CN111808306B - Polyimide film with low thermal expansion coefficient and preparation method thereof - Google Patents
Polyimide film with low thermal expansion coefficient and preparation method thereof Download PDFInfo
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- CN111808306B CN111808306B CN202010548121.5A CN202010548121A CN111808306B CN 111808306 B CN111808306 B CN 111808306B CN 202010548121 A CN202010548121 A CN 202010548121A CN 111808306 B CN111808306 B CN 111808306B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims description 48
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 21
- 229920005575 poly(amic acid) Polymers 0.000 claims description 19
- 239000007822 coupling agent Substances 0.000 claims description 18
- 150000004984 aromatic diamines Chemical class 0.000 claims description 17
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 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
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-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
- VQFBXSRZSUJGOF-UHFFFAOYSA-N 4-(1h-benzimidazol-2-yl)aniline Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=CC=C2N1 VQFBXSRZSUJGOF-UHFFFAOYSA-N 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 3
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical group C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical group NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 2
- IWFSADBGACLBMH-UHFFFAOYSA-N 4-[4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenyl]phenoxy]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C(=CC(N)=CC=3)C(F)(F)F)=CC=2)C=C1 IWFSADBGACLBMH-UHFFFAOYSA-N 0.000 claims description 2
- GLVOXGPMYXJKGS-UHFFFAOYSA-N 4-phenoxy-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC1=CC=CC=C1 GLVOXGPMYXJKGS-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 claims description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 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
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- JHTBOVFZNCAYFZ-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)aniline Chemical compound NC1=CC=CC(C=2NC3=CC=CC=C3N=2)=C1 JHTBOVFZNCAYFZ-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 description 20
- 150000004985 diamines Chemical class 0.000 description 16
- 239000011521 glass Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- -1 2,2 '-bis (4-aminophenyl) -5,5' -biphenyl imidazole Chemical group 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a polyimide film with low thermal expansion coefficient and a preparation method thereof, which effectively bonds polyimide containing imidazolyl and silicon dioxide, so that the thermal expansion coefficient of the polyimide is obviously reduced, and the polyimide is endowed with unique comprehensive performance.
Description
Technical Field
The invention relates to the technical field of optical materials, in particular to a polyimide film with a low thermal expansion coefficient and a preparation method thereof.
Background
Polyimides are usually prepared by condensation of aromatic organic dianhydrides and aromatic organic diamines, and their properties vary with the introduction of different precursors. Therefore, by adjusting dianhydride and diamine monomers or a synthetic route, polyimide materials with different properties (such as glass transition temperature, oxidation stability, toughness, cohesiveness, permeability and the like) can be synthesized. In recent years, a large number of novel polyimide polymer materials are synthesized by modifying the composition and structure of polyimide or modifying the polyimide by copolymerization, blending and other methods.
In the industries of photoelectric display and the like, the novel polyimide film is used for replacing a glass material, so that the characteristics of lightness, thinness, folding and the like of a screen can be realized. Polyimide films are often used in combination with inorganic materials, but during processing, the materials are subjected to high heat environments, which is difficult to meet with current state-of-the-art conventional polyimide materials. And if in the synthesis stage of the polyimide, the polyimide and the inorganic material can be effectively combined, so that the polyimide material is prevented from deforming due to high temperature, and the unique comprehensive performance of the polyimide can be endowed.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides the polyimide film with the low thermal expansion coefficient and the preparation method thereof, the polyimide containing the imidazolyl is effectively bonded with the silicon dioxide, so that the thermal expansion coefficient of the polyimide is obviously reduced, and the polyimide has unique comprehensive performance.
The invention provides a preparation method of a solvent-resistant polyimide film with low thermal expansion coefficient, which comprises the following steps:
s1, carrying out polycondensation reaction on an aromatic diamine monomer containing an imidazolyl group and a tetracarboxylic dianhydride monomer to obtain polyamic acid;
and S2, adding silicon dioxide modified by an epoxy end coupling agent into the polyamic acid, adding a dehydrating agent and an imidizing agent, reacting, and forming a film to obtain the polyimide film.
Preferably, the polyamide acid further comprises other aromatic diamine monomers, wherein the other aromatic diamine monomers and the aromatic diamine monomer containing the imidazolyl are subjected to polycondensation reaction with the tetracarboxylic dianhydride monomer to obtain polyamide acid; the molar ratio of the other aromatic diamine monomer to the aromatic diamine monomer having an imidazole group is 1:2-4.
Preferably, the imidazolyl-containing aromatic diamine monomer is 2,2 '-bis (4-aminophenyl) -5,5' -biphenyl imidazole
2,2 '-bis (3-aminophenyl) -5,5' -bibenzimidazole->
2,2' -bis (4-aminophenyl) benzimidazole->
2,2' -bis (3-aminophenyl) benzimidazole
One or a combination of more of the same.
Preferably, the other aromatic diamine monomer is 4,4' -diaminodiphenyl ether
2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl
4,4' -diaminodiphenyl sulfone->
4,4' -bis (2-trifluoromethyl-4-aminophenoxy) benzene->
4,4' -bis (2-trifluoromethyl-4-aminophenoxy) biphenyl->
One or a combination of more of the same.
Preferably, the tetracarboxylic dianhydride monomer is 4,4' - (hexafluoroisopropylene) diphthalic anhydride
4,4' -oxydiphthalic anhydride>
4,4' -biphenyltetracarboxylic dianhydride->
1,2,3,4 cyclobutanetetracarboxylic dianhydride->
1,2,4,5-cyclopentanetetracarboxylic dianhydride->
One or a combination of more of the same.
Preferably, the silica modified with the epoxy-terminated coupling agent is 1 to 20wt% of the polyamic acid.
Preferably, the silica modified by the epoxy-terminated coupling agent is prepared by the following method: and adding the epoxy group terminal coupling agent into an alcohol solvent, heating until the epoxy group terminal coupling agent is completely dissolved, adding the silicon dioxide nanoparticles, stirring and mixing fully, and drying to obtain the silicon dioxide modified by the epoxy group terminal coupling agent.
Preferably, the epoxy terminal coupling agent is one or more of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane.
Preferably, the dehydrating agent is one or more of acetic anhydride, propionic anhydride or trifluoroacetic anhydride, and the imidizing agent is one or more of pyridine, picoline, quinoline or isoquinoline.
The invention also provides a polyimide film with low thermal expansion coefficient, which is prepared by the preparation method.
In the invention, the polyimide main chain structure obtained by adopting the imidazole-group-containing aromatic diamine and the tetracarboxylic dianhydride monomer for polycondensation is characterized by containing a benzimidazole group structure, and the benzimidazole group structure can be crosslinked and bonded with epoxy groups on silica modified by an epoxy group terminal coupling agent, so that the silica is uniformly dispersed in a polyimide matrix as reinforcing particles, and the thermal expansion coefficient of the polyimide can be reduced because the Si-O bond in the silica is extremely high and has an extremely low thermal expansion coefficient and an interpenetrating network structure can be formed in the polyimide matrix.
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 the polyimide film comprises the following steps:
s1, under the protection of nitrogen, dissolving 10mmol of 2,2' -bis (4-aminophenyl) -5,5' -biphenyl benzimidazole serving as a diamine monomer raw material in 50mL of N, N-dimethylacetamide solvent, stirring until the diamine monomer raw material is completely dissolved, adding 10mmol of 4,4' - (hexafluoroisopropylene) diphthalic anhydride serving as a tetracarboxylic dianhydride monomer raw material, continuously stirring until the diamine monomer raw material is completely dissolved, and reacting at room temperature for 6 hours to obtain a polyamic acid solution;
s2, adding silicon dioxide modified by an epoxy group terminal coupling agent into the polyamic acid solution, adding 0.8g of pyridine as an imidizing agent, adding 5.5g of acetic anhydride as a dehydrating agent after completely dispersing, stirring for 4 hours, performing vacuum defoaming treatment, coating the glass plate on the glass plate, placing the glass plate in a drying oven at 80 ℃ for 0.5 hour, heating to 200 ℃, drying for 0.5 hour, heating to 300 ℃, drying for 0.5 hour, taking out the glass plate after the temperature is reduced to 25 ℃, placing the glass plate in water for demolding, placing the film in a drying oven at 100 ℃ for drying and dehydrating to obtain the film, namely the polyimide film, wherein the thickness is controlled to be 50 mu m;
wherein, the silicon dioxide modified by the epoxy group terminal coupling agent is prepared by the following method: dissolving 0.2mmol of 2- (3,4-epoxycyclohexyl) ethyl trimethoxy silane in absolute ethyl alcohol, heating to 50 ℃, stirring for 10min, adding 10mmol of silica particles (the average particle size is 50 nm), heating to 100 ℃, stirring for 5h, drying at 140 ℃, washing with absolute ethyl alcohol, drying in vacuum, and grinding to obtain the silica particles modified by the coupling agent.
The results of the performance test on the polyimide film are shown in table 1.
Example 2
A polyimide film was produced in the same manner as in example 1 except that in the production of the polyamic acid solution, 10mmol of 2,2' -bis (4-aminophenyl) -5,5' -biphenylimidazole as a diamine monomer raw material and 10mmol of 4,4' -oxydiphthalic anhydride as a tetracarboxylic dianhydride monomer raw material were used, and the results of the performance-related tests of the polyimide film thus obtained were also shown in Table 1.
Example 3
A polyimide film was produced in the same manner as in example 1 except that in the production of the polyamic acid solution, 10mmol of 2,2' -bis (4-aminophenyl) -5,5' -biphenylimidazole as a diamine monomer raw material and 10mmol of 4,4' -biphenyltetracarboxylic dianhydride as a tetracarboxylic dianhydride monomer raw material were used, and the results of the performance-related tests of the polyimide film thus obtained were also shown in Table 1.
Example 4
A polyimide film was produced in the same manner as in example 1 except that in the preparation of the polyamic acid solution, 10mmol of 2,2 '-bis (4-aminophenyl) -5,5' -biphenylimidazole as a diamine monomer raw material and 10mmol of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride monomer raw material were used, and the results of the performance-related tests of the polyimide film thus obtained were also shown in Table 1.
Example 5
A polyimide film was produced in the same manner as in example 1 except that in the production of the polyamic acid solution, 10mmol of 2,2 '-bis (4-aminophenyl) benzimidazole as the raw material of the diamine monomer and 10mmol of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride as the raw material of the tetracarboxylic dianhydride monomer were used, and the results of the performance-related tests of the polyimide film thus obtained were also shown in Table 1.
Example 6
A polyimide film was produced in the same manner as in example 1 except that 2mmol of 4,4 '-diaminodiphenyl ether and 8mmol of 2,2' -bis (4-aminophenyl) -5,5 '-biphenylimidazole were used as the diamine monomer raw materials and 10mmol of 4,4' - (hexafluoroisopropylene) diphthalic anhydride was used as the tetracarboxylic dianhydride monomer raw material in the production of the polyamic acid solution, and the results of the performance-related tests of the polyimide film thus obtained were also shown in table 1.
Example 7
A polyimide film was produced in the same manner as in example 1 except that in the polyamic acid solution production, 2mmol of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl and 8mmol of 2,2' -bis (4-aminophenyl) -5,5' -biphenylimidazole were used as the diamine monomer raw materials and 10mmol of 4,4' -oxydiphthalic anhydride was used as the tetracarboxylic dianhydride monomer raw material, and the results of the performance test concerning the polyimide film thus obtained were also shown in Table 1.
Example 8
A polyimide film was produced in the same manner as in example 1 except that in the preparation of the polyamic acid solution, 2mmol of 4,4' -diaminodiphenyl sulfone and 8mmol of 2,2' -bis (4-aminophenyl) -5,5' -biphenylimidazole were used as the starting diamine monomer materials and 10mmol of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride was used as the starting tetracarboxylic dianhydride monomer material, and the results of the performance-related tests of the polyimide film thus obtained were also shown in Table 1.
Comparative example 1
A polyimide film, the preparation method of which comprises:
s1, under the protection of nitrogen, dissolving 10mmol of 2,2' -bis (4-aminophenyl) -5,5' -biphenyl benzimidazole serving as a diamine monomer raw material in 50ml of N, N-dimethylacetamide solvent, stirring until the diamine monomer raw material is completely dissolved, adding 10mmol of 4,4' - (hexafluoroisopropylene) diphthalic anhydride serving as a tetracarboxylic dianhydride monomer raw material, continuously stirring until the diamine monomer raw material is completely dissolved, and reacting at room temperature for 6 hours to obtain a polyamic acid solution;
s2, adding 10mmol of silicon dioxide particles (the average particle size is 50 nm) into the polyamic acid solution, adding 0.8g of pyridine as an imidizing agent, adding 5.5g of acetic anhydride as a dehydrating agent after completely dispersing, stirring for 4 hours again, coating on a glass plate, placing the glass plate in a drying oven at 80 ℃ for 0.5 hour, heating to 200 ℃, drying for 0.5 hour, heating to 300 ℃, drying for 0.5 hour, taking out the glass plate after the temperature is reduced to 25 ℃, placing the glass plate in water for demoulding, then placing the film in a drying oven at 100 ℃ for drying and dehydrating to obtain the polyimide film, wherein the thickness of the polyimide film is controlled to be 50 microns. The results of the performance test on the polyimide film are shown in table 1.
Comparative example 2
A polyimide film was produced in the same manner as in comparative example 1, except that in the preparation of the polyamic acid solution, 2mmol of 4,4 '-diaminodiphenyl ether and 8mmol of 2,2' -bis (4-aminophenyl) -5,5 '-biphenylimidazole were used as the starting diamine monomer, and 10mmol of 4,4' - (hexafluoroisopropylene) diphthalic anhydride was used as the starting tetracarboxylic dianhydride monomer, and the results of the performance-related tests of the polyimide film thus obtained were also shown in Table 1.
The polyimide films obtained in examples 1 to 8 and comparative examples 1 to 2 were subjected to the performance tests shown in the following methods, and the results are shown in Table 1.
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.
The mechanical properties of the polyimide film were measured by a universal material testing machine in accordance with GB/T1040.3-2006.
TABLE 1 test results of polyimide films obtained in examples 1 to 8 and comparative examples 1 to 2
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 polyimide film with low thermal expansion coefficient is characterized by comprising the following steps:
s1, carrying out polycondensation reaction on an aromatic diamine monomer containing an imidazolyl group and a tetracarboxylic dianhydride monomer to obtain polyamic acid;
s2, adding silicon dioxide modified by an epoxy end coupling agent into the polyamic acid, adding a dehydrating agent and an imidizing agent for reaction, and forming a film to obtain the polyimide film;
the silicon dioxide modified by the epoxy group terminal coupling agent is prepared by the following method: and adding the epoxy group terminal coupling agent into the solvent, heating until the epoxy group terminal coupling agent is completely dissolved, adding the silicon dioxide nanoparticles, stirring and mixing fully, and drying to obtain the silicon dioxide modified by the epoxy group terminal coupling agent.
2. The method for preparing a polyimide film with a low coefficient of thermal expansion according to claim 1, further comprising other aromatic diamine monomers, wherein the other aromatic diamine monomers and the aromatic diamine monomer containing an imidazole group are subjected to a polycondensation reaction with a tetracarboxylic dianhydride monomer to obtain a polyamic acid; the molar ratio of the other aromatic diamine monomer to the aromatic diamine monomer having an imidazole group is 1:2-4.
3. The method for preparing a polyimide film with a low coefficient of thermal expansion according to claim 1 or 2, wherein the aromatic diamine monomer containing an imidazole group is one or more of 2,2 '-bis (4-aminophenyl) -5,5' -bibenzoimidazole, 2,2 '-bis (3-aminophenyl) -5,5' -bibenzoimidazole, 2,2 '-bis (4-aminophenyl) benzimidazole, or 2,2' -bis (3-aminophenyl) benzimidazole.
4. The method of claim 2, wherein the other aromatic diamine monomer is 4,4 '-diaminodiphenyl ether, 2,2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 4,4' -diaminodiphenyl sulfone, 4,4 '-bis (2-trifluoromethyl-4-aminophenoxy) benzene, or 4,4' -bis (2-trifluoromethyl-4-aminophenoxy) biphenyl.
5. The method for preparing a polyimide film having a low coefficient of thermal expansion according to claim 1 or 2, wherein the tetracarboxylic dianhydride monomer is one or a combination of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, 4,4' -oxydiphthalic anhydride, 4,4' -biphenyltetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride.
6. The method for preparing a polyimide film having a low coefficient of thermal expansion according to claim 1 or 2, wherein the silica modified with the epoxy terminal coupling agent is 1 to 20wt% of the amount of polyamic acid.
7. The method of claim 1, wherein the epoxy-terminated coupling agent is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, or 3-glycidoxypropyltriethoxysilane.
8. The method for preparing a polyimide film with a low thermal expansion coefficient according to claim 1 or 2, wherein the dehydrating agent is one or more of acetic anhydride, propionic anhydride or trifluoroacetic anhydride; the imidizing agent is one or a combination of more of pyridine, picoline, quinoline or isoquinoline.
9. A polyimide film having a low coefficient of thermal expansion, which is produced by the production method according to any one of claims 1 to 8.
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| CN112662177B (en) * | 2020-11-30 | 2022-05-20 | 浙江中科玖源新材料有限公司 | High-modulus and high-hardness polyimide film |
| CN113284646B (en) * | 2021-03-31 | 2023-03-31 | 浙江中科玖源新材料有限公司 | Flexible transparent conductive film and preparation method thereof |
| CN113629250B (en) * | 2021-06-25 | 2023-01-17 | 浙江中科玖源新材料有限公司 | Polyimide binder for lithium battery cathode and silicon-based cathode plate |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007106836A (en) * | 2005-10-12 | 2007-04-26 | Toyobo Co Ltd | Silane-modified polyamic acid resin composition |
| CN101289542A (en) * | 2007-04-17 | 2008-10-22 | 中国科学院化学研究所 | Spherical silica/polyimides composite membrane, preparation thereof and applications |
| CN101407590A (en) * | 2008-11-27 | 2009-04-15 | 南京工业大学 | Preparation method of high-modulus and low-thermal expansion coefficient polyimide hybrid film |
| CN103483608A (en) * | 2013-09-13 | 2014-01-01 | 华南师范大学 | Preparing method for organosilicone modification PI/SiO2 hybrid membrane with low coefficient of thermal expansion |
| CN108727587A (en) * | 2018-06-26 | 2018-11-02 | 同济大学 | A kind of heat-proof polyimide of the ring structure containing imidazolyl aromatic and preparation method thereof |
| CN111269421A (en) * | 2020-04-15 | 2020-06-12 | 浙江中科玖源新材料有限公司 | Polyamide acid, polyimide film and film preparation method |
-
2020
- 2020-06-16 CN CN202010548121.5A patent/CN111808306B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007106836A (en) * | 2005-10-12 | 2007-04-26 | Toyobo Co Ltd | Silane-modified polyamic acid resin composition |
| CN101289542A (en) * | 2007-04-17 | 2008-10-22 | 中国科学院化学研究所 | Spherical silica/polyimides composite membrane, preparation thereof and applications |
| CN101407590A (en) * | 2008-11-27 | 2009-04-15 | 南京工业大学 | Preparation method of high-modulus and low-thermal expansion coefficient polyimide hybrid film |
| CN103483608A (en) * | 2013-09-13 | 2014-01-01 | 华南师范大学 | Preparing method for organosilicone modification PI/SiO2 hybrid membrane with low coefficient of thermal expansion |
| CN108727587A (en) * | 2018-06-26 | 2018-11-02 | 同济大学 | A kind of heat-proof polyimide of the ring structure containing imidazolyl aromatic and preparation method thereof |
| CN111269421A (en) * | 2020-04-15 | 2020-06-12 | 浙江中科玖源新材料有限公司 | Polyamide acid, polyimide film and film preparation method |
Non-Patent Citations (2)
| Title |
|---|
| Preparation and properties of imidazole-containing polyimide/silica hybrid films;MA Xiaoye et al;《Chem.Res.Chin.Univ.》;20141231;第30卷(第6期);第1047-1050页 * |
| 王海臣 译.化学亚胺化.《聚酰亚胺》.机械工业出版社,1981,第17-18页. * |
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