CN117343325A - Polyimide, transparent polyimide film material and preparation method thereof - Google Patents
Polyimide, transparent polyimide film material and preparation method thereof Download PDFInfo
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- CN117343325A CN117343325A CN202311326683.5A CN202311326683A CN117343325A CN 117343325 A CN117343325 A CN 117343325A CN 202311326683 A CN202311326683 A CN 202311326683A CN 117343325 A CN117343325 A CN 117343325A
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- diamine
- polyimide
- dianhydride
- anhydride
- polyimide film
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 90
- 239000004642 Polyimide Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 150000004985 diamines Chemical class 0.000 claims abstract description 91
- 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 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 43
- 239000011521 glass Substances 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 8
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- -1 diphenyl anhydride Chemical class 0.000 claims description 4
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 claims description 3
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 3
- 229960005206 pyrazinamide Drugs 0.000 claims description 3
- IPEHBUMCGVEMRF-UHFFFAOYSA-N pyrazinecarboxamide Chemical compound NC(=O)C1=CN=CC=N1 IPEHBUMCGVEMRF-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- AGULWIQIYWWFBJ-UHFFFAOYSA-N 3,4-dichlorofuran-2,5-dione Chemical compound ClC1=C(Cl)C(=O)OC1=O AGULWIQIYWWFBJ-UHFFFAOYSA-N 0.000 claims description 2
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical compound ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 claims description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- BJDDKZDZTHIIJB-UHFFFAOYSA-N 4,5,6,7-tetrafluoro-2-benzofuran-1,3-dione Chemical compound FC1=C(F)C(F)=C2C(=O)OC(=O)C2=C1F BJDDKZDZTHIIJB-UHFFFAOYSA-N 0.000 claims description 2
- WWJAZKZLSDRAIV-UHFFFAOYSA-N 4-fluoro-2-benzofuran-1,3-dione Chemical compound FC1=CC=CC2=C1C(=O)OC2=O WWJAZKZLSDRAIV-UHFFFAOYSA-N 0.000 claims description 2
- JYCTWJFSRDBYJX-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3a,4,5,9b-tetrahydrobenzo[e][2]benzofuran-1,3-dione Chemical compound O=C1OC(=O)CC1C1C2=CC=CC=C2C(C(=O)OC2=O)C2C1 JYCTWJFSRDBYJX-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 claims description 2
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 claims description 2
- 229960003805 amantadine Drugs 0.000 claims description 2
- URSBMMUQJIMLKA-UHFFFAOYSA-N azulen-2-amine Chemical compound C1=CC=CC2=CC(N)=CC2=C1 URSBMMUQJIMLKA-UHFFFAOYSA-N 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- GECHUMIMRBOMGK-UHFFFAOYSA-N sulfapyridine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=CC=CC=N1 GECHUMIMRBOMGK-UHFFFAOYSA-N 0.000 claims description 2
- 229960002211 sulfapyridine Drugs 0.000 claims description 2
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 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 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 10
- 238000007790 scraping Methods 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920005575 poly(amic acid) Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RXYVNNWGXQRJAC-UHFFFAOYSA-N 1-chloro-1-[3-(trifluoromethyl)phenyl]propan-2-one Chemical compound CC(=O)C(Cl)C1=CC=CC(C(F)(F)F)=C1 RXYVNNWGXQRJAC-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polyimide, a transparent polyimide film and a preparation method thereof, wherein the polyimide is prepared by polymerizing dianhydride and diamine, the dianhydride is fluorine-containing dianhydride or alicyclic dianhydride, and hydroxyl-containing diamine in the polyimide accounts for more than 10 percent of the total molar weight of diamine participating in polymerization, and the hydroxyl-containing diamine has a general formula shown in the following structural formula:
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyimide film, a transparent polyimide film and a preparation method thereof.
Background
Polyimide materials have excellent characteristics of high temperature resistance, good mechanical properties, stable properties and the like, and are increasingly gaining attention in a plurality of fields. With the development of display panels toward flexibility and thinning, the use of transparent organic materials instead of conventional rigid glass is a major method for achieving device flexibility. However, inorganic materials replacing organic glass are required to have the characteristics of high temperature resistance, bending resistance, good dimensional stability and the like, and only transparent polyimide can meet the requirements at present. Also, in the photovoltaic power generation field, the flexibility of the battery panel can be achieved by using a transparent polyimide film as a cover plate material. In the field of electronic circuits, certain specific devices (e.g., optical sensors) require the use of transparent encapsulation materials, and the characteristics of good insulation and good dimensional stability of transparent polyimide are the best candidates.
The core technology of the development of the transparent polyimide material is to select synthetic monomers, and select proper monomers to prepare polyimide with excellent performance.
Chinese patent document CN107722268A provides a polyimide precursor, a polyimide and a method for producing a transparent polyimide film. The polyimide precursor disclosed in the patent has a structural unit derived from 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and a structural unit derived from 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, and the polyimide precursor has a transmittance of 5% or less at 308nm, 70% or more at 400nm, and a thermal expansion coefficient of 45ppm/K or less. Chinese patent document CN105694035B provides a high-transparency polyimide film material containing tetramethyl diphenyl sulfone diether structure and a preparation method thereof, and the polyimide film material has excellent dissolving film forming property, high optical transparency and good thermal stability. The transparent polyimide material in the above patent generally has the problem of low temperature resistance and dimensional stability.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides polyimide, a transparent polyimide film and a preparation method thereof, which improve the glass transition temperature of a transparent polyimide material, reduce the thermal expansion coefficient of the material, improve the transparency of the material and better meet the application of downstream industries.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the first aspect of the present invention provides a polyimide, which is a linear structure and is prepared by polymerizing dianhydride and diamine, wherein the dianhydride is fluorine-containing dianhydride or alicyclic dianhydride, the hydroxyl-containing diamine in the polyimide accounts for more than 10% of the total molar amount of diamine participating in polymerization, and the hydroxyl-containing diamine has a general formula shown in the following structural formula (X):
in the present invention, the hydroxyl-containing diamine has a structure in which the 2 and 2 '-positions of the benzene ring are hydroxyl groups and the 5 and 5' -positions are other functional groups (R2 and R3), with the purpose of: on the one hand, the steric hindrance of the hydroxyl group is smaller, the electron withdrawing effect is weaker, the reaction activity of the amino group is not obviously reduced when the hydroxyl group is adjacent to the amino group, if the reaction activity is too low, the phenomena of low polymerization degree and low polymer molecular weight can be caused, and the comprehensive performance is poor after the film is finally solidified and formed; on the other hand, other functional groups are placed at the 5 and 5' positions, so that the reactivity of amino groups is not influenced, meanwhile, the electron complexing effect (CTC effect) in a polymer can be reduced, and the final transparency of the material is improved.
Meanwhile, in the hydroxyl-containing diamine structure, amino and R1 are para-position structures, so that the linearity of a polymer formed by reaction is higher, molecular chain accumulation is compact, and the mechanical properties (strength, elongation and modulus) of the final polyimide material are improved.
The polyimide prepared by using the diamine and the dianhydride has a general formula shown in the following structural formula (Y):
in the invention, the hydrogen bonding action of hydroxyl in polyimide, the cutting conjugated electron action of main chain R1 group and side chain R2 and R3 group are synergistic, and under the combined action of a plurality of groups, the balance point of comprehensive performance is found, the glass transition temperature of the transparent polyimide material is improved, the thermal expansion coefficient of the material is reduced, and the transparency of the material is improved.
As an alternative embodiment, in the polyimide provided by the present invention, R1 is selected from one of the following structural formulas (1) to (14):
in the invention, R1 is a main chain structure and is responsible for the rotation and flexibility of the main chain, and finally the mechanical property and the thermal property of the material are influenced.
In an alternative embodiment, in the polyimide provided by the invention, R2 and R3 are selected from the same or different groups with electron withdrawing effect.
As an alternative embodiment, in the polyimide provided by the present invention, R2 and R3 are independently selected from one of the following structural formulas (16) - (66):
in the invention, R2 and R3 groups can destroy the CTC effect of molecular chains and molecules to different degrees, so that the transparency of the material is improved.
As an alternative embodiment, in the polyimide provided by the present invention, the fluorine-containing dianhydride is selected from one or more of 6FDA, 3FDA, 8FDA, 3 FCDA.
The chemical structural formulas of the 6FDA, the 3FDA, the 8FDA and the 3FCDA are shown as follows:
as an alternative embodiment, in the polyimide provided by the present invention, the alicyclic dianhydride is selected from one or more of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentanedicarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, octahydrobiphenylene-4 a,8b:4b,8 a-tetracarboxylic dianhydride, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride, meso-butane-1, 2,3, 4-tetracarboxylic anhydride.
The chemical structural formula of the substances is shown as follows:
as an alternative embodiment, in the polyimide provided by the invention, the molar ratio of the dianhydride to the diamine is 0.9 to 1.1.
In the present invention, the molar ratio of dianhydride to diamine is controlled within the range of 0.9 to 1.1, and a polymer having a high polymerization degree can be obtained, and beyond this range, the molecular weight of the polymer is too low to be practical.
As an alternative embodiment, in the polyimide provided by the invention, after the polymerization of dianhydride and diamine is completed, a capping agent is added for capping;
when the molar ratio of dianhydride to diamine is 0.9-1, this includes the case where the molar ratio of dianhydride to diamine is 1, the end-capping agent is selected from one or more of phthalic anhydride, 2, 3-dichloromaleic anhydride, tetrafluorophthalic anhydride, diphenic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, chlorobridge anhydride, 3-fluorophthalic anhydride, 3-chlorophthalic anhydride, nadic anhydride, tetrabromophthalic anhydride, citraconic anhydride;
when the molar ratio of dianhydride to diamine is 1-1.1, the case that the molar ratio of dianhydride to diamine is 1 is not included, and the end capping agent is selected from one or more of aminofluorene, pyrazinamide, aniline, azulene-2-amine, phenylmethylamine, amantadine and sulfapyridine.
In an alternative embodiment, the polyimide provided by the invention is characterized in that the solvent is selected from one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, gamma-butyrolactone and dimethyl sulfoxide.
As an alternative embodiment, in the polyimide provided by the invention, the dianhydride is 6FDA, the hydroxyl-containing diamine accounts for 10% of the total molar amount of diamine participating in polymerization, the molar ratio of the dianhydride to the diamine is 0.9, and the structural formula of the diamine is shown in the following formulas a and B:
in the invention, polyimide prepared by compounding the dianhydride and the diamine has the most excellent comprehensive performance.
Based on the same technical conception, the invention also provides a transparent polyimide film material, which is obtained by imidizing the polyimide.
Based on the same technical conception, the invention also provides a preparation method of the transparent polyimide film material, which comprises the following steps:
and coating the polyimide solution on the surface of a supporting substrate, heating the polyimide coating to imidize, forming an imide layer on the surface of the supporting substrate, and stripping the polyimide layer from the surface of the supporting substrate to obtain the transparent polyimide film material.
In an alternative embodiment, in the preparation method provided by the invention, the supporting substrate is glass, and the polyimide layer is peeled off from the glass supporting substrate by a laser irradiation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention uses diamine containing hydroxyl, and the molecular chain of the prepared polyimide contains hydroxyl groups, so that intermolecular hydrogen bonding can be formed, the heat resistance and the dimensional stability of the transparent polyimide film are improved, and the polyimide film can better meet the application fields of flexible display, photovoltaic power generation and electronic circuits.
(2) The hydroxyl-containing diamine used in the invention has the hydroxyl groups positioned at the 2 and 2 '-positions of the benzene ring and the R2 and R3 groups positioned at the 5 and 5' -positions of the benzene ring, and compared with the hydroxyl-containing diamine without the R2 and R3 groups in the prior art, the hydroxyl-containing diamine can reduce the electron complexing effect (CTC effect) in the macromolecule and improve the transparency of the material.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, to facilitate understanding of the invention, but the scope of the invention is not limited to the specific embodiments described.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
6FDA (4, 4' - (hexafluoroisopropenyl) diphthalic anhydride) is selected for reaction with diamine with the following structure:
the molar ratio of 4,4' - (hexafluoroisopropenyl) isophthalic anhydride to diamine is 90/100, phthalic anhydride is adopted as a blocking agent, N-dimethylformamide is adopted as a solvent, and the polyamide acid slurry solution is prepared. The specific process is as follows: dissolving diamine in a solvent, adding dianhydride in three equal parts, fully reacting, adding a blocking agent, and uniformly stirring to obtain a polyamic acid slurry solution. The solution is coated on a glass substrate in a scraping way, and is placed in an oven for programmed heating, specifically: heat preservation at 100 ℃ for 30min, heat preservation at 150 ℃ for 20min, heat preservation at 200 ℃ for 10min, heat preservation at 250 ℃ for 10min, and heat preservation at 320 ℃ for 5min, and imidization is carried out to obtain the transparent polyimide film.
Example 2
6FDA is selected to react with diamine A and diamine B with the following structures:
the molar ratio of diamine A to diamine B is 10/90,4,4' - (hexafluoro-isopropenyl) diphthalic anhydride to (diamine A+diamine B) is 90/100, the end capping agent adopts phthalic anhydride, and the solvent adopts N, N-dimethylformamide, so as to prepare the polyamic acid slurry solution. And (3) scraping the solution on a glass substrate, placing the glass substrate in an oven, heating the glass substrate in a program, and imidizing the glass substrate to obtain the transparent polyimide film. The specific preparation process and the temperature rise procedure in the oven are the same as in example 1.
Example 3
3FDA is selected to react with diamine A and diamine B with the following structures:
the molar ratio of diamine A to diamine B is 50/50,3FDA and the molar ratio of (diamine A+diamine B) is 95/100, the end capping agent adopts phthalic anhydride, and the solvent adopts N-methyl pyrrolidone to prepare the polyamic acid slurry solution. And (3) scraping the solution on a glass substrate, placing the glass substrate in an oven, heating the glass substrate in a program, and imidizing the glass substrate to obtain the transparent polyimide film. The specific preparation process and the temperature rise procedure in the oven are the same as in example 1.
Example 4
8FDA is selected to react with diamine A and diamine B with the following structures:
the molar ratio of diamine A to diamine B is 90/100,8FDA to (diamine A+diamine B) is 105/100, the end capping agent adopts aminofluorene, and the solvent adopts gamma-butyrolactone, so as to prepare the polyamide acid slurry solution. And (3) scraping the solution on a glass substrate, placing the glass substrate in an oven, heating the glass substrate in a program, and imidizing the glass substrate to obtain the transparent polyimide film. The specific preparation process and the temperature rise procedure in the oven are the same as in example 1.
Example 5
The preparation method comprises the following steps of reacting cyclobutane tetracarboxylic dianhydride with diamine A and diamine B with the following structures:
the molar ratio of diamine A to diamine B is 90/100, the molar ratio of cyclobutane tetracarboxylic dianhydride to (diamine A+diamine B) is 105/100, the end capping agent adopts pyrazinamide, and the solvent adopts gamma-butyrolactone to prepare the polyamic acid slurry solution. And (3) scraping the solution on a glass substrate, placing the glass substrate in an oven, heating the glass substrate in a program, and imidizing the glass substrate to obtain the transparent polyimide film. The specific preparation process and the temperature rise procedure in the oven are the same as in example 1.
Example 6
3FCDA is selected to react with diamine A and diamine B with the following structures:
the molar ratio of diamine A to diamine B is 90/100,3FCDA to (diamine A+diamine B) is 105/100, the end capping agent adopts aniline, and the solvent adopts gamma-butyrolactone to prepare the polyamide acid slurry solution. And (3) scraping the solution on a glass substrate, placing the glass substrate in an oven, heating the glass substrate in a program, and imidizing the glass substrate to obtain the transparent polyimide film. The specific preparation process and the temperature rise procedure in the oven are the same as in example 1.
Comparative example 1
6FDA is selected to react with diamine A and diamine B with the following structures:
the molar ratio of diamine A to diamine B is 10/90,6FDA and the molar ratio of (diamine A+diamine B) is 90/100, the end capping agent adopts phthalic anhydride, and the solvent adopts N, N-dimethylformamide to prepare the polyamic acid slurry solution. And (3) scraping the solution on a glass substrate, placing the glass substrate in an oven, heating the glass substrate in a program, and imidizing the glass substrate to obtain the transparent polyimide film. The specific preparation process and the temperature rise procedure in the oven are the same as in example 1.
Comparative example 2
6FDA is selected to react with diamine A and diamine B with the following structures:
the molar ratio of diamine A to diamine B is 10/90,6FDA and the molar ratio of (diamine A+diamine B) is 90/100, the end capping agent adopts phthalic anhydride, and the solvent adopts N, N-dimethylformamide to prepare the polyamic acid slurry solution. And (3) scraping the solution on a glass substrate, placing the glass substrate in an oven, heating the glass substrate in a program, and imidizing the glass substrate to obtain the transparent polyimide film. The specific preparation process and the temperature rise procedure in the oven are the same as in example 1.
Comparative example 3
6FDA is selected to react with diamine A and diamine B with the following structures:
the molar ratio of diamine A to diamine B is 10/90,6FDA and the molar ratio of (diamine A+diamine B) is 90/100, the end capping agent adopts phthalic anhydride, and the solvent adopts N, N-dimethylformamide to prepare the polyamic acid slurry solution. And (3) scraping the solution on a glass substrate, placing the glass substrate in an oven, heating the glass substrate in a program, and imidizing the glass substrate to obtain the transparent polyimide film. The specific preparation process and the temperature rise procedure in the oven are the same as in example 1.
Performance detection
The transparent polyimide films prepared in examples 1 to 6 and comparative examples 1 to 3 were tested for their combination properties, and the test results are shown in Table 1 below.
Table 1: results of testing the properties of polyimide films of examples and comparative examples
| Transmittance/450 nm | Transmittance/500 nm | Coefficient of linear expansion | Glass transition temperature | |
| Example 1 | 81％ | 89％ | 22 | 347 |
| Example 2 | 80.5％ | 88.7％ | 19 | 364 |
| Example 3 | 82％ | 90％ | 27 | 339 |
| Example 4 | 81.5％ | 90％ | 25 | 351 |
| Example 5 | 83％ | 91％ | 29 | 336 |
| Example 6 | 82％ | 92％ | 26 | 331 |
| Comparative example 1 | 81％ | 89％ | 55 | 308 |
| Comparative example 2 | 81％ | 89％ | 22 | 352 |
| Comparative example 3 | 78％ | 85％ | 18 | 366 |
As can be seen from Table 1, when preparing polyimide film, the introduction of diamine with hydroxyl group structure can enhance the thermal performance of the material, and mainly shows the reduction of the on-line expansion coefficient and the improvement of the glass transition temperature. Polyimide film with hydroxyl diamine in 2,2' position of benzene ring has optimal performance, and the hydroxyl diamine has certain proportion of groups capable of reducing CTC effect in molecule to raise the optical performance of the material. By adjusting the proportion of the hydroxyl-containing diamine and the structure of R1, R2 and R3, a polyimide product with excellent performance can be obtained.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (10)
1. The polyimide is characterized in that the polyimide is of a linear structure and is prepared by polymerizing dianhydride and diamine, the dianhydride is fluorine-containing dianhydride or alicyclic dianhydride, the hydroxyl-containing diamine in the polyimide accounts for more than 10% of the total molar amount of diamine participating in polymerization, and the hydroxyl-containing diamine has a general formula shown in the following structural formula (X):
wherein R1 is selected from one of the following structural formulas (1) - (14):
r2 and R3 are selected from the same or different groups with electron withdrawing effect.
2. The polyimide according to claim 1, wherein R2 and R3 are independently selected from one of the following structural formulas (16) to (66):
3. the polyimide according to claim 1, wherein the fluorine-containing dianhydride is one or more selected from the group consisting of 6FDA, 3FDA, 8FDA, and 3 FCDA.
4. The polyimide according to claim 1, wherein the alicyclic dianhydride is one or more selected from the group consisting of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, octahydrobiphenylene-4 a,8b:4b,8 a-tetracarboxylic dianhydride, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride, meso-butane-1, 2,3, 4-tetracarboxylic anhydride.
5. The polyimide according to claim 1, wherein the molar ratio of dianhydride to diamine is 0.9 to 1.1.
6. The polyimide according to claim 1, wherein after the polymerization of the dianhydride and the diamine is completed, a capping agent is added to carry out capping;
when the mole ratio of dianhydride to diamine is 0.9-1, the end-capping agent is selected from one or more of phthalic anhydride, 2, 3-dichloro maleic anhydride, tetrafluorophthalic anhydride, diphenyl anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, chlorobridge anhydride, 3-fluorophthalic anhydride, 3-chlorophthalic anhydride, nadic anhydride, tetrabromophthalic anhydride and citraconic anhydride;
when the molar ratio of dianhydride to diamine is 1-1.1, the end capping agent is one or more selected from aminofluorene, pyrazinamide, aniline, azulene-2-amine, benzyl amine, amantadine and sulfapyridine.
7. The polyimide according to claim 1, wherein the dianhydride is 6FDA, the hydroxyl group-containing diamine accounts for 10% of the total molar amount of diamine involved in polymerization, the molar ratio of the dianhydride to diamine is 0.9, and the structural formulae of the diamine are shown in the following formulae (a) and (B):
8. a transparent polyimide film material, wherein the transparent polyimide film material is obtained by imidizing the polyimide according to any one of claims 1 to 7.
9. The method for preparing a polyimide film material according to claim 8, comprising the steps of:
coating a solution containing the polyimide according to any one of claims 1 to 7 on the surface of a supporting substrate, heating the polyimide coating to imidize, forming an imide layer on the surface of the supporting substrate, and peeling the polyimide layer from the surface of the supporting substrate to obtain a transparent polyimide film material.
10. The method for producing a polyimide film material according to claim 9, wherein the supporting substrate is glass, and the polyimide layer is peeled off from the glass supporting substrate by a laser irradiation method.
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| CN117567742B (en) * | 2024-01-17 | 2024-03-29 | 株洲时代新材料科技股份有限公司 | Preparation method of yellowing-resistant transparent polyimide substrate material |
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