtained precursor liquid on a glass substrate and removing part of the solvent in an oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Comparative example 2
150g of N, N-dimethylacetamide solvent, then 0.1mol of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine (HNDA) were added to a three-necked round bottom flask, stirred at room temperature to dissolve the diamine and obtain a clear solution, then 0.07mol of diphenylether tetracarboxylic anhydride (ODPA) and 0.03mol of norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5', 6' -tetracarboxylic dianhydride (CpODA) were slowly added to react with the diamine, and then the mixture was stirred under nitrogen atmosphere for 36 hours to obtain a polyamic acid mixture having a viscosity of 1920 poise;
uniformly stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine to obtain a precursor solution; casting the obtained precursor liquid on a glass substrate and removing part of the solvent in an oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Comparative example 3
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.08mol of 4,4' -diaminodicyclohexylmethane (HMDA) and 0.02mol of 2,2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether (6 FODA), stirred at room temperature to dissolve diamine and obtain a clear solution, followed by slow addition of 0.06mol of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA) and 0.04mol of 1, 3-dimethyl-cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (DM-CBDA) to react with diamine, and then stirring the mixture under nitrogen atmosphere for 36 hours to obtain a polyamic acid mixture having a viscosity of 1720 poise;
stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine together to obtain a precursor solution; adding the nano silicon dioxide dispersion liquid into the mixed liquid according to the solid content of 20%, fully mixing until the mixture is uniformly stirred, and finally casting the obtained precursor liquid on a glass substrate and removing part of the solvent in a baking oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
Comparative example 4
150g of N, N-dimethylacetamide solvent was added to a three-necked round bottom flask, followed by 0.06mol of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine (HNDA) and 0.04mol of 9, 9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA), stirred at room temperature to dissolve the diamine and obtain a clear solution, then 0.1mol of 2, 3',4' -biphenyltetracarboxylic dianhydride (a-BPDA) was slowly added to react with the diamine, and then the mixture was stirred under nitrogen atmosphere for 36 hours to obtain a polyamic acid mixture having a viscosity of 1920 poise;
uniformly stirring the obtained polyamic acid mixed solution and 0.0015mol of pyridine to obtain a precursor solution; casting the obtained precursor liquid on a glass substrate and removing part of the solvent in an oven at 100 ℃/10 min; the semi-dried film was finally imidized by heating in a nitrogen oven at 250 ℃/30min with an oxygen concentration <100ppm, and the resulting film was removed from the substrate and analyzed.
And (3) performance detection:
the film performance test method is as follows:
(1) The transmittance (Tr 550 nm), yellowness index, haze and the like of the polyimide film are tested by an X-rite Ci7800 spectrophotometer;
(2) The tensile strength, elongation at break and elastic modulus of the polyimide film were measured using Shimadzu AG-X plus,1KN at a measuring speed of 5mm/min, a sample size of 10mm wide by 15mm long, and a measuring gauge length: 50mm, extensometer gauge length 20mm.
(3) Glass transition temperature (Tg), measured using a dynamic mechanical analyzer (DMA 850), the test conditions were as follows: the inflection point of the curve with the maximum value was recorded as the glass transition temperature, measured under a nitrogen atmosphere at a load of 0.05N and a heating rate of 3 ℃/min in the temperature range of 200-400 ℃.
(4) The Coefficient of Thermal Expansion (CTE) was measured using a thermo-mechanical analyzer (TMA 7100C) as follows: the load is 20mN, the heating rate is 5 ℃/min, and the temperature range is 50-200 ℃.
The results are shown in Table 1.
TABLE 1 film Performance test results
As can be seen from the detection data in the table 1, the polyimide films in the embodiments 1 to 8 of the invention have light transmittance of more than 88 percent and Tg of more than 250 ℃, combine good optical transmittance and heat resistance, have better comprehensive mechanical strength and flexibility, and are beneficial to processing and forming.
Meanwhile, according to comparative example 1, although Tg of the film prepared by TFMB and a-BPDA\CBDA can reach 357 ℃, the film is yellow in color, the film flexibility is poor, and the elongation at break is only 2.1%; the film prepared in comparative example 2 was excellent in heat resistance and mechanical properties, but the yellowness index reached 7.2; in comparative example 3, the heat resistance of the film is improved along with the improvement of the content of the filler, but the high content of the filler causes difficult dispersion, the filler is easy to agglomerate, and finally the haze of the film is obviously deteriorated, so that the film does not meet the optical performance requirement; in comparative example 4, the film has good mechanical strength, but poor flexibility and optical properties, and the elongation at break is only 4.2%, which is unfavorable for processing and molding.
As can be seen from the above, the polyimide film provided by the invention introduces diamine with a specific structure and two kinds of dianhydride into the main chain structure of the polyimide film, and simultaneously adds specific auxiliary agents, so that the copolymer film has the characteristics of higher transmittance and heat resistance, and simultaneously has excellent mechanical strength and flexibility.
The invention has been further described above in connection with specific embodiments, which are exemplary only and do not limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes and substitutions of details and forms of the technical solution of the present invention may be made without departing from the spirit and scope of the present invention, but these changes and substitutions fall within the scope of the present invention.
Claims (14)
1. A precursor solution for polyimide, characterized by: the precursor solution is prepared by polymerization reaction of dianhydride and diamine;
the diamine comprises a first diamine and a second diamine; the first diamine is aliphatic diamine with dicyclohexyl group; the second dianhydride is a diamine other than the first diamine;
the dianhydride comprises a first dianhydride and a second dianhydride; the first dianhydride is alicyclic dianhydride; the second dianhydride is other dianhydrides different from the first dianhydride;
the molar ratio of the total diamine to the total dianhydride is 1:0.9-1.1.
2. The precursor solution of claim 1, wherein: the polymerization is carried out in the presence of an organic solvent; the organic solvent is selected from one or more of N-methyl-2-pyrrolidone, dimethylacetamide, r-butyrolactone, dimethyl sulfoxide, dimethylformamide, m-cresol, ethyl acetate and acetone.
3. The precursor solution of claim 1, wherein: the first diamine has a structure shown in a general formula (1):
wherein R1 is selected from single bond, carbon atom, oxygen atom, amino group, C 1-6 One of alkyl or aryl;
r2 and R3 are each independently selected from the group consisting of a hydrogen atom, a methyl group, a halogen atom, a hydroxyl group, and C 1-4 One of alkyl or aryl.
4. A precursor solution according to claim 3, characterized in that: the first diamine is selected from one of 4,4' -diamino dicyclohexylmethane, bis (4-aminocyclohexyl) ether, N- (4-aminocyclohexyl) -1, 4-cyclohexane diamine or 3,3' -dimethyl-4, 4' -diamino dicyclohexylmethane;
the second diamine is selected from one of 4,4' -diamino-2, 2' -bistrifluoromethyl biphenyl, 9' -bis (3-fluoro-4-aminophenyl) fluorene, 2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane or 2, 2-bis (3-aminophenyl) hexafluoropropane.
5. The precursor solution of claim 1, wherein: the first dianhydride is selected from one of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, hydrogenated biphenyl tetracarboxylic dianhydride, 1, 3-dimethyl-cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-cyclobutane, 1,2,3, 4-tetracarboxylic 1,2,3, 4-dianhydride and norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5', 6' -tetracarboxylic dianhydride;
the second dianhydride comprises one of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic anhydride (OPDA), 3',4' -benzophenone tetracarboxylic dianhydride or 4,4' - (4, 4' -hexafluoroisopropyldiphenoxy) bis (phthalic anhydride).
6. The precursor solution of claim 1, wherein: the polymerization may be carried out in the presence of an auxiliary.
7. The precursor solution of claim 6, wherein: the auxiliary agent comprises a catalyst; the catalyst is selected from one or more of pyridine, isoquinoline compounds, quinolone compounds, imidazole compounds and benzimidazole compounds; the molar ratio of the catalyst to the total amount of diamine is 1:0.005-0.03.
8. The precursor solution of claim 6, wherein: the auxiliary agent also comprises one or more of an antioxidant, a heat stabilizer, a color regulator, an antistatic agent and a tearing-resistant agent.
9. The precursor solution of claim 6, wherein: the auxiliary agent also comprises a filler, wherein the filler is selected from one or more of nano silicon dioxide, glass fiber, graphene, carbon nano tube, inorganic fiber, aluminum oxide and calcium carbonate; the addition amount of the filler is 0.1-15% of the solid content of the precursor mixed liquid.
10. Use of the precursor solution according to any one of claims 1-9 for the preparation of polyimide films.
11. A polyimide film, characterized in that: the film is prepared from the precursor solution of any one of claims 1-9.
12. A method for preparing the polyimide film according to claim 11, characterized in that: the method comprises the following steps:
s1, mixing diamine and dianhydride, dissolving in a solvent, and stirring and mixing to obtain a mixed solution;
s2, adding a catalyst into the mixed solution, and stirring and mixing to obtain a precursor solution;
s3, pouring the precursor solution onto a substrate, drying, and removing part of the solvent to obtain a semi-dried film;
s4, placing the semi-dried film in an inert gas oven, and imidizing at a high temperature to obtain the film;
the high temperature imidization temperature is 200-300 ℃ and the high temperature imidization time is 5-60min.
13. The method of manufacturing according to claim 12, wherein: the step S3 is performed with drying, the temperature range is 50-180 ℃, and the drying time is 8-60min; the high temperature imidization in the step S4 is carried out at 200-300 ℃ for 5-60min.
14. The use of the polyimide film of claim 11 in the flexible photovoltaic and aerospace fields.
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| US20190153158A1 (en) * | 2016-04-07 | 2019-05-23 | Kaneka Corporation | Polyimide resin, polyimide solution, film, and method for producing same |
| CN112194791A (en) * | 2020-06-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | Transparent polyimide film and preparation method thereof |
| CN112480442A (en) * | 2019-09-12 | 2021-03-12 | 杜邦电子公司 | Polyimide film and electronic device |
| CN114426693A (en) * | 2021-12-29 | 2022-05-03 | 宁波长阳科技股份有限公司 | Preparation method of colorless transparent polyimide film with low yellowness and high mechanical property |
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| US20190153158A1 (en) * | 2016-04-07 | 2019-05-23 | Kaneka Corporation | Polyimide resin, polyimide solution, film, and method for producing same |
| CN112480442A (en) * | 2019-09-12 | 2021-03-12 | 杜邦电子公司 | Polyimide film and electronic device |
| US20210079182A1 (en) * | 2019-09-12 | 2021-03-18 | Dupont Electronics, Inc. | Polyimide films and electronic devices |
| CN112194791A (en) * | 2020-06-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | Transparent polyimide film and preparation method thereof |
| CN114426693A (en) * | 2021-12-29 | 2022-05-03 | 宁波长阳科技股份有限公司 | Preparation method of colorless transparent polyimide film with low yellowness and high mechanical property |
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