CN113549234A - Production process of hydrophobic polyimide film - Google Patents
Production process of hydrophobic polyimide film Download PDFInfo
- Publication number
- CN113549234A CN113549234A CN202110831433.1A CN202110831433A CN113549234A CN 113549234 A CN113549234 A CN 113549234A CN 202110831433 A CN202110831433 A CN 202110831433A CN 113549234 A CN113549234 A CN 113549234A
- Authority
- CN
- China
- Prior art keywords
- flask
- polyimide film
- mol
- mmol
- diamine monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 33
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 150000004985 diamines Chemical class 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 76
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 31
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 claims description 22
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- HQROXDLWVGFPDE-UHFFFAOYSA-N 1-chloro-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(C(F)(F)F)=C1 HQROXDLWVGFPDE-UHFFFAOYSA-N 0.000 claims description 11
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical group Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000004642 Polyimide Substances 0.000 abstract description 6
- 239000013081 microcrystal Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- -1 siloxane chains Chemical group 0.000 abstract description 4
- 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 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- HWAQOZGATRIYQG-UHFFFAOYSA-N 4-sulfobenzoic acid Chemical compound OC(=O)C1=CC=C(S(O)(=O)=O)C=C1 HWAQOZGATRIYQG-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 150000001263 acyl chlorides Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a production process of a hydrophobic polyimide film, belonging to the technical field of modified polyimide film preparation, and the production process of the hydrophobic polyimide film comprises the following steps: preparing a diamine monomer A; diamine monomer A and dianhydride monomer react to prepare polyamic acid solution; imidizing to obtain a polyimide film; the prepared polyimide has C-F bonds and siloxane chains with excellent hydrophobic property, ester groups are arranged in the middle of the diamine monomer A, the structural symmetry degree of the diamine monomer A is high, the polymer can form microcrystals locally, diffusion of water molecules in the polymer is hindered due to the existence of the local microcrystals, when the water molecules meet the local microcrystals of the high molecular chains, high molecular chain segments in the crystalline structure are tightly piled, the water molecules cannot permeate and diffuse, the water molecules are finally retarded to advance, and the hydrophobic property of the film is further improved.
Description
Technical Field
The invention relates to the technical field of preparation of modified polyimide films, in particular to a production process of a hydrophobic polyimide film.
Background
Polyimide is a polymer containing imide ring (-CO-N-CO-) on the main chain, is one of organic polymer materials with the best comprehensive performance, has excellent performances such as high strength, low dielectric, high modulus, high temperature resistance and radiation resistance, and attracts attention and application due to the excellent performances such as high strength, low dielectric, high modulus, high temperature resistance and radiation resistance. Among aromatic heterocyclic polymer materials, aromatic polyimide materials are representative of high-performance polymer materials due to the characteristics of excellent heat resistance stability, radiation resistance, excellent mechanical properties, lower dielectric properties, processability and the like, and are widely applied to the high and new technology fields of aviation, aerospace, microelectronics and the like.
Despite its high chemical stability, the polyimide still absorbs some moisture, causing problems of metal corrosion, package cracking, film-to-metal adhesion failure, and dielectric property degradation, and the dielectric property thereof is significantly degraded due to its water absorption, which limits its further application in the rapidly developing electronic product field.
Disclosure of Invention
The invention aims to provide a production process of a hydrophobic polyimide film, which is used for solving the technical problems that the existing polyimide film has certain water absorption and limits the application range of the polyimide film.
The purpose of the invention can be realized by the following technical scheme:
a production process of a hydrophobic polyimide film comprises the following steps:
step S1: adding p-methylbenzoic acid and p-methylphenol into a flask, then adding p-toluenesulfonic acid and toluene, reacting for 4-5h at the temperature of 115 ℃ and 120 ℃, after the reaction is finished, cooling a reaction product to 70 ℃, transferring the reaction product into a separating funnel, adding a saturated sodium chloride aqueous solution at the temperature of 70 ℃, shaking, standing for 30min for layering, adding an organic phase into the flask, carrying out reduced pressure distillation to remove the toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid, the p-methylphenol, the p-sulfobenzoic acid and the toluene is 0.05 mol: 0.05 mol: 1.8 g: 45 mL;
the reaction process is as follows:
step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and performing reflux reaction for 3 hours to obtain an intermediate 2; then adding the intermediate 2 and deionized water into a flask, dropwise adding DMF and thionyl chloride, and carrying out reflux reaction for 2 hours to obtain an intermediate 3; the molar ratio of the intermediate 1 to the potassium permanganate is 1:1, the dosage ratio of the intermediate 2, DMF and thionyl chloride is 1 mol: 0.5 mL: 2.1 mol;
the reaction process is as follows:
step S3: adding 3, 5-dihydroxybenzoic acid and DMF (dimethyl formamide) into a flask, then adding aminopropyltriethoxysilane, then adding a catalyst, and stirring to react for 2 hours at the temperature of 30 ℃ to obtain an intermediate 4; the dosage ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane and catalyst is 0.1 mol: 100mL of: 0.11 mol: 0.5g, the catalyst is EDCI/HOBt with a molar ratio of 1: 1;
the reaction process is as follows:
step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reacting for 3 hours to obtain an intermediate 5; the dosage ratio of the intermediate 4, the 2-chloro-5-nitrobenzotrifluoride and the toluene is 2 mmol: 2 mmol: 10 mL;
the reaction process is as follows:
step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring and reacting at the temperature of 0-5 ℃ for 3 hours, and obtaining an intermediate 6 after the reaction is finished; the dosage ratio of the intermediate 3 to the intermediate 5 to the tetrahydrofuran to the pyridine is 1 mmol: 1 mmol: 10mL of: 1mmol of the active component;
the reaction process is as follows:
step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, reacting at 38 ℃ for 30-32h, removing the catalyst and the solvent after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10 percent Pd/C catalyst and the 1, 4-dioxane is 0.03 mol: 1.3 g: 300 mL;
the reaction process is as follows:
step S7: adding a diamine monomer A and DMF (dimethyl formamide) into a flask, then adding 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, reacting for 24h at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, vacuum-drying at the temperature of 60 ℃ to remove a solvent, then introducing nitrogen, heating to the temperature of 140 ℃ and 150 ℃, and keeping for 1h to obtain a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is as follows: 1 mmol: 5mL of: 1mmol of the active component;
the reaction process is as follows:
the invention provides a production process of a hydrophobic polyimide film. Compared with the prior art, the method has the following beneficial effects: the invention has prepared a polyimide film, prepare a diamine monomer A at first, and then react with dianhydride monomer 3,3 ', 4, 4' -benzophenone tetracarboxylic acid dianhydride by diamine monomer A, make polyamic acid solution, imidize and make polyimide film, wherein diamine monomer A is reacted by p-methylbenzoic acid and p-methylphenol esterification at first, make intermediate 1, then oxidize methyl of both ends of intermediate 1, become carboxyl, and then acidylate, make carboxyl turn into acyl chloride group, make intermediate 3, then utilize amino of aminopropyl triethoxysilane and carboxyl of 3, 5-dihydroxy benzoic acid to react, make intermediate 4, intermediate 4 and one active chlorine of 2-chloro-5-nitro benzotrifluoride take place the substitution reaction, make intermediate 5, then make hydroxyl of intermediate 5 react with acyl chloride of both ends of intermediate 3, preparing an intermediate 6, converting nitro groups of the intermediate 6 into amino groups under the action of a catalyst to prepare a diamine monomer A, wherein the amino groups at two ends of the diamine monomer A can participate in a reaction to prepare polyimide, the middle of the diamine monomer A is provided with an ester group, the structural symmetry of the diamine monomer A is high, the polymer can locally form microcrystals, due to the existence of the local microcrystals, diffusion of water molecules in the polymer is hindered, when the water molecules meet the local microcrystals of a high molecular chain, polymer chain segments in a crystalline structure are tightly piled up, the water molecules cannot permeate and diffuse, and finally the water molecules are retarded, meanwhile, the polymer in the crystalline structure forms good steric hindrance due to the existence of the crystalline structure, adsorption sites of the water molecules are reduced, the hydrogen bond water absorption effect is weakened, meanwhile, the diamine monomer also has a siloxane structure, and the introduction of the siloxane chain can reduce the glass transition temperature of the polymer, the diamine monomer A also has a C-F bond with high electronegativity, and fluorine atoms are difficult to form a hydrogen bond with hydrogen in water molecules as an electron donor, so that the hydrophobic property of the prepared polyimide is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a diamine monomer A, wherein the diamine monomer A is prepared by the following steps:
step S1: adding p-methylbenzoic acid and p-methylphenol into a flask, then adding p-toluenesulfonic acid and toluene, reacting for 4 hours at the temperature of 115 ℃, after the reaction is finished, cooling a reaction product to 70 ℃, transferring the reaction product into a separating funnel, adding a saturated sodium chloride aqueous solution at the temperature of 70 ℃, shaking, standing for 30min for layering, adding an organic phase into the flask, distilling under reduced pressure to remove the toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid, the p-methylphenol, the p-sulfobenzoic acid and the toluene is 0.05 mol: 0.05 mol: 1.8 g: 45 mL;
step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and performing reflux reaction for 3 hours to obtain an intermediate 2; then adding the intermediate 2 and deionized water into a flask, dropwise adding DMF and thionyl chloride, and carrying out reflux reaction for 2 hours to obtain an intermediate 3; the molar ratio of the intermediate 1 to the potassium permanganate is 1:1, the dosage ratio of the intermediate 2, DMF and thionyl chloride is 1 mol: 0.5 mL: 2.1 mol;
step S3: adding 3, 5-dihydroxybenzoic acid and DMF (dimethyl formamide) into a flask, then adding aminopropyltriethoxysilane, then adding a catalyst, and stirring to react for 2 hours at the temperature of 30 ℃ to obtain an intermediate 4; the dosage ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane and catalyst is 0.1 mol: 100mL of: 0.11 mol: 0.5g, the catalyst is EDCI/HOBt with a molar ratio of 1: 1;
step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reacting for 3 hours to obtain an intermediate 5; the dosage ratio of the intermediate 4, the 2-chloro-5-nitrobenzotrifluoride and the toluene is 2 mmol: 2 mmol: 10 mL;
step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring and reacting at the temperature of 0 ℃ for 3 hours, and obtaining an intermediate 6 after the reaction is finished; the dosage ratio of the intermediate 3 to the intermediate 5 to the tetrahydrofuran to the pyridine is 1 mmol: 1 mmol: 10mL of: 1mmol of the active component;
step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, reacting at 38 ℃ for 30 hours, removing the catalyst and the solvent after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10 percent Pd/C catalyst and the 1, 4-dioxane is 0.03 mol: 1.3 g: 300 mL.
Example 2
Preparing a diamine monomer A, wherein the diamine monomer A is prepared by the following steps:
step S1: adding p-methylbenzoic acid and p-methylphenol into a flask, then adding p-toluenesulfonic acid and toluene, reacting for 4.5 hours at 117.5 ℃, after the reaction is finished, cooling a reaction product to 70 ℃, transferring the reaction product into a separating funnel, adding a saturated sodium chloride aqueous solution at 70 ℃, shaking, standing for 30min for layering, adding an organic phase into the flask, distilling under reduced pressure to remove the toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid, the p-methylphenol, the p-sulfobenzoic acid and the toluene is 0.05 mol: 0.05 mol: 1.8 g: 45 mL;
step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and performing reflux reaction for 3 hours to obtain an intermediate 2; then adding the intermediate 2 and deionized water into a flask, dropwise adding DMF and thionyl chloride, and carrying out reflux reaction for 2 hours to obtain an intermediate 3; the molar ratio of the intermediate 1 to the potassium permanganate is 1:1, the dosage ratio of the intermediate 2, DMF and thionyl chloride is 1 mol: 0.5 mL: 2.1 mol;
step S3: adding 3, 5-dihydroxybenzoic acid and DMF (dimethyl formamide) into a flask, then adding aminopropyltriethoxysilane, then adding a catalyst, and stirring to react for 2 hours at the temperature of 30 ℃ to obtain an intermediate 4; the dosage ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane and catalyst is 0.1 mol: 100mL of: 0.11 mol: 0.5g, the catalyst is EDCI/HOBt with a molar ratio of 1: 1;
step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reacting for 3 hours to obtain an intermediate 5; the dosage ratio of the intermediate 4, the 2-chloro-5-nitrobenzotrifluoride and the toluene is 2 mmol: 2 mmol: 10 mL;
step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring and reacting at the temperature of 3 ℃ for 3 hours, and obtaining an intermediate 6 after the reaction is finished; the dosage ratio of the intermediate 3 to the intermediate 5 to the tetrahydrofuran to the pyridine is 1 mmol: 1 mmol: 10mL of: 1mmol of the active component;
step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, reacting at 38 ℃ for 31 hours, removing the catalyst and the solvent after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10 percent Pd/C catalyst and the 1, 4-dioxane is 0.03 mol: 1.3 g: 300 mL.
Example 3
Preparing a diamine monomer A, wherein the diamine monomer A is prepared by the following steps:
step S1: adding p-methylbenzoic acid and p-methylphenol into a flask, then adding p-toluenesulfonic acid and toluene, reacting for 5 hours at the temperature of 120 ℃, after the reaction is finished, cooling a reaction product to 70 ℃, transferring the reaction product into a separating funnel, adding a saturated sodium chloride aqueous solution at the temperature of 70 ℃, shaking, standing for 30min for layering, adding an organic phase into the flask, distilling under reduced pressure to remove the toluene, and filtering to obtain an intermediate 1; the dosage ratio of the p-methylbenzoic acid, the p-methylphenol, the p-sulfobenzoic acid and the toluene is 0.05 mol: 0.05 mol: 1.8 g: 45 mL;
step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and performing reflux reaction for 3 hours to obtain an intermediate 2; then adding the intermediate 2 and deionized water into a flask, dropwise adding DMF and thionyl chloride, and carrying out reflux reaction for 2 hours to obtain an intermediate 3; the molar ratio of the intermediate 1 to the potassium permanganate is 1:1, the dosage ratio of the intermediate 2, DMF and thionyl chloride is 1 mol: 0.5 mL: 2.1 mol;
step S3: adding 3, 5-dihydroxybenzoic acid and DMF (dimethyl formamide) into a flask, then adding aminopropyltriethoxysilane, then adding a catalyst, and stirring to react for 2 hours at the temperature of 30 ℃ to obtain an intermediate 4; the dosage ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane and catalyst is 0.1 mol: 100mL of: 0.11 mol: 0.5g, the catalyst is EDCI/HOBt with a molar ratio of 1: 1;
step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reacting for 3 hours to obtain an intermediate 5; the dosage ratio of the intermediate 4, the 2-chloro-5-nitrobenzotrifluoride and the toluene is 2 mmol: 2 mmol: 10 mL;
step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring and reacting at the temperature of 5 ℃ for 3 hours, and obtaining an intermediate 6 after the reaction is finished; the dosage ratio of the intermediate 3 to the intermediate 5 to the tetrahydrofuran to the pyridine is 1 mmol: 1 mmol: 10mL of: 1mmol of the active component;
step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, reacting at 38 ℃ for 32 hours, removing the catalyst and the solvent after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain a diamine monomer A; the dosage ratio of the intermediate 6, the 10 percent Pd/C catalyst and the 1, 4-dioxane is 0.03 mol: 1.3 g: 300 mL.
Example 4
The preparation method of the hydrophobic polyimide film comprises the following steps:
adding the diamine monomer A prepared in the example 2 and DMF into a flask, then adding 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, reacting for 24h at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, drying in vacuum at the temperature of 60 ℃ to remove a solvent, then introducing nitrogen, heating to 140 ℃, and keeping for 1h to prepare a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is as follows: 1 mmol: 5mL of: 1 mmol.
Example 5
The preparation method of the hydrophobic polyimide film comprises the following steps:
adding the diamine monomer A prepared in the example 2 and DMF into a flask, then adding 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, reacting for 24h at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, drying in vacuum at the temperature of 60 ℃ to remove a solvent, then introducing nitrogen, heating to 145 ℃, and keeping for 1h to obtain a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is as follows: 1 mmol: 5mL of: 1 mmol.
Example 6
The preparation method of the hydrophobic polyimide film comprises the following steps:
adding the diamine monomer A prepared in the example 2 and DMF into a flask, then adding 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, reacting for 24h at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, drying in vacuum at the temperature of 60 ℃ to remove a solvent, then introducing nitrogen, heating to 150 ℃, and keeping for 1h to prepare a polyimide film; the dosage ratio of the diamine monomer A, DMF to the 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is as follows: 1 mmol: 5mL of: 1 mmol.
Comparative example 1: compared to example 5, 4' -diaminodiphenyl sulfone was used as diamine monomer.
Comparative example 2: compared to example 5, hexafluoromethyl diphenyl diamine was used as the diamine monomer.
Comparative example 3: 1, 3-bis (3-aminopropyl) tetramethyldisiloxane was used as the diamine monomer compared to example 5.
The examples 4 to 6 and comparative examples 1 to 3 were subjected to the performance test, and the results are shown in the following table:
the tensile strength and elongation at break were tested in reference to GB13022-91, and the hydrophobicity was judged by measuring the contact angle, the results are given in the following table:
tensile Strength (MPa) | Elongation at Break (%) | Contact angle | |
Example 4 | 181 | 49 | 153° |
Example 5 | 180 | 49 | 154° |
Example 6 | 182 | 50 | 151° |
Comparative example 1 | 126 | 40 | 45° |
Comparative example 2 | 131 | 42 | 70° |
Comparative example 3 | 132 | 43 | 82° |
The table shows that examples 4-6 have good mechanical properties and hydrophobic properties.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A production process of a hydrophobic polyimide film is characterized by comprising the following steps:
adding a diamine monomer A and DMF (dimethyl formamide) into a flask, then adding 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, reacting for 24h at the temperature of 5 ℃ to obtain a polyamic acid solution, then coating the polyamic acid solution on a glass plate, drying in vacuum at the temperature of 60 ℃ to remove the solvent, then introducing nitrogen, heating to the temperature of 140 ℃ and 150 ℃, and keeping for 1h to obtain the polyimide film.
2. The process for preparing a hydrophobic polyimide film according to claim 1, wherein the diamine monomer A, DMF and the 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride are used in the following ratio: 1 mmol: 5mL of: 1 mmol.
3. The process for producing a hydrophobic polyimide film according to claim 1, wherein the diamine monomer A is prepared by the following steps:
step S1: adding p-methylbenzoic acid and p-methylphenol into a flask, then adding p-toluenesulfonic acid and toluene, and reacting for 4-5h at the temperature of 115 ℃ and 120 ℃ to obtain an intermediate 1;
step S2: adding the intermediate 1 and deionized water into a flask, refluxing, adding potassium permanganate, and performing reflux reaction for 3 hours to obtain an intermediate 2; then adding the intermediate 2 and deionized water into a flask, dropwise adding DMF and thionyl chloride, and carrying out reflux reaction for 2 hours to obtain an intermediate 3;
step S3: adding 3, 5-dihydroxybenzoic acid and DMF (dimethyl formamide) into a flask, then adding aminopropyltriethoxysilane, then adding a catalyst, and stirring to react for 2 hours at the temperature of 30 ℃ to obtain an intermediate 4;
step S4: adding the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene into a flask, heating to 80 ℃, and stirring for reacting for 3 hours to obtain an intermediate 5;
step S5: adding the intermediate 3, the intermediate 5, tetrahydrofuran and pyridine into a flask, introducing nitrogen for protection, stirring and reacting at the temperature of 0-5 ℃ for 3 hours, and obtaining an intermediate 6 after the reaction is finished;
step S6: adding the intermediate 6, a 10% Pd/C catalyst and 1, 4-dioxane into a flask, introducing hydrogen while stirring, reacting at 38 ℃ for 30-32h, removing the catalyst and the solvent after the reaction is finished, and recrystallizing with absolute ethyl alcohol to obtain the diamine monomer A.
4. The process of claim 3, wherein the amount ratio of p-toluic acid, p-methylphenol, p-sulfanylbenzoic acid, and toluene in step S1 is 0.05 mol: 0.05 mol: 1.8 g: 45 mL.
5. The process for preparing a hydrophobic polyimide film according to claim 3, wherein the molar ratio of the intermediate 1 to the potassium permanganate used in step S2 is 1:1, the dosage ratio of the intermediate 2, DMF and thionyl chloride is 1 mol: 0.5 mL: 2.1 mol.
6. The process of claim 3, wherein the amount ratio of the 3, 5-dihydroxybenzoic acid, DMF, aminopropyl triethoxysilane, and catalyst used in step S3 is 0.1 mol: 100mL of: 0.11 mol: 0.5g, the catalyst is EDCI/HOBt with a molar ratio of 1: 1.
7. The process of claim 3, wherein the ratio of the intermediate 4, 2-chloro-5-nitrobenzotrifluoride and toluene in step S4 is 2 mmol: 2 mmol: 10 mL.
8. The process of claim 3, wherein the ratio of the intermediate 3, the intermediate 5, the tetrahydrofuran and the pyridine in step S5 is 1 mmol: 1 mmol: 10mL of: 1 mmol.
9. The process of claim 3, wherein the intermediate 6, the 10% Pd/C catalyst, and the 1, 4-dioxane are used in a ratio of 0.03 mol: 1.3 g: 300 mL.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110831433.1A CN113549234B (en) | 2021-07-22 | 2021-07-22 | Production process of hydrophobic polyimide film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110831433.1A CN113549234B (en) | 2021-07-22 | 2021-07-22 | Production process of hydrophobic polyimide film |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113549234A true CN113549234A (en) | 2021-10-26 |
CN113549234B CN113549234B (en) | 2023-05-16 |
Family
ID=78132515
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110831433.1A Active CN113549234B (en) | 2021-07-22 | 2021-07-22 | Production process of hydrophobic polyimide film |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113549234B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115710375A (en) * | 2022-11-21 | 2023-02-24 | 中山大学 | Modification method and application of polyimide material |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5340888A (en) * | 1988-12-22 | 1994-08-23 | Borden Inc. | Phenolic resin composition |
CN108017786A (en) * | 2017-12-24 | 2018-05-11 | 桂林理工大学 | The method that Kapton is prepared using benzophenone tetracarboxylic dianhydride |
CN108102094A (en) * | 2017-12-24 | 2018-06-01 | 桂林理工大学 | The method that Kapton is prepared using hexafluorodianhydride (6FDA) |
WO2020175838A1 (en) * | 2019-02-28 | 2020-09-03 | 주식회사 엘지화학 | Diamine compound, and polyimide precursor and polyimide film using same |
-
2021
- 2021-07-22 CN CN202110831433.1A patent/CN113549234B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5340888A (en) * | 1988-12-22 | 1994-08-23 | Borden Inc. | Phenolic resin composition |
CN108017786A (en) * | 2017-12-24 | 2018-05-11 | 桂林理工大学 | The method that Kapton is prepared using benzophenone tetracarboxylic dianhydride |
CN108102094A (en) * | 2017-12-24 | 2018-06-01 | 桂林理工大学 | The method that Kapton is prepared using hexafluorodianhydride (6FDA) |
WO2020175838A1 (en) * | 2019-02-28 | 2020-09-03 | 주식회사 엘지화학 | Diamine compound, and polyimide precursor and polyimide film using same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115710375A (en) * | 2022-11-21 | 2023-02-24 | 中山大学 | Modification method and application of polyimide material |
CN115710375B (en) * | 2022-11-21 | 2024-01-12 | 中山大学 | Modification method and application of polyimide material |
Also Published As
Publication number | Publication date |
---|---|
CN113549234B (en) | 2023-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5845911B2 (en) | Polyimide precursor aqueous solution composition and method for producing polyimide precursor aqueous solution composition | |
JP2010538144A (en) | Polyimide polymer with oligomeric silsesquioxane | |
CN110229340B (en) | Polyimide aerogel based on silane hydrophobic modification and preparation method thereof | |
CN113185693B (en) | Polyamide acid solution and preparation method thereof, polyimide and polyimide film | |
CN113667120B (en) | Polyimide and preparation method thereof | |
CN113549234A (en) | Production process of hydrophobic polyimide film | |
CN112029099A (en) | Preparation method of polyamide acid solution and polyimide film | |
CN117362741A (en) | Heat treated polyamide-amide aerogel | |
CN112679734B (en) | Soluble polyimide containing bis (trifluoromethyl) benzene substituted asymmetric meta-position structure and preparation method thereof | |
CN101775138B (en) | Novel polytriazoles imide resin and preparation method thereof | |
CN114479076A (en) | Low-dielectric polyimide film and preparation method and application thereof | |
CN114591503B (en) | Soluble poly (benzimidazole-co-imide) polymer and preparation and application thereof | |
CN111808423B (en) | Polyimide film with high heat resistance and low thermal expansion coefficient and preparation method thereof | |
Chen et al. | Synthesis of colorless transparent poly (amide-imide) with high modulus and low thermal expansion coefficient and its performance study | |
US6046303A (en) | Soluble polyimide resin having alkoxy substituents and the preparation method thereof | |
CN111647270A (en) | Insulating polyimide film and preparation method thereof | |
JP2006131706A (en) | Low-dielectric polyimide material and high-efficiency separation membrane | |
CN114479074B (en) | High-temperature-resistant transparent polyimide film and preparation method and application thereof | |
KR102439488B1 (en) | Method for producing polyimide film with excellent transparency and flexibility | |
CN115286793A (en) | Polyimide resin composition and preparation method and application thereof | |
CN112708132B (en) | High-transparency low-expansion polyimide film containing benzimidazole structure and preparation method thereof | |
CN115612097A (en) | Nano composite material with low dielectric constant and high strength and preparation method thereof | |
CN113754571A (en) | Diamine monomer, intrinsic high-dielectric low-loss polyimide, and preparation method and application thereof | |
WO2004111108A1 (en) | Diamine having quinoxaline unit, polyimide precursor, polyimide and use thereof | |
CN111500065A (en) | High-barrier polyimide film and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |