CN109438704B - Polyimide film and preparation method thereof - Google Patents
Polyimide film and preparation method thereof Download PDFInfo
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- CN109438704B CN109438704B CN201811340531.XA CN201811340531A CN109438704B CN 109438704 B CN109438704 B CN 109438704B CN 201811340531 A CN201811340531 A CN 201811340531A CN 109438704 B CN109438704 B CN 109438704B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003292 glue Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 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 9
- 239000004952 Polyamide Substances 0.000 claims abstract 3
- 239000002253 acid Substances 0.000 claims abstract 3
- 229920002647 polyamide Polymers 0.000 claims abstract 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 20
- 229920005575 poly(amic acid) Polymers 0.000 claims description 19
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007790 scraping Methods 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 238000005303 weighing Methods 0.000 claims 6
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 16
- 125000003118 aryl group Chemical group 0.000 abstract description 14
- 150000004984 aromatic diamines Chemical class 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention discloses a polyimide film and a preparation method thereof, wherein a small amount of triamino monomer is added as a cross-linking agent in the preparation of polyamide acid glue solution (in the condensation polymerization process of aromatic diamine and aromatic dianhydride), and then blade coating and temperature programming are carried out to prepare the polyimide film with a small amount of cross-linking points. The method has the advantages of easily obtained raw materials, simple and convenient reaction process and wide applicability, and the prepared polyimide film has greatly improved mechanical properties such as tensile strength and elongation at break.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a polyimide film and a preparation method thereof.
Background
Polyimide is a special engineering plastic with excellent comprehensive performance, has the advantages of high temperature resistance, high mechanical strength, low thermal expansion coefficient, excellent dielectric property, excellent ultraviolet radiation resistance and the like, and is widely applied to the fields of aerospace, microelectronics, displays, new energy sources, separation membranes, IT machines, lasers and the like. The most common method for preparing polyimide at present in China is a casting-thermal imide method, the technical threshold and equipment cost of the method are low, but the polyimide film produced by the method has general mechanical properties (such as tensile strength, elongation at break, modulus, shrinkage rate and the like).
With the continuous development of electronic devices, the demand for high-performance polyimide films is more urgent, and high-performance polyimides can be prepared by changing the production mode, such as introducing a biaxial stretching method, a chemical imide method and the like, but the method needs expensive equipment, has high technical requirements, and is not suitable for large-scale industrial popularization because few enterprises can use the biaxial stretching method, particularly the chemical imide method, at present in China.
Therefore, the problem to be solved by the technical personnel in the field is how to provide a high-performance polyimide film and a preparation method of the polyimide film with simple preparation process, low cost and wide applicability.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a polyimide film with excellent mechanical properties; and a preparation method of the polyimide film, which has the advantages of simple preparation process, low cost, wide applicability and easy industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyimide film is prepared from aromatic diamine monomer, aromatic dianhydride monomer and cross-linking agent through condensation polymerization of aromatic triamine and coating.
Preferably, in one of the polyimide films, the molar ratio of the aromatic diamine monomer, the aromatic triamine monomer and the aromatic dianhydride monomer is 1: (0.001-0.01): (0.97-1.03), the addition amount of the aromatic triamine needs to be controlled in a proper range, if the addition amount is too small, the crosslinking point is insufficient, the film performance is not obviously improved, and if the addition amount is too large, the system forms jelly gel, and the subsequent knife coating cannot form a film.
Specifically, the addition amount of the aromatic dianhydride monomer is regulated and controlled according to the requirement of the viscosity of the glue solution. Theoretically, high molecular weight polyimide can be obtained by ensuring that the amine and the anhydride react at an equal molar ratio, the film performance is good, but because the subsequent process is to scrape coating glue solution on a substrate, if the viscosity is too high due to equal molar feeding, scraping coating cannot be performed, the addition amount of the dianhydride needs to be slightly reduced on the theoretical calculation amount of the equal molar ratio, and the specific addition amount is regulated according to the viscosity.
Preferably, in the above one polyimide film, the aromatic diamine monomer is one or more of the following compounds:
preferably, in the polyimide film, the aromatic dianhydride monomer is one or more of the following compounds:
preferably, in one of the polyimide films, the aromatic triamine monomer is one or more of the following compounds:
the invention also discloses a preparation method of the polyimide film, which comprises the following steps:
(1) dissolving an aromatic diamine monomer and an aromatic triamine monomer in a polar aprotic solvent, adding an aromatic dianhydride monomer after complete dissolution, and stirring for reaction for 5-24h to obtain a polyamic acid glue solution;
(2) and (3) blade-coating the polyamic acid glue solution on a substrate, then carrying out temperature programming, and naturally cooling to obtain the polyimide film.
Preferably, in the above method for preparing a polyimide film, the polar aprotic solvent in step (1) is one or more selected from N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and m-cresol.
Preferably, in the preparation method of the polyimide film, the reaction temperature in the step (1) is-5-30 ℃, the solid content is 15-20%, and inert protective gas such as nitrogen or argon is introduced in the whole reaction process.
Preferably, in the above preparation method of the polyimide film, the polyamic acid glue solution is placed in a negative pressure environment of 0.1MPa for 1-2h before blade coating in step (2), bubbles are removed, then blade coating is performed on a clean substrate, and the substrate is placed in an oven for heating.
Preferably, in the above one polyimide film production method, the substrate in step (2) includes, but is not limited to, a glass plate, an iron plate, a copper plate, an aluminum plate, and a steel plate.
Preferably, in the above polyimide film production method, the temperature increase procedure in step (2) is:
the room temperature is increased to 150 ℃ and 180 ℃, and the temperature rising rate is controlled to be 0.5-2 ℃/min;
heating to 200-220 ℃ at the temperature of 150-;
the temperature is increased to 300-400 ℃ at 200 ℃ and 220 ℃, and the temperature increase rate is controlled to be 2-4 ℃/min.
The highest temperature has different requirements on polyimides of different systems, the polyimide is possibly partially decomposed when the temperature is too high, the film performance is poor, the imidization is incomplete when the temperature is too low, the film performance is insufficient, and the specific temperature requirements are met for different systems.
According to the technical scheme, compared with the prior art, the polyimide film prepared by the method has excellent mechanical property, is remarkably improved compared with the traditional film, can be directly used for a polyimide film production line, and realizes industrial production; the polyimide film prepared by the invention can be applied to reinforcing plates and the like with higher requirements on the mechanical properties of materials, and is widely applied to the fields of high and new technology industries such as electronics, microelectronics, information, aerospace and the like; in addition, the preparation method of the polyimide film disclosed by the invention is simple in process, low in cost and easy to popularize and apply in industrial production.
Detailed Description
The following will clearly and completely describe the technical solutions of 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 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
The molecular structural formula of the polyimide film PI-1 in this example 1 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100.
The preparation method of the polyimide film PI-1 comprises the following steps:
(1) 6.0072g (0.03mol) of 4,4' -diaminodiphenyl ether (ODA), 0.0105g (0.03mmol) of 1,3, 5-tris (4-aminophenyl) benzene (TAPB) and 50g of N, N-dimethylacetamide (DMAc) are weighed into a 100mL round-bottomed flask at room temperature, argon is introduced, 6.4050g (0.029mol) of pyromellitic dianhydride (PMDA) is added after complete dissolution, and stirring is continued for 12 hours at room temperature to obtain a transparent, homogeneous and viscous polyamic acid (PAA) glue solution.
(2) Placing the prepared glue solution under the negative pressure condition of 0.1MPa for 1-2h, removing bubbles, then scraping and coating the glue solution on a clean glass plate, and placing the clean glass plate in an oven for programmed temperature rise: heating the mixture to 170 ℃ at room temperature, and controlling the heating rate at 2 ℃/min; heating to 200 ℃ at 170 ℃, and controlling the heating rate at 4 ℃/min; the temperature is increased to 400 ℃ from 200 ℃, and the temperature increase rate is controlled to be 3 ℃/min. And naturally cooling to room temperature after heating to obtain the PI-1 polyimide film.
The detection results of the PI-1 polyimide film are as follows: PI-1 had a tensile strength of 113MPa, an elongation at break of 21.0% and a modulus of 2.72 GPa.
Example 2
The molecular structural formula of the polyimide film PI-2 in this example 2 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100.
The preparation method of the polyimide film PI-2 comprises the following steps:
(1) 6.0072g (0.03mol) of 4,4' -diaminodiphenyl ether (ODA), 0.0087g (0.03mmol) of tris (4-aminophenyl) amine (TAPA) and 50g of N, N-dimethylacetamide (DMAc) are weighed into a 100mL round-bottomed flask at room temperature, argon is introduced, 6.4050g (0.029mol) of pyromellitic dianhydride (PMDA) is added after complete dissolution, and stirring is continued for 12 hours at room temperature to obtain a transparent, homogeneous and viscous polyamic acid (PAA) glue solution.
Step (2) the PI-2 polyimide film was obtained in the same manner as in example 1.
The detection results of the PI-2 polyimide film are as follows: the tensile strength of PI-2 was 128MPa, the elongation at break was 24.2%, and the modulus was 2.68 GPa.
Example 3
The molecular structural formula of the polyimide film PI-3 in this example 3 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100.
The preparation method of the polyimide film PI-3 comprises the following steps:
(1) 6.0072g (0.03mol) of 4,4 '-diaminodiphenyl ether (ODA), 0.0087g (0.03mmol) of 4,4' -Triaminotriphenylmethane (TAPM) and 50g of N, N-dimethylacetamide (DMAc) are weighed into a 100mL round-bottomed flask at room temperature, argon is introduced, 6.4050g (0.029mol) of pyromellitic dianhydride (PMDA) is added after complete dissolution, and stirring is continued for 12 hours at room temperature to obtain a transparent, homogeneous and viscous polyamic acid (PAA) glue solution.
Step (2) the PI-3 polyimide film was obtained as in example 1.
The detection results of the PI-3 polyimide film are as follows: PI-3 has a tensile strength of 131MPa, an elongation at break of 29.4% and a modulus of 2.70 GPa.
Example 4
The molecular structural formula of the polyimide film PI-4 in this example 4 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100.
The preparation method of the polyimide film PI-4 comprises the following steps:
(1) 6.0072g (0.03mol) of 4,4' -diaminodiphenyl ether (ODA), 0.0173g (0.06mmol) of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (TAPT) and 50g of N, N-dimethylacetamide (DMAc) are weighed into a 100mL round-bottomed flask at room temperature, argon is introduced, after complete dissolution, 6.4704g (0.029mol) of pyromellitic dianhydride (PMDA) are added, and stirring is continued for 12 hours at room temperature, so that transparent, homogeneous and viscous polyamic acid (PAA) glue solution is obtained.
Step (2) the PI-4 polyimide film was obtained as in example 1.
The detection results of the PI-4 polyimide film are as follows: PI-4 had a tensile strength of 118MPa, an elongation at break of 23.7% and a modulus of 2.74 GPa.
Example 5
The molecular structural formula of the polyimide film PI-5 in this example 5 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100.
The preparation method of the polyimide film PI-5 comprises the following steps:
(1) 4.0048g (0.02mol) of 4,4 '-diaminodiphenyl ether (ODA), 0.5407g (0.005mol) of p-phenylenediamine (PPD), 0.5407g (0.005mol) of m-phenylenediamine (MPD), 0.0087g (0.03mmol) of 4,4' -Triaminotriphenylmethane (TAPM), 0.0087g (0.03mmol) of tris (4-aminophenyl) amine (TAPA) and 50g of N, N-dimethylacetamide (DMAc) are weighed into a 100mL round-bottomed flask at room temperature, argon is introduced, 1.4711g (0.005mol) of 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA) and 5.4530g (0.025mol) of pyromellitic dianhydride (PMDA) are added after complete dissolution, and stirring is continued for 12 hours at room temperature, so as to obtain a transparent, homogeneous and viscous polyamic acid solution (PAA).
Step (2) the PI-5 polyimide film was obtained in the same manner as in example 1.
The detection results of the PI-5 polyimide film are as follows: PI-5 had a tensile strength of 127MPa, an elongation at break of 24.2% and a modulus of 3.37 GPa.
Example 6
The molecular structural formula of the polyimide film PI-6 in this example 6 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100.
The preparation method of the polyimide film PI-6 comprises the following steps:
(1) 1.2014g (0.006mol) of 4,4 '-diaminodiphenyl ether (ODA), 1.1896g (0.006mol) of 4,4' -diaminodiphenylmethane (DDM), 2.56g (0.008mol) of 2,2 '-bis (trifluoromethyl) diaminobiphenyl (TFMB), 0.0116g (0.04mmol) of 4,4' -Triaminotriphenylmethane (TAPM) and 50g of N, N-dimethylacetamide (DMAc) are weighed in a 100mL round-bottomed flask at room temperature, argon is introduced, after complete dissolution, 2.0820g (0.004mol) of bisphenol A type diether dianhydride (BPADA) and 3.4899g (0.016mol) of pyromellitic dianhydride (PMDA) are added, and stirring is continued at room temperature for 12 hours to obtain a transparent, homogeneous and viscous polyamic acid (PAA) glue solution.
(2) Placing the prepared glue solution under the negative pressure condition of 0.1MPa for 1-2h, removing bubbles, then scraping and coating the glue solution on a clean glass plate, and placing the clean glass plate in an oven for programmed temperature rise: heating the mixture to 170 ℃ at room temperature, and controlling the heating rate at 2 ℃/min; heating to 200 ℃ at 170 ℃, and controlling the heating rate at 4 ℃/min; the temperature is increased to 300 ℃ from 200 ℃, and the temperature increase rate is controlled to be 2 ℃/min. And naturally cooling to room temperature after heating to obtain the PI-1 polyimide film.
The detection results of the PI-6 polyimide film are as follows: PI-6 had a tensile strength of 102MPa, an elongation at break of 8.0% and a modulus of 3.49 GPa.
Comparative example 1
The molecular structural formula of the polyimide film PI-01 in this comparative example 1 is as follows:
comparative example 1 was prepared as in examples 1-4, but without the addition of aromatic triamine monomer to provide a PI-01 polyimide film;
the detection results of the PI-01 polyimide film are as follows: the tensile strength of PI-01 was 106MPa, the elongation at break was 15.2%, and the modulus was 2.71 GPa.
Comparative example 2
Comparative example 2 was prepared as in example 5, but without the addition of aromatic triamine monomer, to give a PI-02 polyimide film;
the detection results of the PI-02 polyimide film are as follows: the tensile strength of PI-02 was 116MPa, the elongation at break was 16.1%, and the modulus was 3.38 GPa.
Comparative example 3
Comparative example 3 was prepared as in example 6, except that no aromatic triamine monomer was added, to obtain a PI-03 polyimide film;
the detection result of the PI-03 polyimide film is as follows: the tensile strength of PI-03 was 83MPa, the elongation at break was 4.8%, and the modulus was 3.47 GPa.
The invention mainly tests and characterizes the mechanical properties, and the results are shown in table 1.
TABLE 1 mechanical Property test results of polyimide films of the present invention
As can be seen from the comparison of the data, the mechanical properties of the polyimide film prepared by the invention are greatly improved compared with those of the polyimide film prepared by the comparative example, the tensile strength is improved by 23.6 percent to the maximum, the elongation at break is improved by 93.4 percent to the maximum, and the modulus is basically unchanged.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. The polyimide film is characterized in that the molecular structural formula of the polyimide film PI-1 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100;
the preparation method of the polyimide film PI-1 comprises the following steps:
(1) weighing 6.0072g of 4,4' -diaminodiphenyl ether, 0.0105g of 1,3, 5-tris (4-aminophenyl) benzene and 50g of N, N-dimethylacetamide in a 100mL round-bottom flask at room temperature, introducing argon, adding 6.4050g of pyromellitic dianhydride after completely dissolving, and continuously stirring for 12 hours at room temperature to obtain a transparent, homogeneous and viscous polyamide acid PA glue solution;
(2) placing the prepared glue solution under the negative pressure condition of 0.1MPa for 1-2h, removing bubbles, then scraping and coating the glue solution on a clean glass plate, and placing the clean glass plate in an oven for programmed temperature rise: heating the mixture to 170 ℃ at room temperature, and controlling the heating rate at 2 ℃/min; heating to 200 ℃ at 170 ℃, and controlling the heating rate at 4 ℃/min; heating to 400 ℃ at 200 ℃, and controlling the heating rate at 3 ℃/min; and naturally cooling to room temperature after heating to obtain the PI-1 polyimide film.
2. The polyimide film is characterized in that the molecular structural formula of the polyimide film PI-2 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100;
the preparation method of the polyimide film PI-2 comprises the following steps:
(1) weighing 6.0072g of 4,4' -diaminodiphenyl ether, 0.0087g of tri (4-aminophenyl) amine and 50g of N, N-dimethylacetamide in a 100mL round-bottom flask at room temperature, introducing argon, adding 6.4050g of pyromellitic dianhydride after completely dissolving, and continuously stirring for 12 hours at room temperature to obtain a transparent, homogeneous and viscous polyamic acid glue solution;
step (2) the PI-2 polyimide film is obtained by the method of claim 1.
3. The polyimide film is characterized in that the molecular structural formula of the polyimide film PI-3 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100;
the preparation method of the polyimide film PI-3 comprises the following steps:
(1) weighing 6.0072g of 4,4 '-diaminodiphenyl ether, 0.0087g of 4,4' -triaminotriphenylmethane and 50g of N, N-dimethylacetamide into a 100mL round-bottom flask at room temperature, introducing argon, adding 6.4050g of pyromellitic dianhydride after completely dissolving, and continuously stirring for 12 hours at room temperature to obtain transparent, homogeneous and viscous polyamide acid (PAA) glue solution;
step (2) the PI-3 polyimide film is obtained by the method of claim 1.
4. The polyimide film is characterized in that the molecular structural formula of the polyimide film PI-4 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100;
the preparation method of the polyimide film PI-4 comprises the following steps:
(1) weighing 6.0072g of 4,4' -diaminodiphenyl ether, 0.0173g of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and 50g of N, N-dimethylacetamide in a 100mL round-bottom flask at room temperature, introducing argon, adding 6.4704g of pyromellitic dianhydride after completely dissolving, and continuously stirring for 12 hours at room temperature to obtain a transparent, homogeneous and viscous polyamic acid glue solution;
step (2) the PI-4 polyimide film is obtained by the method of claim 1.
5. The polyimide film is characterized in that the molecular structural formula of the polyimide film PI-5 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100;
the preparation method of the polyimide film PI-5 comprises the following steps:
(1) weighing 4.0048g of 4,4 '-diaminodiphenyl ether, 0.5407g of p-phenylenediamine, 0.5407g of m-phenylenediamine, 0.0087g of 4,4' -triaminotriphenylmethane, 0.0087g of tri (4-aminophenyl) amine and 50g of N, N-dimethylacetamide in a 100mL round-bottom flask at room temperature, introducing argon, adding 1.4711g of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 5.4530g of pyromellitic dianhydride after completely dissolving, and continuously stirring for 12 hours at room temperature to obtain a transparent, homogeneous and viscous polyamic acid glue solution;
step (2) the PI-5 polyimide film is obtained by the method of claim 1.
6. The polyimide film is characterized in that the molecular structural formula of the polyimide film PI-6 is as follows:
wherein x is 1-100, y is 1-100, and z is 1-100;
the preparation method of the polyimide film PI-6 comprises the following steps:
(1) weighing 1.2014g of 4,4 '-diaminodiphenyl ether, 1.1896g of 4,4' -diaminodiphenylmethane, 2 '-bis (trifluoromethyl) diaminobiphenyl, 2.56g of 4,4' -triaminotriphenylmethane and 50g of N, N-dimethylacetamide in a 100mL round-bottom flask at room temperature, introducing argon, adding 2.0820g of bisphenol A type diether dianhydride and 3.4899g of pyromellitic dianhydride after complete dissolution, and continuously stirring at room temperature for 12 hours to obtain a transparent, homogeneous and viscous polyamic acid glue solution;
(2) placing the prepared glue solution under the negative pressure condition of 0.1MPa for 1-2h, removing bubbles, then scraping and coating the glue solution on a clean glass plate, and placing the clean glass plate in an oven for programmed temperature rise: heating the mixture to 170 ℃ at room temperature, and controlling the heating rate at 2 ℃/min; heating to 200 ℃ at 170 ℃, and controlling the heating rate at 4 ℃/min; heating to 200 deg.C to 300 deg.C, and controlling the heating rate at 2 deg.C/min; and naturally cooling to room temperature after heating to obtain the PI-1 polyimide film.
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| JP4428491B2 (en) * | 2000-02-28 | 2010-03-10 | 大日本印刷株式会社 | Electrodeposition polyimide resin composition, method for producing the same, electrodeposition molded article, and method for producing the same |
| CN102134395A (en) * | 2010-12-22 | 2011-07-27 | 北京航空航天大学 | Modified light flexible polyimide foam material and preparation method thereof |
| CN105237785A (en) * | 2015-10-30 | 2016-01-13 | 南京理工大学 | Preparation method for polyimide thin film |
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| JP4428491B2 (en) * | 2000-02-28 | 2010-03-10 | 大日本印刷株式会社 | Electrodeposition polyimide resin composition, method for producing the same, electrodeposition molded article, and method for producing the same |
| CN102134395A (en) * | 2010-12-22 | 2011-07-27 | 北京航空航天大学 | Modified light flexible polyimide foam material and preparation method thereof |
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