CN112321825A - Heat-resistant transparent polyimide film and preparation method thereof - Google Patents
Heat-resistant transparent polyimide film and preparation method thereof Download PDFInfo
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- CN112321825A CN112321825A CN202011035526.5A CN202011035526A CN112321825A CN 112321825 A CN112321825 A CN 112321825A CN 202011035526 A CN202011035526 A CN 202011035526A CN 112321825 A CN112321825 A CN 112321825A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 36
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 30
- 239000004642 Polyimide Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 13
- 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 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 150000003949 imides Chemical class 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- 238000010345 tape casting Methods 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- -1 p-pyrroline Chemical compound 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 claims description 2
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical class CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 5
- 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 4
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000005266 casting Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004262 Ethyl gallate Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002438 flame photometric detection Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C08G73/1067—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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- 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)
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
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- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention provides a preparation method of a heat-resistant transparent polyimide film, which comprises the following steps: performing polycondensation reaction on dianhydride and diamine to obtain polyamic acid, and performing tape casting on a support to form a film to obtain a polyamic acid film; dipping the polyamic acid membrane into a solution containing inorganic nano-particles and an imide reagent, and taking out to obtain a polyimide wet membrane; and stretching and drying the polyimide wet film to obtain the heat-resistant transparent polyimide film. The preparation method provided by the invention overcomes the defect that polyimide and inorganic oxide cannot be effectively combined, and improves the transparency of the polyimide film and the heat resistance of the polyimide film.
Description
Technical Field
The invention relates to the technical field of polyimide, in particular to a heat-resistant transparent polyimide film and a preparation method thereof.
Background
Polyimide (PI) is a resin prepared by solution polymerization of aromatic dianhydride and aromatic diamine or aromatic diisocyanate, followed by dehydration, ring-closure and ammoniation at high temperature or under the action of an imide reagent.
Resins such as polyimides have many excellent characteristics such as thermal oxidation resistance, heat resistance, radiation resistance, low temperature resistance and chemical resistance, and thus are used in various fields, for example, as advanced heat-resistant materials for automobile materials, aircraft materials or spacecraft materials, or as base materials in the fields of displays (FPDs: e.g., liquid crystal display devices, organic EL display devices) and the like.
With the increasing demand for material properties, especially in the fields of advanced optical manufacturing and organic electroluminescent (OLED) display, the substrate material is often required to have better optical properties and mechanical properties, and a lower thermal expansion coefficient. At present, when the polyimide is used in the field of displays, the properties of the polyimide in the aspects of transparency, thermal stability and the like cannot meet the requirement. For this purpose, the materials scientist has used colorless transparent polyimide and silicon dioxide (SiO)2) Titanium dioxide (TiO)2) Zirconium oxide (ZrO)2) Alumina (Al)2O3) And Carbon Nano Tubes (CNT) and other inorganic materials are compounded to obtain the polyimide-based inorganic-organic composite material, so that the composite material has the optical performance of a high-molecular body material, has the advantages of high rigidity, low thermal expansion coefficient and the like of the inorganic material, and the optical performance, the mechanical performance, the thermal performance and the like of the composite material are comprehensively improved.
However, the interface compatibility of polyimide and inorganic oxide is very different, the combination difficulty is very high, and the performance improvement effect is limited at present, so that the polyimide and inorganic oxide can not be widely used.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of a heat-resistant transparent polyimide film, which overcomes the defect that polyimide and inorganic oxide cannot be effectively combined, and further improves the heat resistance of the polyimide film while improving the transparency of the polyimide film.
The invention provides a preparation method of a heat-resistant transparent polyimide film, which comprises the following steps:
s1, carrying out polycondensation reaction on dianhydride and diamine to obtain polyamic acid, and then carrying out tape casting on a support to form a film so as to obtain a polyamic acid film;
s2, dipping the polyamic acid membrane into a solution containing inorganic nano-particles and an imide reagent, and taking out to obtain a polyimide wet membrane;
and S3, stretching and drying the polyimide wet film to obtain the heat-resistant transparent polyimide film.
Preferably, the dianhydride is an aromatic or alicyclic tetracarboxylic dianhydride, and the diamine is an aromatic diamine; preferably, the dianhydride is a fluorine-containing substituted aromatic tetracarboxylic dianhydride, and the diamine is a fluorine-containing substituted aromatic diamine.
Preferably, the inorganic nanoparticles are SiO2、Al2O3、TiO2Or ZnO.
Preferably, the inorganic nanoparticles are amino-functionalized inorganic nanoparticles; preferably, the amino-functionalized inorganic nanoparticles are obtained by reacting 3-aminopropyltriethoxysilane and an inorganic nanoparticle precursor under alkaline conditions.
Preferably, the inorganic nanoparticle precursor is at least one of ethyl orthosilicate or aluminum isopropoxide.
Preferably, the imide reagent comprises a catalyst and a dehydrating agent; preferably, the catalyst is at least one of pyridine, p-pyrroline, lutidine, collidine or quinoline, and the dehydrating agent is at least one of trifluoroacetic anhydride, acetic anhydride or propionic anhydride.
Preferably, the stretching comprises: longitudinally stretched to 1.01-1.5 times and transversely stretched to 1.01-1.3 times at 140-170 ℃.
Preferably, the drying comprises: drying at 200-400 deg.C for 10-40 min.
The invention also provides a heat-resistant transparent polyimide film which is prepared by the preparation method.
According to the preparation method of the heat-resistant transparent polyimide film, the polyamic acid is dipped in the solution containing the inorganic nano-particles and the imide reagent after film formation, so that the inorganic nano-particles and the imide reagent can be uniformly distributed on the surface of the polyamic acid film, and then the imide reagent is utilized to enable the polyamic acid film to generate imidization reaction, so that the inorganic nano-particles can be promoted to be effectively attached to the polyimide film, and the optical and heat-resistant properties of the polyimide film are improved.
Meanwhile, in order to further enhance the adhesion effect of the inorganic nanoparticles to the polyimide film, the inorganic nanoparticles are limited to be amino-functionalized inorganic nanoparticles, and the amino groups are grafted on the surface of the amino-functionalized inorganic nanoparticles, so that the amino-functionalized inorganic nanoparticles can be compounded with organic amine compounds (pyridine, p-pyrroline, lutidine and the like) in an imide reagent to form a reaction on the polyamic acid film, thereby further improving the interface bonding performance between the polyimide and the inorganic nanoparticles, enabling the inorganic nanoparticles to be more effectively and uniformly dispersed on the polyimide film, and effectively improving the heat resistance and the light transmittance of the obtained polyimide film.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of a heat-resistant transparent polyimide film specifically comprises the following steps:
(1) in N2Adding 0.16kg (0.5mol) of 4, 4' -diamino-2, 2 ' -bistrifluoromethylbiphenyl (TFDB) and 1500mL of dehydrated N, N-dimethylacetamide into a reactor under a protective environment, stirring and dissolving completely, adding 0.076kg (0.26mol) of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) and 0.11kg (0.25mol) of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), and stirring and reacting at 30 ℃ and a stirring speed of 300rpm for 3 hours after the addition is finished to obtain a polyamic acid solution;
controlling the thickness of the wet film of the polyamic acid solution to be 100 mu m by a scraper, casting the polyamic acid solution on a smooth steel belt to form a film, heating the film to 80 ℃ under the protection of nitrogen, and carrying out heat treatment for 5min to obtain a polyamic acid film;
(2) the polyamic acid film was peeled off from the steel strip and then dipped in a solution containing 0.08kg of SiO2Heating the nano particles (with the average particle size of 80nm), 350mL of acetic anhydride, 200mL of pyridine and 1500mL of N, N-dimethylacetamide to a soaking solution consisting of 50 ℃, keeping the temperature for 30min, taking out the nano particles, soaking the nano particles into 1500mL of N, N-dimethylacetamide to keep the temperature for 20min, and taking out the nano particles to obtain a polyimide wet film;
(3) drying the polyimide wet film in hot air at 150 ℃ for 15min, removing most of solvent, performing longitudinal stretching by 1.3 times and transverse stretching by 1.2 times at 160 ℃, heating to 320 ℃ in a hot air furnace, and performing heat treatment for 20min to obtain the heat-resistant transparent polyimide film.
Example 2
A preparation method of a heat-resistant transparent polyimide film specifically comprises the following steps:
(1) in N2Adding 0.16kg (0.5mol) of 4, 4' -diamino-2, 2 ' -bistrifluoromethylbiphenyl (TFDB) and 1500mL of dehydrated N, N-dimethylacetamide into a reactor under a protective environment, stirring and dissolving completely, adding 0.076kg (0.26mol) of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) and 0.11kg (0.25mol) of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), and stirring and reacting at 30 ℃ and a stirring speed of 300rpm for 3 hours after the addition is finished to obtain a polyamic acid solution;
controlling the thickness of the wet film of the polyamic acid solution to be 100 mu m by a scraper, casting the polyamic acid solution on a smooth steel belt to form a film, heating the film to 80 ℃ under the protection of nitrogen, and carrying out heat treatment for 5min to obtain a polyamic acid film;
(2) the polyamic acid film was peeled off from the steel strip and then dipped in 0.08kg of amino-functionalized SiO2Heating the nano particles, 350mL of acetic anhydride, 200mL of pyridine and 1500mL of N, N-dimethylacetamide to 50 ℃ in an impregnation solution, keeping the temperature for 30min, taking out the solution, and then impregnating the solution in 1500mL of N, N-dimethylacetamide for 20min to obtain a polyimide wet film;
wherein the amino group is functionalized SiO2The nanoparticles are prepared byThe preparation method comprises the following steps: adding tetraethoxysilane and 3-aminopropyltriethoxysilane in a volume ratio of 5:2 into ethanol, adding ammonia water (1mol/L) with the volume of 0.8 time of tetraethoxysilane under the condition of stirring, stirring and reacting for 6 hours at room temperature, filtering, washing and drying the obtained solid powder to obtain the amino functionalized SiO2A nanoparticle;
(3) drying the polyimide wet film in hot air at 150 ℃ for 15min, removing most of solvent, performing longitudinal stretching by 1.3 times and transverse stretching by 1.2 times at 160 ℃, heating to 320 ℃ in a hot air furnace, and performing heat treatment for 20min to obtain the heat-resistant transparent polyimide film.
Example 3
A preparation method of a heat-resistant transparent polyimide film specifically comprises the following steps:
(1) in N2Adding 0.16kg (0.5mol) of 4, 4' -diamino-2, 2 ' -bistrifluoromethylbiphenyl (TFDB) and 1500mL of dehydrated N, N-dimethylacetamide into a reactor under a protective environment, stirring and dissolving completely, adding 0.076kg (0.26mol) of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) and 0.11kg (0.25mol) of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), and stirring and reacting at 30 ℃ and a stirring speed of 300rpm for 3 hours after the addition is finished to obtain a polyamic acid solution;
controlling the thickness of the wet film of the polyamic acid solution to be 100 mu m by a scraper, casting the polyamic acid solution on a smooth steel belt to form a film, heating the film to 80 ℃ under the protection of nitrogen, and carrying out heat treatment for 5min to obtain a polyamic acid film;
(2) the polyamic acid film was peeled off from the steel strip, and then dipped in 0.08kg of amino-functionalized Al2O3Heating the nano particles, 350mL of acetic anhydride, 200mL of pyridine and 1500mL of N, N-dimethylacetamide to 50 ℃ in an impregnation solution, keeping the temperature for 30min, taking out the solution, and then impregnating the solution in 1500mL of N, N-dimethylacetamide for 20min to obtain a polyimide wet film;
wherein the amino group is functionalized Al2O3The nano particles are prepared by the following method: adding aluminum isopropoxide and 3-aminopropyltriethoxysilane in a volume ratio of 5:2 to ethanol at a stirring rate of 400rpmAdding ammonia water (1mol/L) with the volume of 0.8 time of that of the aluminum isopropoxide, stirring and reacting for 6 hours at room temperature, filtering, washing and drying the obtained solid powder to obtain the amino functionalized Al2O3A nanoparticle;
(3) drying the polyimide wet film in hot air at 150 ℃ for 15min, removing most of solvent, performing longitudinal stretching by 1.4 times and transverse stretching by 1.2 times at 160 ℃, heating to 320 ℃ in a hot air furnace, and performing heat treatment for 20min to obtain the heat-resistant transparent polyimide film.
Comparative example 1
A preparation method of a heat-resistant transparent polyimide film specifically comprises the following steps:
(1) in N2Adding 0.16kg (0.5mol) of 4, 4' -diamino-2, 2 ' -bistrifluoromethylbiphenyl (TFDB) and 1500mL of dehydrated N, N-dimethylacetamide into a reactor under a protective environment, stirring and dissolving completely, adding 0.076kg (0.26mol) of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) and 0.11kg (0.25mol) of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), and stirring and reacting at 30 ℃ and a stirring speed of 300rpm for 3 hours after the addition is finished to obtain a polyamic acid solution;
(2) adding 0.08kg of inorganic nanoparticles, 350mL of acetic anhydride, 200mL of pyridine and 1500mL of N, N-dimethylacetamide into the polyamic acid solution under the stirring condition, heating to 50 ℃, then preserving heat and stirring for 30min, and filtering to obtain a polyimide solution;
(3) controlling the thickness of the wet film of the polyimide solution to be 100 mu m by a scraper, casting the solution on a smooth steel belt to form a film, heating the film to 80 ℃ under the protection of nitrogen, carrying out heat treatment for 5min, and stripping the film to obtain the polyimide wet film; drying the polyimide wet film in hot air at 150 ℃ for 15min, removing most of solvent, performing longitudinal stretching by 1.3 times and transverse stretching by 1.2 times at 160 ℃, heating to 320 ℃ in a hot air furnace, and performing heat treatment for 20min to obtain the polyimide film.
The polyimide films obtained in the above examples and comparative examples were subjected to the performance tests shown in the following methods, and the results thereof are shown in the following table 1:
light transmittance: uv-vis spectroscopy measures the visible light transmission.
Coefficient of linear thermal expansion: a thermal mechanical analyzer was used to apply a 50mN load under a nitrogen atmosphere, and the temperature was measured at a temperature rise rate of 10 ℃/min to obtain an average value.
Glass transition temperature: DSC measurement was performed at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere using a differential scanning calorimeter, and the glass transition temperature was determined.
Yellowness index: yellowness index was measured according to ASTM E313.
TABLE 1 results of Performance test of examples 1-3 and comparative example 1
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A preparation method of a heat-resistant transparent polyimide film is characterized by comprising the following steps:
s1, carrying out polycondensation reaction on dianhydride and diamine to obtain polyamic acid, and then carrying out tape casting on a support to form a film so as to obtain a polyamic acid film;
s2, dipping the polyamic acid membrane into a solution containing inorganic nano-particles and an imide reagent, and taking out to obtain a polyimide wet membrane;
and S3, stretching and drying the polyimide wet film to obtain the heat-resistant transparent polyimide film.
2. The method for preparing a heat-resistant transparent polyimide film according to claim 1, wherein the dianhydride is an aromatic or alicyclic tetracarboxylic dianhydride, and the diamine is an aromatic diamine; preferably, the dianhydride is a fluorine-containing substituted aromatic tetracarboxylic dianhydride, and the diamine is a fluorine-containing substituted aromatic diamine.
3. The method for preparing the heat-resistant transparent polyimide film according to claim 1 or 2, wherein the inorganic nanoparticles are SiO2、Al2O3、TiO2Or ZnO.
4. The method for preparing the heat-resistant transparent polyimide film according to claim 3, wherein the inorganic nanoparticles are amino-functionalized inorganic nanoparticles; preferably, the amino-functionalized inorganic nanoparticles are obtained by reacting 3-aminopropyltriethoxysilane and an inorganic nanoparticle precursor under alkaline conditions.
5. The method of claim 4, wherein the inorganic nanoparticle precursor is at least one of ethyl orthosilicate or aluminum isopropoxide.
6. The method for preparing a heat-resistant transparent polyimide film according to any one of claims 1 to 5, wherein the imide reagent comprises a catalyst and a dehydrating agent; preferably, the catalyst is at least one of pyridine, p-pyrroline, lutidine, collidine or quinoline, and the dehydrating agent is at least one of trifluoroacetic anhydride, acetic anhydride or propionic anhydride.
7. The method for preparing the heat-resistant transparent polyimide film according to any one of claims 1 to 6, wherein the stretching comprises: longitudinally stretched to 1.01-1.5 times and transversely stretched to 1.01-1.3 times at 140-170 ℃.
8. The method for preparing a heat-resistant transparent polyimide film according to any one of claims 1 to 7, wherein the drying comprises: drying at 200-400 deg.C for 10-40 min.
9. A heat-resistant transparent polyimide film produced by the method according to any one of claims 1 to 8.
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