CN112646183A - Polyimide material and preparation method and application thereof - Google Patents
Polyimide material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112646183A CN112646183A CN202011527391.4A CN202011527391A CN112646183A CN 112646183 A CN112646183 A CN 112646183A CN 202011527391 A CN202011527391 A CN 202011527391A CN 112646183 A CN112646183 A CN 112646183A
- Authority
- CN
- China
- Prior art keywords
- dianhydride
- polyimide material
- diamine
- film
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 104
- 239000004642 Polyimide Substances 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 54
- 150000004985 diamines Chemical group 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 57
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 39
- 229920005575 poly(amic acid) Polymers 0.000 claims description 36
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 29
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 26
- 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 18
- 238000000034 method Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 14
- -1 ethynyl dianhydride Chemical compound 0.000 claims description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012024 dehydrating agents Substances 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 6
- 238000003303 reheating Methods 0.000 claims description 6
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- SFAZBJLFDAGITE-UHFFFAOYSA-N C1(C=2C(C(=O)O1)=CC=CC2)=O.C2(=CC=CC=C2)C#C Chemical compound C1(C=2C(C(=O)O1)=CC=CC2)=O.C2(=CC=CC=C2)C#C SFAZBJLFDAGITE-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052987 metal hydride Inorganic materials 0.000 claims description 3
- 150000004681 metal hydrides Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 125000006159 dianhydride group Chemical group 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 97
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 90
- 229910052757 nitrogen Inorganic materials 0.000 description 45
- 239000011521 glass Substances 0.000 description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000011347 resin Substances 0.000 description 21
- 229920005989 resin Polymers 0.000 description 21
- 238000011056 performance test Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000001816 cooling Methods 0.000 description 18
- 238000002791 soaking Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 238000001291 vacuum drying Methods 0.000 description 18
- 239000005457 ice water Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 9
- 238000007605 air drying Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 4
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 3
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XUKLTPZEKXTPBT-UHFFFAOYSA-N 3-oxatricyclo[5.2.1.01,5]dec-5-ene-2,4-dione Chemical compound C1CC2C=C3C(=O)OC(=O)C13C2 XUKLTPZEKXTPBT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NFSQGQXKVFGKSO-UHFFFAOYSA-N 3-(2-phenylphenoxy)aniline Chemical group NC1=CC=CC(OC=2C(=CC=CC=2)C=2C=CC=CC=2)=C1 NFSQGQXKVFGKSO-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- ZWQOXRDNGHWDBS-UHFFFAOYSA-N 4-(2-phenylphenoxy)aniline Chemical group C1=CC(N)=CC=C1OC1=CC=CC=C1C1=CC=CC=C1 ZWQOXRDNGHWDBS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- OPVHOFITDJSMOD-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1OC1=CC=CC2=C1C(=O)OC2=O OPVHOFITDJSMOD-UHFFFAOYSA-N 0.000 description 1
- 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 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
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-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
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000801593 Pida Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZBIKORITPGTTGI-UHFFFAOYSA-N [acetyloxy(phenyl)-$l^{3}-iodanyl] acetate Chemical compound CC(=O)OI(OC(C)=O)C1=CC=CC=C1 ZBIKORITPGTTGI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 125000006160 pyromellitic dianhydride group Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
-
- 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
- C08G73/1057—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
- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention relates to the technical field of materials, and particularly relates to a polyimide material, and a preparation method and application thereof. The polyimide material prepared by the invention has a structure shown in a formula (I), wherein R is selected from diamine with a relative molecular mass of more than 260 and large volume or benzene ring number>2, removing residual groups after the amino end groups are removed by the aromatic diamine; ar is selected from a group remained after the terminal oxygen group of aliphatic dianhydride is removed or a group remained after the terminal oxygen group of aromatic dianhydride is removed; m and n are independently selected from natural numbers of 100-300. The polyimide material prepared by the invention has excellent solvent resistance, thermal stability, high glass transition temperature, light transmittance, low phase difference and low thermal expansion coefficient.
Description
Technical Field
The invention relates to the technical field of materials, and particularly relates to a polyimide material, and a preparation method and application thereof.
Background
In the field of displays, flexible and rollable Liquid Crystal Displays (LCDs) and organic light emitting diode displays (OLEDs) have become the direction of technological development. The most common material for manufacturing OLED and LCD display substrates and cover plates is glass at present, but the glass cannot meet the requirements of the new generation of flexible display screens due to the problems of being thick, heavy, hard and fragile. Compared with glass, the flexible polymer material with the characteristics of light weight, thinness and the like has inherent advantages, so that the polymer material can be used for the field of flexible display instead of glass. For example, polyethylene naphthalate (PEN) polymer materials and poly (cycloolefin) (COP) films have promise for applications in the display field, but cannot be widely used in the flexible display field due to their poor thermal stability, high retardation, and poor resistance to bending. Therefore, it is of great interest to provide polymer materials suitable for the display field.
Polyimide is a polymer having a repeating unit structure of imide ring (-CO-N-CO) in its main chain. They are generally classified into three types, aliphatic, aromatic and semi-aromatic, according to their chemical structures. The product forms mainly comprise polyimide films, plastics, fibers, adhesives and the like. Polyimide has excellent high temperature resistance and high insulating property, so that the polyimide is widely applied to the fields of aerospace, microelectronics, liquid crystal and the like. However, the conventional polyimide material also has the defects of high phase difference, poor thermal stability and the like, so that the application of the conventional polyimide material in the field of displays is limited.
Disclosure of Invention
Based on the above, the invention provides a polyimide material, and a preparation method and application thereof.
In one aspect of the present invention, a polyimide material is provided, wherein the polyimide material has a structure represented by formula (I):
wherein R is selected from bulky diamine with relative molecular mass of 260 or aromatic diamine with benzene ring number of 2, and the residual group after removing terminal amino;
ar is selected from a group remained after the terminal oxygen group of aliphatic dianhydride is removed or a group remained after the terminal oxygen group of aromatic dianhydride is removed;
m and n are independently selected from natural numbers of 100-300.
In one specific embodiment, R in formula (I) is selected from one of the groups of structures shown in formula 1 to formula 13:
in one specific embodiment, Ar in formula (I) is selected from one of the groups of structures represented by formula 14 to formula 29:
in another aspect of the present invention, a method for preparing the polyimide material is further provided, which comprises the following steps:
(1) mixing mixed dianhydride consisting of norbornane-2-spiro-2 '-cyclopentanone-5' -spiro-2 '-norbornyl-5, 5',6,6 '-tetracarboxylic dianhydride and other dianhydride, mixed diamine consisting of 4,4' -diamino-2, 2 '-bistrifluoromethylbiphenyl and other diamine and end-capping reagent in a solvent to prepare a polyamic acid solution, wherein the structural formula of the norbornane-2-spiro-2' -cyclopentanone-5 '-spiro-2' -norbornyl-5, 5',6,6' -tetracarboxylic dianhydride is shown in the specification
The structural formula of the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl is shown in the specification
The other dianhydride is dianhydride containing Ar group in the structure, and the other diamine is diamine containing R group in the structure; and
(2) and carrying out imidization treatment on the polyamic acid solution.
In one specific embodiment, the weight percentage of the norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornyl-5, 5',6,6' -tetracarboxylic dianhydride in the mixed dianhydride is 20-95%; and/or
The weight percentage of the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl in the mixed diamine is 20-95%.
In one specific embodiment, the capping agent is selected from at least one of maleic anhydride, phenylacetylene phthalic anhydride, nadic anhydride, and ethynyl dianhydride.
In one specific embodiment, the solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, γ -butyrolactone, propylene glycol methyl ether acetate, sulfolane, m-cresol, methyl sulfoxide, N-methylpyrrolidone, and diphenylsulfone.
In one embodiment, the method of imidization in step (2) is at least one of thermal imidization and chemical imidization.
In one specific embodiment, the heating temperature of the imine in the step (2) is 180-380 ℃, and the heating time is 5-60 min.
In one specific embodiment, the method further comprises the step of adding a catalyst and a dehydrating agent to the polyamic acid solution, wherein the catalyst is at least one of carbonate, bicarbonate, hydroxide, organic base, alkali metal salt of alcohol, metal hydride, pyridine, isoquinoline, methylpiperidine and triethylamine, and the dehydrating agent is at least one of acetic anhydride and trifluoroacetic anhydride.
In one specific embodiment, the method further comprises the step of reheating the material obtained by the imidization treatment, wherein the reheating temperature is 300-380 ℃ and the time is 0.5-3 min.
In another aspect of the present invention, there is further provided an application of the polyimide material as a substrate or a cover plate of a display, or in manufacturing a touch panel.
The invention introduces norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornane-5, 5',6,6' -tetracarboxylic dianhydride with rigid alicyclic structure and diamine with more benzene rings into the polyimide molecular structure, thereby destroying the orderliness of the polyimide molecular structure, reducing the phase difference of the polyimide material and being beneficial to improving the thermal stability and the light transmittance of the polyimide material.
And a blocking agent capable of crosslinking at high temperature is further introduced in the process of preparing the polyimide material, so that the entanglement effect among molecular chains is enhanced, the solvent resistance of the polyimide material is further improved, and the Coefficient of Thermal Expansion (CTE) of the polyimide material is reduced, so that the polyimide material has good thermal stability. The mutual matching of the monomers enables the finally prepared polyimide film to have excellent solvent resistance, thermal stability, high light transmittance and low phase difference. And the prepared polyimide material also has excellent properties of transparency, high glass transition temperature (Tg), low yellowness index and the like.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one aspect of the present invention, a polyimide material is provided, wherein the polyimide material has a structure represented by formula (I):
wherein R is selected from bulky diamine with relative molecular mass of 260 or aromatic diamine with benzene ring number of 2, and the residual group after removing terminal amino;
ar is selected from a group remained after the terminal oxygen group of aliphatic dianhydride is removed or a group remained after the terminal oxygen group of aromatic dianhydride is removed;
m and n are independently selected from natural numbers of 100-300.
According to the invention, researches show that dianhydride with a rigid alicyclic structure and diamine with a large number of benzene rings are introduced into a polyimide polymer structure to destroy the molecular structure order of the polyimide polymer, so that the light transmittance and the thermal stability of the polyimide film are effectively improved, and the phase difference is reduced.
In the present invention, as further illustration, the bulky diamine having a relative molecular mass of >260 or the aromatic diamine having a number of benzene rings of >2 is selected from 1, 3-bis (4-aminophenoxy) benzene (TPE-R), 1, 3-bis (3-aminophenoxy) benzene (1,3,3-APB), 1, 4-bis (4-aminophenoxy) benzene (TPE-Q), 4 '-bis (4-aminophenoxy) biphenyl (BAPB), 4' -bis (3-aminophenoxy) biphenyl (m-BAPB), 5(6) -1- (4-aminophenyl) -1,3, 3-trimethylindane (PIDA), 9-bis (4-aminophenyl) fluorene (BAFL), 9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA), At least one of 2,2 '-bis (4-aminophenoxyphenyl) propane (BAPP), 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane (HF-BAPP), 4' -bis (3-aminophenoxy) diphenyl sulfone (m-BAPS), 4 '-bis (4-aminophenoxy) diphenyl sulfone (BAPS), and 4,4' -bis (3-hexafluoropropyl-4-aminophenoxy) diphenyl sulfone (6F-BAPS). Specifically, the structural formula of each substance is as follows:
in the present invention, as a further explanation, the aliphatic dianhydride or the aromatic dianhydride is selected from 3,3,4',4' -biphenyltetracarboxylic dianhydride (BPDA), 2,3,3',4' -biphenyltetracarboxylic dianhydride (a-BPDA), 4 '-hexafluoroisopropylphthalic anhydride (6FDA), 4' -oxydihexafluoroisopropylphthalic anhydride (6F-CDA), 3,3,4',4' -diphenylsulfone tetracarboxylic dianhydride (DSDA), 3,3,4',4' -diphenylether tetracarboxylic dianhydride (ODPA), 2,3,3',4' -diphenylether tetracarboxylic dianhydride (a-ODPA), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoro dianhydride (6F-BPADA), hydrogenated pyromellitic dianhydride (HPMDA), cyclobutane tetracarboxylic dianhydride (CBDA), 2',3,3' -triphendiether dianhydride (3,3' -HQDPA), 2,3',3,4' -triphendiether dianhydride (3,4' -HQDPA), 3,3',4,4' -triphendiether dianhydride (4,4' -HQDPA), 1,2,3, 4-Butanetetracarboxylic Dianhydride (BDA), and 4- (2, 5-dioxytetrahydrofuran) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride (TDA). Specifically, the structural formula of each substance is as follows:
in another aspect of the present invention, a method for preparing the polyimide material is further provided, which comprises the following steps:
(1) mixing mixed dianhydride consisting of norbornane-2-spiro-2 '-cyclopentanone-5' -spiro-2 '-norbornyl-5, 5',6,6 '-tetracarboxylic dianhydride and other dianhydride, mixed diamine consisting of 4,4' -diamino-2, 2 '-bistrifluoromethylbiphenyl and other diamine and end-capping reagent in a solvent to prepare a polyamide acid solution, wherein the structural formula of the norbornane-2-spiro-2' -cyclopentanone-5 '-spiro-2' -norbornyl-5, 5',6,6' -tetracarboxylic dianhydride is shown in the specification
The structural formula of the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl is shown in the specification
The other dianhydride isDianhydride containing Ar group in the structure, and the other diamine is diamine containing R group in the structure; and
(2) and carrying out imidization treatment on the polyamic acid solution.
In the process of preparing the polyimide film, the end-capping reagent is introduced to enhance the entanglement among molecular chains, thereby reducing the Coefficient of Thermal Expansion (CTE) of the polyimide film and improving the thermal stability and solvent resistance of the polyimide film. The cooperation of the monomers enables the finally prepared polyimide film to have excellent solvent resistance, thermal stability, high glass transition temperature (Tg), high light transmittance and low retardation.
In the invention, as further illustration, the weight percentage content of the norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornyl-5, 5',6,6' -tetracarboxylic dianhydride in the mixed dianhydride is 20-95%; and/or
The weight percentage of the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl in the mixed diamine is 20-95%.
In the invention, as further illustration, the weight percentage content of the norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornyl-5, 5',6,6' -tetracarboxylic dianhydride in the mixed dianhydride is 50-70%; and/or
The weight percentage of the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl in the mixed diamine is 30-50%.
In the present invention, as a further explanation, the end capping agent is at least one selected from the group consisting of Maleic Anhydride (MAH), phenylacetylene phthalic anhydride (PEPA), norbornene dicarboxylic anhydride (NA), and ethynyl dicarboxylic anhydride (EPA). Specifically, the structural formula of each substance is as follows:
in the invention, as a further illustration, the weight percentage content of the added end-capping reagent is 0.01-2%. In a preferred embodiment, the capping agent is added in an amount of 0.2% by weight.
In the present invention, the solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, γ -butyrolactone, propylene glycol methyl ether acetate, sulfolane, m-cresol, methyl sulfoxide, N-methylpyrrolidone, and diphenylsulfone. In a preferred embodiment, the solvent is selected from N, N-dimethylformamide.
In the present invention, as a further explanation, the method of imidization in the step (2) is at least one of thermal imidization and chemical imidization.
In the present invention, as a further explanation, the heating temperature of the imidization in the step (2) is 180 ℃ to 380 ℃ and the heating time is 5min to 60 min. In a preferred embodiment, the imidization is carried out at a heating temperature of 300 ℃ for a heating time of 20 min.
In the present invention, as a further description, the method further includes a step of adding a catalyst and a dehydrating agent to the polyamic acid solution, the catalyst is at least one of carbonate, bicarbonate, hydroxide, organic base, alkali metal salt of alcohol, metal hydride, pyridine, isoquinoline, methylpiperidine and triethylamine, and the dehydrating agent is at least one of acetic anhydride and trifluoroacetic anhydride. In a preferred embodiment, the catalyst is pyridine and the dehydrating agent is acetic anhydride.
The present invention further includes a step of reheating the material obtained by the imidization treatment at a temperature of 300 to 380 ℃ for 0.5 to 3 minutes. In a preferred embodiment, the reheating is at a temperature of 360 ℃ for a period of 1 min.
In another aspect of the present invention, there is further provided an application of the polyimide material as a substrate or a cover plate of a display, or in manufacturing a touch panel.
The polyimide film of the present invention, the method for preparing the same, and the use thereof will be described in further detail below with reference to specific examples and comparative examples.
EXAMPLE 1 preparation of polyimide Material
60g N, N-dimethylacetamide, 3.2023g (10mmol) of 4,4' -diamino-2, 2' -bistrifluoromethylbiphenyl and 4.3249g (10mmol) of 4,4' -bistrifluoromethylbiphenyl(3-aminophenoxy) diphenyl sulfone was charged into a 250mL three-necked flask equipped with a nitrogen blanket and mechanical stirring, and stirred at 30 ℃ until completely dissolved to prepare a diamine solution. 5.3813g (14mmol) of norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornane-5, 5',6,6' -tetracarboxylic dianhydride, 1.7506g (5.95mmol) of 2,3,3',4' -biphenyltetracarboxylic dianhydride and 0.1721g (0.1mmol) of ethynyl dianhydride were added to the diamine solution, and the mixture was stirred in an ice-water bath for 20 hours to obtain a mixture having an apparent viscosity of 3.5X 104cPs, polyamic acid solution with 20% solid content.
Thermal imidization: at room temperature, 25g of the polyamic acid solution is defoamed in a vacuum drying oven for 3 hours, the defoamed solution is coated on a glass plate to form a film, then the film is placed in a nitrogen oven to be heated to 80 ℃ for 30min, then heated to 180 ℃ for 10min, then heated to 260 ℃ for 10min, then heated to 300 ℃ for 5min, and finally heated to 320 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, and soaking in hot water to remove the film from the glass plate to obtain the polyimide film. And performance tests were performed as shown in table 1.
Chemical imidization: 25g of the above polyamic acid solution was taken, 2.04g (20mmol) of acetic anhydride and 0.79g (10mmol) of pyridine were added thereto, and the mixture was stirred for 8 hours in an ice-water bath, followed by addition of 120g N, N-dimethylacetamide and dilution. The diluted solution was slowly poured into 1L of methanol stirred at a high speed to obtain white flocculent resin, and after filtering with a sand core funnel having a pore size of 30 μm, the resin was placed in a forced air drying oven at 100 ℃ to dry for 5 hours to obtain 5g of white flocculent resin. Then it was dissolved in 20g N, N-dimethylacetamide to give a viscosity of 3.6X 104cPs, polyimide solution with 20% solid content. At room temperature, defoaming the polyimide solution in a vacuum drying oven for 3 hours, coating the defoamed solution on a glass plate to form a film, then putting the film into a nitrogen oven, heating to 80 ℃ for 30min, then heating to 150 ℃ for 10min, then heating to 200 ℃ for 10min, then heating to 300 ℃ for 3min, and finally heating to 340 ℃ for 3 min. Closing the nitrogen oven, taking out the film for natural cooling, soaking in hot water to remove the film from the glass plate,and (5) preparing the polyimide film. And performance tests were performed as shown in table 1.
Example 2 preparation of polyimide Material
66g N, N-dimethylacetamide, 1.9214g (6mmol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl and 7.2583g (14mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl]Hexafluoropropane was charged into a 250mL three-necked flask equipped with nitrogen blanket and mechanical stirring, and stirred at 30 ℃ until completely dissolved to prepare a diamine solution. 5.3813g (10mmol) of norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornane-5, 5',6,6' -tetracarboxylic dianhydride, 1.9415g (9.9mmol) of cyclobutanetetracarboxylic dianhydride and 0.1961g (0.2mmol) of maleic anhydride are added into the diamine solution, and the mixture is stirred for 20 hours under the condition of ice-water bath to obtain the product with the apparent viscosity of 2.3X 104cPs, polyamic acid solution with 20% solid content.
Thermal imidization: at room temperature, 25g of the polyamic acid solution is defoamed in a vacuum drying oven for 3 hours, the defoamed solution is coated on a glass plate to form a film, then the film is placed in a nitrogen oven to be heated to 80 ℃ for 30min, then heated to 150 ℃ for 10min, then heated to 250 ℃ for 10min, then heated to 300 ℃ for 5min, and finally heated to 340 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, soaking in hot water to remove the film from the glass plate, and preparing the polyimide film. And performance tests were performed as shown in table 1.
Chemical imidization: 25g of the above polyamic acid solution was taken, 2.04g (20mmol) of acetic anhydride and 0.79g (10mmol) of pyridine were added thereto, and the mixture was stirred in an ice-water bath for 12 hours, followed by addition of 120g N, N-dimethylacetamide and dilution. The diluted solution was slowly poured into 1L of methanol stirred at a high speed to obtain white flocculent resin, and after filtering with a sand core funnel having a pore size of 30 μm, the resin was placed in a forced air drying oven at 100 ℃ to dry for 5 hours to obtain 5g of white flocculent resin. Then it was dissolved in 20g N, N-dimethylacetamide to give a viscosity of 2.6X 104cPs, polyimide solution with 20% solid content. Defoaming the polyimide solution in a vacuum drying oven for 2 hours at room temperature, coating the defoamed solution on a glass plate to form a film, and then placing the film on the glass plateHeating in a nitrogen oven to 80 deg.C for 30min, heating to 120 deg.C for 10min, heating to 180 deg.C for 10min, heating to 250 deg.C for 3min, and heating to 340 deg.C for 3 min. And closing the nitrogen oven, taking out the film, naturally cooling, and soaking in hot water to remove the film from the glass plate to obtain the polyimide film. And performance tests were performed as shown in table 1.
Example 3 preparation of polyimide Material
58g N, N-dimethylacetamide, 3.2023g (10mmol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl and 3.4844g (10mmol) of 9, 9-bis (4-aminophenyl) fluorene were added to a 250mL three-necked flask equipped with nitrogen blanket and mechanical stirring and stirred at 30 ℃ until completely dissolved to prepare a diamine solution. 6.9189g (18mmol) of norbornane-2-spiro-2 '-cyclopentanone-5' -spiro-2 '-norbornane-5, 5',6,6 '-tetracarboxylic dianhydride, 0.8663g (1.95mmol) of 4,4' -hexafluoroisopropylphthalic anhydride and 0.1642g (0.1mmol) of nadic anhydride were then added to the diamine solution, and the mixture was stirred in an ice-water bath for 30 hours to obtain a mixture having an apparent viscosity of 4.2X 104cPs, polyamic acid solution with 20% solid content.
Thermal imidization: at room temperature, 25g of the polyamic acid solution is defoamed in a vacuum drying oven for 3 hours, the defoamed solution is coated on a glass plate to form a film, then the film is placed in a nitrogen oven to be heated to 80 ℃ for 30min, then heated to 150 ℃ for 10min, then heated to 250 ℃ for 10min, then heated to 280 ℃ for 5min, and finally heated to 300 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, soaking in hot water to remove the film from the glass plate, and preparing the polyimide film. And performance tests were performed as shown in table 1.
Chemical imidization: 25g of the above polyamic acid solution was added with 2.04g (20mmol) of acetic anhydride and 0.79g (10mmol) of pyridine, and stirred in an ice-water bath for 12 hours, followed by dilution with 140g N, N-dimethylacetamide. Slowly pouring the diluted solution into 1L methanol stirred at high speed to obtain white flocculent resin, filtering with sand core funnel with aperture of 30 μm, and drying in blast drying oven at 100 deg.C for 5 hr to obtain 6g white flocculent resinAnd (3) flocculent resin. It was then dissolved in 24g N, N-dimethylacetamide to give a viscosity of 4.6X 104cPs, polyimide solution with 20% solid content. At room temperature, defoaming the polyimide solution in a vacuum drying oven for 5 hours, coating the defoamed solution on a glass plate to form a film, then putting the film into a nitrogen oven, heating to 80 ℃ for 30min, then heating to 120 ℃ for 10min, then heating to 180 ℃ for 10min, then heating to 250 ℃ for 3min, and finally heating to 300 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, and soaking in hot water to remove the film from the glass plate to obtain the polyimide film. And performance tests were performed as shown in table 1.
Example 4 preparation of polyimide Material
54g N, N-dimethylacetamide, 5.1237g (16mmol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl and 1.7133g (4mmol) of 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene were added to a 250mL three-necked flask equipped with nitrogen blanket and mechanical stirring and stirred at 30 ℃ until completely dissolved to prepare a diamine solution. Then adding 1.5375g (4mmol) of norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornane-5, 5',6,6' -tetracarboxylic dianhydride, 4.9018g (15.8mmol) of 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride and 0.0993g (0.4mmol) of phenylacetylene phthalic anhydride into the diamine solution, and stirring for 24 hours under the condition of ice-water bath to obtain the product with the apparent viscosity of 5.2X 104cPs, polyamic acid solution with 20% solid content.
Thermal imidization: at room temperature, 25g of the polyamic acid solution is defoamed in a vacuum drying oven for 5 hours, the defoamed solution is coated on a glass plate to form a film, then the film is placed in a nitrogen oven to be heated to 80 ℃ for 40min, then to 160 ℃ for 10min, then to 220 ℃ for 10min, then to 280 ℃ for 5min, then to 300 ℃ for 5min, and finally to 380 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, soaking in hot water to remove the film from the glass plate, and preparing the polyimide film. And performance tests were performed as shown in table 1.
Chemical imidization: 25g of the above polyamic acid solution was added2.04g (20mmol) of acetic anhydride and 0.79g (10mmol) of pyridine are added and stirred in an ice-water bath for 16h, then 160g N, N-dimethylacetamide is added for dilution. The diluted solution was slowly poured into 1.5L of methanol stirred at a high speed to obtain white flocculent resin, and after filtering with a sand core funnel having a pore size of 30 μm, it was placed in a forced air drying oven at 100 ℃ to dry for 5 hours to obtain 6g of white flocculent resin. It was then dissolved in 24g N, N-dimethylacetamide to give a viscosity of 5.6X 104cPs, polyimide solution with 20% solid content. At room temperature, defoaming the polyimide solution in a vacuum drying oven for 5 hours, coating the defoamed solution on a glass plate to form a film, then putting the film into a nitrogen oven, heating to 80 ℃ for 30min, then heating to 120 ℃ for 10min, then heating to 180 ℃ for 10min, then heating to 250 ℃ for 3min, then heating to 300 ℃ for 5min, and finally heating to 380 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, and soaking in hot water to remove the film from the glass plate to obtain the polyimide film. And performance tests were performed as shown in table 1.
EXAMPLE 5 preparation of polyimide Material
A diamine solution was prepared by charging 58g N, N-dimethylacetamide, 1.92143g (6mmol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl and 4.0926g (14mmol) of 1, 3-bis (4-aminophenoxy) benzene into a 250mL three-necked flask equipped with nitrogen blanket and mechanical stirring and stirring at 30 ℃ until complete dissolution. 5.3813g (14mmol) of norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornane-5, 5',6,6' -tetracarboxylic dianhydride, 2.3334g (5.8mmol) of 3,3',4,4' -triphendiether dianhydride and 0.0689g (0.4mmol) of ethynyl dianhydride were added to the diamine solution, and the mixture was stirred in an ice-water bath for 20 hours to obtain a solution having an apparent viscosity of 2.5X 104cPs, polyamic acid solution with 20% solid content.
Thermal imidization: at room temperature, 25g of the polyamic acid solution is defoamed in a vacuum drying oven for 3 hours, the defoamed solution is coated on a glass plate to form a film, then the film is placed in a nitrogen oven to be heated to 80 ℃ for 40min, then heated to 120 ℃ for 10min, then heated to 220 ℃ for 10min, then heated to 280 ℃ for 5min, then heated to 300 ℃ for 5min, and finally heated to 340 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, soaking in hot water to remove the film from the glass plate, and preparing the polyimide film. And performance tests were performed as shown in table 1.
Chemical imidization: 25g of the above polyamic acid solution was taken, 2.04g (20mmol) of acetic anhydride and 0.79g (10mmol) of pyridine were added thereto, and the mixture was stirred for 8 hours in an ice-water bath, followed by addition of 120g N, N-dimethylacetamide and dilution. The diluted solution was slowly poured into 1.5L of methanol stirred at a high speed to obtain white flocculent resin, and after filtering with a sand core funnel having a pore size of 30 μm, it was placed in a forced air drying oven at 100 ℃ to dry for 5 hours to obtain 6g of white flocculent resin. It was then dissolved in 24g N, N-dimethylacetamide to give a viscosity of 2.6X 104cPs, polyimide solution with 20% solid content. At room temperature, defoaming the polyimide solution in a vacuum drying oven for 5 hours, coating the defoamed solution on a glass plate to form a film, then putting the film into a nitrogen oven, heating to 80 ℃ for 30min, then heating to 120 ℃ for 10min, then heating to 180 ℃ for 10min, then heating to 250 ℃ for 3min, then heating to 300 ℃ for 5min, and finally heating to 340 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, and soaking in hot water to remove the film from the glass plate to obtain the polyimide film. And performance tests were performed as shown in table 1.
Comparative example 1 preparation of polyimide Material
60g N, N-dimethylacetamide, 3.2023g (10mmol) of 4,4' -diamino-2, 2' -bistrifluoromethylbiphenyl and 4.3249g (10mmol) of 4,4' -bis (3-aminophenoxy) diphenylsulfone were added to a 250mL three-necked flask equipped with nitrogen blanket and mechanical stirring and stirred at 30 ℃ until completely dissolved to prepare a diamine solution. 5.3813g (14mmol) of norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornane-5, 5',6,6' -tetracarboxylic dianhydride and 1.7653g (6mmol) of 2,3,3',4' -biphenyltetracarboxylic dianhydride were added to the diamine solution, and the mixture was stirred in an ice-water bath for 20 hours to obtain a mixture having an apparent viscosity of 3.5X 104cPs solid content 20% polyamic acid solutionAnd (4) liquid.
Thermal imidization: at room temperature, 25g of the polyamic acid solution is defoamed in a vacuum drying oven for 3 hours, the defoamed solution is coated on a glass plate to form a film, then the film is placed in a nitrogen oven to be heated to 80 ℃ for 30min, then heated to 180 ℃ for 10min, then heated to 260 ℃ for 10min, then heated to 300 ℃ for 5min, and finally heated to 320 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, and soaking in hot water to remove the film from the glass plate to obtain the polyimide film. And performance tests were performed as shown in table 1.
Chemical imidization: 25g of the above polyamic acid solution was taken, 2.04g (20mmol) of acetic anhydride and 0.79g (10mmol) of pyridine were added thereto, and the mixture was stirred for 8 hours in an ice-water bath, followed by addition of 120g N, N-dimethylacetamide and dilution. The diluted solution was slowly poured into 1L of methanol stirred at a high speed to obtain white flocculent resin, and after filtering with a sand core funnel having a pore size of 30 μm, the resin was placed in a forced air drying oven at 100 ℃ to dry for 5 hours to obtain 5g of white flocculent resin. Then it was dissolved in 20g N, N-dimethylacetamide to give a viscosity of 3.6X 104cPs, polyimide solution with 20% solid content. At room temperature, defoaming the polyimide solution in a vacuum drying oven for 3 hours, coating the defoamed solution on a glass plate to form a film, then putting the film into a nitrogen oven, heating to 80 ℃ for 30min, then heating to 150 ℃ for 10min, then heating to 200 ℃ for 10min, and finally heating to 300 ℃ for 3 min. And closing the nitrogen oven, taking out the film, naturally cooling, and soaking in hot water to remove the film from the glass plate to obtain the polyimide film. And performance tests were performed as shown in table 1.
Comparative example 2 preparation of polyimide Material
A diamine solution was prepared by charging a solution of 56g N, N-dimethylacetamide diamine, 6.4046g (20mmol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl into a 250mL three-necked flask equipped with nitrogen blanket and mechanical stirring and stirring at 30 ℃ until completely dissolved. 7.6876g (20mmol) of norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornyl-5, 5',6,6' -tetracarboxylic dianhydride was added to the diamine solutionStirring for 30h under the condition of water bath to obtain the product with the apparent viscosity of 2.8 multiplied by 104cPs, polyamic acid solution with 20% solid content.
Thermal imidization: at room temperature, 25g of the polyamic acid solution is defoamed in a vacuum drying oven for 3 hours, the defoamed solution is coated on a glass plate to form a film, then the film is placed in a nitrogen oven to be heated to 80 ℃ for 40min, then heated to 120 ℃ for 10min, then heated to 220 ℃ for 10min, then heated to 280 ℃ for 5min, then heated to 300 ℃ for 5min, and finally heated to 340 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, soaking in hot water to remove the film from the glass plate, and preparing the polyimide film. And performance tests were performed as shown in table 1.
Chemical imidization: 25g of the above polyamic acid solution was taken, 2.04g (20mmol) of acetic anhydride and 0.79g (10mmol) of pyridine were added thereto, and the mixture was stirred in an ice-water bath for 18 hours, followed by dilution with 120g N, N-dimethylacetamide. The diluted solution was slowly poured into 1.5L of methanol stirred at a high speed to obtain white flocculent resin, and after filtering with a sand core funnel having a pore size of 30 μm, it was placed in a forced air drying oven at 100 ℃ to dry for 5 hours to obtain 6g of white flocculent resin. Then it was dissolved in 24g N, N-dimethylacetamide to give a viscosity of 3.1X 104cPs, polyimide solution with 20% solid content. At room temperature, defoaming the polyimide solution in a vacuum drying oven for 5 hours, coating the defoamed solution on a glass plate to form a film, then putting the film into a nitrogen oven, heating to 80 ℃ for 30min, then heating to 120 ℃ for 10min, then heating to 180 ℃ for 10min, then heating to 250 ℃ for 3min, then heating to 300 ℃ for 5min, and finally heating to 340 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, and soaking in hot water to remove the film from the glass plate to obtain the polyimide film. And performance tests were performed as shown in table 1.
Comparative example 3 preparation of polyimide Material
50g N, N-dimethylacetamide, 4.0046g (20mmol) of 4,4' -diaminodiphenyl ether are placed in a 250mL three-necked flask equipped with nitrogen blanket and mechanical stirring, andthe diamine solution was prepared by stirring at 30 ℃ until completely dissolved. 7.6876g (20mmol) of norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornyl-5, 5',6,6' -tetracarboxylic dianhydride was added to the diamine solution, and the mixture was stirred for 30 hours in an ice-water bath to obtain a mixture having an apparent viscosity of 2.8X 104cPs, polyamic acid solution with 20% solid content.
Thermal imidization: at room temperature, 25g of the polyamic acid solution is defoamed in a vacuum drying oven for 3 hours, the defoamed solution is coated on a glass plate to form a film, then the film is placed in a nitrogen oven to be heated to 80 ℃ for 40min, then heated to 120 ℃ for 10min, then heated to 220 ℃ for 10min, then heated to 280 ℃ for 5min, then heated to 300 ℃ for 5min, and finally heated to 320 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, soaking in hot water to remove the film from the glass plate, and preparing the polyimide film. And performance tests were performed as shown in table 1.
Chemical imidization: 25g of the above polyamic acid solution was taken, 2.04g (20mmol) of acetic anhydride and 0.79g (10mmol) of pyridine were added thereto, and the mixture was stirred in an ice-water bath for 18 hours, followed by dilution with 120g N, N-dimethylacetamide. The diluted solution was slowly poured into 1.5L of methanol stirred at a high speed to obtain white flocculent resin, and after filtering with a sand core funnel having a pore size of 30 μm, it was placed in a forced air drying oven at 100 ℃ to dry for 5 hours to obtain 6g of white flocculent resin. Then it was dissolved in 24g N, N-dimethylacetamide to give a viscosity of 3.1X 104cPs, polyimide solution with 20% solid content. At room temperature, defoaming the polyimide solution in a vacuum drying oven for 5 hours, coating the defoamed solution on a glass plate to form a film, then putting the film into a nitrogen oven, heating to 80 ℃ for 30min, then heating to 120 ℃ for 10min, then heating to 180 ℃ for 10min, then heating to 250 ℃ for 3min, then heating to 300 ℃ for 5min, and finally heating to 320 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, and soaking in hot water to remove the film from the glass plate to obtain the polyimide film. And performance tests were performed as shown in table 1.
Comparative example 4 preparation of polyimide Material
A diamine solution was prepared by charging 50g N, N-dimethylacetamide and 6.4046g (20mmol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl into a 250mL three-necked flask equipped with nitrogen blanket and mechanical stirring and stirring at 30 ℃ until completely dissolved. 6.2048g (20mmol) of 3,3,4',4' -diphenyl ether tetracarboxylic dianhydride was then added to the diamine solution and stirred for 24 hours in an ice-water bath to give an apparent viscosity of 5.8X 104cPs, polyamic acid solution with 20% solid content.
Thermal imidization: at room temperature, 25g of the polyamic acid solution is defoamed in a vacuum drying oven for 3 hours, the defoamed solution is coated on a glass plate to form a film, then the film is placed in a nitrogen oven to be heated to 80 ℃ for 40min, then heated to 120 ℃ for 10min, then heated to 220 ℃ for 10min, then heated to 280 ℃ for 5min, then heated to 300 ℃ for 5min, and finally heated to 340 ℃ for 5 min. And closing the nitrogen oven, taking out the film, naturally cooling, soaking in hot water to remove the film from the glass plate, and preparing the polyimide film. And performance tests were performed as shown in table 1.
Chemical imidization: 25g of the above polyamic acid solution was taken, 2.04g (20mmol) of acetic anhydride and 0.79g (10mmol) of pyridine were added thereto, and the mixture was stirred in an ice-water bath for 12 hours, followed by addition of 120g N, N-dimethylacetamide and dilution. The diluted solution was slowly poured into 1.5L of methanol stirred at a high speed to obtain white flocculent resin, and after filtering with a sand core funnel having a pore size of 30 μm, it was placed in a forced air drying oven at 100 ℃ to dry for 5 hours to obtain 6g of white flocculent resin. It was then dissolved in 24g N, N-dimethylacetamide to give a viscosity of 2.6X 104cPs, polyimide solution with 20% solid content. At room temperature, defoaming the polyimide solution in a vacuum drying oven for 5 hours, coating the defoamed solution on a glass plate to form a film, then putting the film into a nitrogen oven, heating to 80 ℃ for 30min, then heating to 120 ℃ for 10min, then heating to 180 ℃ for 10min, then heating to 250 ℃ for 3min, then heating to 300 ℃ for 5min, and finally heating to 340 ℃ for 5 min. Closing the nitrogen oven, taking out the film naturallyThe film was removed from the glass plate by immersion in hot water after cooling to obtain a polyimide film. And performance tests were performed as shown in table 1.
Performance testing
The phase difference of the polyimide film was measured using a Japanese Denshi electronic model RETS-100X phase difference measuring device; the glass transition temperature (Tg) was measured using a TA differential scanning calorimeter model Q20, the range of measurements being: the temperature rise rate is 3K/min at 50-400 ℃; testing the Coefficient of Thermal Expansion (CTE) by using a thermal mechanical analyzer with model TMA 450EM of TA company in America, wherein the temperature range is 25-350 ℃, the heating rate is 5K/min, the load is 50mN, and the CTE value of 100-200 ℃ is marked; the apparent viscosities of the polyamic acid and polyimide solutions were measured at 20 ℃ using a Bohler fly model DV2T apparent viscometer; measuring the light transmittance and the yellowness index of the polyimide film under 400 nm-750 nm by using a UV-visible light spectrometer (Shimadzu UV 2450); soaking equal-mass and equal-volume polyimide films in equal-volume propylene glycol methyl ether acetate, isopropanol, diacetone alcohol, ferric trichloride, hydrochloric acid, potassium chloride, nitric acid, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, ethylenediamine and N-methylpyrrolidone solvents for 10min at room temperature respectively to test the solvent resistance.
TABLE 1 statistical table for polyimide film performance test
Experimental results show that the phase difference can be reduced and the solvent resistance can be improved by regulating and controlling the structure of the polyimide material, and the thermal expansion coefficient of the polyimide material can be further reduced and the thermal stability of the polyimide material can be improved by selecting a proper end-capping reagent.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. A polyimide material, wherein the polyimide material has a structure represented by formula (I):
wherein R is selected from bulky diamine with relative molecular mass of 260 or aromatic diamine with benzene ring number of 2, and the residual group after removing terminal amino;
ar is selected from a group remained after the terminal oxygen group of aliphatic dianhydride is removed or a group remained after the terminal oxygen group of aromatic dianhydride is removed;
m and n are independently selected from natural numbers of 100-300.
2. The polyimide material according to claim 1, wherein R in formula (I) is selected from one of groups having structures represented by formula 1 to formula 13:
3. the polyimide material according to claim 1 or 2, wherein Ar in formula (I) is one selected from the group consisting of structures represented by formulae 14 to 29:
4. the method for preparing a polyimide material according to any one of claims 1 to 3, comprising the steps of:
(1) mixing mixed dianhydride consisting of norbornane-2-spiro-2 '-cyclopentanone-5' -spiro-2 '-norbornyl-5, 5',6,6 '-tetracarboxylic dianhydride and other dianhydride, mixed diamine consisting of 4,4' -diamino-2, 2 '-bistrifluoromethylbiphenyl and other diamine and end-capping reagent in a solvent to prepare a polyamic acid solution, wherein the structural formula of the norbornane-2-spiro-2' -cyclopentanone-5 '-spiro-2' -norbornyl-5, 5',6,6' -tetracarboxylic dianhydride is shown in the specification
The structural formula of the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl is shown in the specification
The other dianhydride is dianhydride containing Ar group in the structure, and the other diamine is diamine containing R group in the structure; and
(2) and carrying out imidization treatment on the polyamic acid solution.
5. The preparation method of the polyimide material according to claim 4, wherein the weight percentage of the norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 ' -norbornyl-5, 5',6,6' -tetracarboxylic dianhydride in the mixed dianhydride is 20-95%; and/or
The weight percentage content of the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl in the mixed diamine is 20-95%.
6. The method of claim 4, wherein the end-capping agent is at least one selected from the group consisting of maleic anhydride, phenylacetylene phthalic anhydride, nadic anhydride, and ethynyl dianhydride.
7. The method for producing a polyimide material according to claim 6, wherein the solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, γ -butyrolactone, propylene glycol methyl ether acetate, sulfolane, m-cresol, methyl sulfoxide, N-methylpyrrolidone, and diphenylsulfone.
8. The method of preparing a polyimide material according to claim 7, wherein the imidization in the step (2) is at least one of thermal imidization and chemical imidization.
9. The method for preparing a polyimide material according to claim 8, wherein the heating temperature of the imidization in the step (2) is 180 ℃ to 380 ℃ and the heating time is 5min to 60 min.
10. The method of preparing a polyimide material according to any one of claims 5 to 9, further comprising a step of adding a catalyst and a dehydrating agent to the polyamic acid solution, wherein the catalyst is at least one of carbonate, bicarbonate, hydroxide, organic base, alkali metal salt of alcohol, metal hydride, pyridine, isoquinoline, methylpiperidine and triethylamine, and the dehydrating agent is at least one of acetic anhydride and trifluoroacetic anhydride.
11. The method for preparing a polyimide material according to any one of claims 5 to 9, further comprising a step of reheating the material obtained by the imidization treatment, wherein the reheating temperature is 300 ℃ to 380 ℃ and the time is 0.5min to 3 min.
12. Use of the polyimide material according to any one of claims 1 to 3 as a substrate or a cover plate of a display or in the manufacture of a touch screen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011527391.4A CN112646183A (en) | 2020-12-22 | 2020-12-22 | Polyimide material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011527391.4A CN112646183A (en) | 2020-12-22 | 2020-12-22 | Polyimide material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112646183A true CN112646183A (en) | 2021-04-13 |
Family
ID=75358950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011527391.4A Pending CN112646183A (en) | 2020-12-22 | 2020-12-22 | Polyimide material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112646183A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372554A (en) * | 2021-06-10 | 2021-09-10 | 中国科学院宁波材料技术与工程研究所 | Semi-alicyclic polyimide and application of film thereof in gas separation |
| CN113388108A (en) * | 2021-06-30 | 2021-09-14 | 宁波长阳科技股份有限公司 | Polyimide resin with self-repairing function, polyimide film, preparation method of polyimide film and flexible foldable display screen cover plate base film |
| CN115254061A (en) * | 2022-08-15 | 2022-11-01 | 齐齐哈尔大学 | Preparation method of ultrahigh cross-linked porous organic polymer iodine adsorbent |
| CN115746301A (en) * | 2022-12-02 | 2023-03-07 | 慧创(东莞)材料技术有限责任公司 | High-transparency polyimide film containing benzonorbornene structure and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107001662A (en) * | 2014-10-23 | 2017-08-01 | 宇部兴产株式会社 | Polyimide film, polyimide precursor and polyimides |
| CN107108886A (en) * | 2014-10-23 | 2017-08-29 | 宇部兴产株式会社 | Polyimide precursor, polyimides and polyimide film |
| CN108822296A (en) * | 2018-06-28 | 2018-11-16 | 上海交通大学 | A kind of all aromatic transparent polyimide film and preparation method thereof |
| CN109922956A (en) * | 2016-11-11 | 2019-06-21 | 宇部兴产株式会社 | Laminate comprising polyimide film and hard conating |
| CN110092908A (en) * | 2019-04-03 | 2019-08-06 | 中国科学院化学研究所 | A kind of Kapton and its preparation method and application |
| CN110790929A (en) * | 2019-09-29 | 2020-02-14 | 上海金門量子科技有限公司 | Colorless transparent high-modulus polyimide film and preparation method thereof |
| CN111133033A (en) * | 2017-09-29 | 2020-05-08 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish, and polyimide film |
| CN111133032A (en) * | 2017-09-29 | 2020-05-08 | 三菱瓦斯化学株式会社 | Polyimide, polyimide varnish, and polyimide film |
| CN111662473A (en) * | 2020-07-24 | 2020-09-15 | 浙江道明光电科技有限公司 | Preparation method of low-yellow-index colorless transparent polyimide film |
| CN111757904A (en) * | 2017-12-28 | 2020-10-09 | 宇部兴产株式会社 | Polyimide precursor, polyimide film, varnish, and substrate |
| CN111770951A (en) * | 2019-02-01 | 2020-10-13 | 胜高科技股份有限公司 | Polyimide compound and molded article comprising same |
| CN112041371A (en) * | 2018-05-01 | 2020-12-04 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish, and polyimide film |
-
2020
- 2020-12-22 CN CN202011527391.4A patent/CN112646183A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107001662A (en) * | 2014-10-23 | 2017-08-01 | 宇部兴产株式会社 | Polyimide film, polyimide precursor and polyimides |
| CN107108886A (en) * | 2014-10-23 | 2017-08-29 | 宇部兴产株式会社 | Polyimide precursor, polyimides and polyimide film |
| CN109922956A (en) * | 2016-11-11 | 2019-06-21 | 宇部兴产株式会社 | Laminate comprising polyimide film and hard conating |
| CN111133033A (en) * | 2017-09-29 | 2020-05-08 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish, and polyimide film |
| CN111133032A (en) * | 2017-09-29 | 2020-05-08 | 三菱瓦斯化学株式会社 | Polyimide, polyimide varnish, and polyimide film |
| CN111757904A (en) * | 2017-12-28 | 2020-10-09 | 宇部兴产株式会社 | Polyimide precursor, polyimide film, varnish, and substrate |
| CN112041371A (en) * | 2018-05-01 | 2020-12-04 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide varnish, and polyimide film |
| CN108822296A (en) * | 2018-06-28 | 2018-11-16 | 上海交通大学 | A kind of all aromatic transparent polyimide film and preparation method thereof |
| CN111770951A (en) * | 2019-02-01 | 2020-10-13 | 胜高科技股份有限公司 | Polyimide compound and molded article comprising same |
| CN110092908A (en) * | 2019-04-03 | 2019-08-06 | 中国科学院化学研究所 | A kind of Kapton and its preparation method and application |
| CN110790929A (en) * | 2019-09-29 | 2020-02-14 | 上海金門量子科技有限公司 | Colorless transparent high-modulus polyimide film and preparation method thereof |
| CN111662473A (en) * | 2020-07-24 | 2020-09-15 | 浙江道明光电科技有限公司 | Preparation method of low-yellow-index colorless transparent polyimide film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372554A (en) * | 2021-06-10 | 2021-09-10 | 中国科学院宁波材料技术与工程研究所 | Semi-alicyclic polyimide and application of film thereof in gas separation |
| CN113372554B (en) * | 2021-06-10 | 2022-08-16 | 中国科学院宁波材料技术与工程研究所 | Semi-alicyclic polyimide and application of film thereof in gas separation |
| CN113388108A (en) * | 2021-06-30 | 2021-09-14 | 宁波长阳科技股份有限公司 | Polyimide resin with self-repairing function, polyimide film, preparation method of polyimide film and flexible foldable display screen cover plate base film |
| CN115254061A (en) * | 2022-08-15 | 2022-11-01 | 齐齐哈尔大学 | Preparation method of ultrahigh cross-linked porous organic polymer iodine adsorbent |
| CN115746301A (en) * | 2022-12-02 | 2023-03-07 | 慧创(东莞)材料技术有限责任公司 | High-transparency polyimide film containing benzonorbornene structure and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI630223B (en) | Polyamide-imide precursor composition, polyamide-imide film and display device | |
| US9061474B2 (en) | Transparent polyimide film and preparation method thereof | |
| CN112646183A (en) | Polyimide material and preparation method and application thereof | |
| JP2018522105A (en) | Polyamide-imide precursor, polyamide-imide film, and display element including the same | |
| KR102059703B1 (en) | Polyamic acid solution composition and polyimide | |
| JP6940507B2 (en) | Polyamic acid, polyamic acid solution, polyimide, polyimide film, laminate and flexible device, and method for producing polyimide film. | |
| TW201734132A (en) | Polyamic acid, polyimide, polyamic acid solution, polyimide laminate, flexible device substrate, and method for producing them | |
| CN113227206B (en) | Imide-amic acid copolymer, process for producing the same, varnish, and polyimide film | |
| WO2008072915A1 (en) | Polyimide resin and liquid crystal alignment layer and polyimide film using the same | |
| CN102634022A (en) | Colorless highly-transparent polyimide film as well as preparation method and application thereof | |
| TWI792303B (en) | A kind of polyimide film and its preparation method and application | |
| WO2022133722A1 (en) | Polyimide material and preparation method therefor and application thereof | |
| US20100048861A1 (en) | Polyimide resin and liquid crystal alignment layer and polyimide film using the same | |
| KR20070017001A (en) | Low Color Polyimide Compositions Useful in Optical Type Applications and Methods and Compositions Relating Thereto | |
| JP7292260B2 (en) | Polyamic acid and its manufacturing method, polyamic acid solution, polyimide, polyimide film, laminate and its manufacturing method, flexible device and its manufacturing method | |
| KR20150031434A (en) | Polyamide acid, polyimide, polyamide acid solution, and use of polyimide | |
| CN110760062A (en) | Optical film, transparent substrate, image display device and solar cell | |
| CN111073008A (en) | Low-yellowing colorless transparent polyimide film and preparation method thereof | |
| JP7084755B2 (en) | A method for producing a polyamic acid, a polyamic acid solution, a polyimide, a polyimide film, a laminate and a flexible device, and a polyimide film. | |
| JP7349253B2 (en) | A polyamic acid, a polyamic acid solution, a polyimide, a polyimide film, a laminate, a flexible device, and a method for producing a polyimide film. | |
| JP7172981B2 (en) | BASE FILM FOR TRANSPARENT ELECTRODE AND METHOD FOR MANUFACTURING THE SAME | |
| CN108587163B (en) | High-transparency low-expansion polyimide film and preparation method and application thereof | |
| CN116199883A (en) | Polyimide resin, polyimide film, preparation method and flexible equipment | |
| WO2021132196A1 (en) | Polyimide resin, polyimide varnish, and polyimide film | |
| CN114085378B (en) | Polyamide acid solution and preparation method thereof, polyimide film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210413 |