CN116162244A - Bending-resistant polyimide film and preparation method thereof - Google Patents
Bending-resistant polyimide film and preparation method thereof Download PDFInfo
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- CN116162244A CN116162244A CN202310195866.1A CN202310195866A CN116162244A CN 116162244 A CN116162244 A CN 116162244A CN 202310195866 A CN202310195866 A CN 202310195866A CN 116162244 A CN116162244 A CN 116162244A
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- 238000005452 bending Methods 0.000 title claims abstract description 103
- 229920001721 polyimide Polymers 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 35
- 150000004985 diamines Chemical class 0.000 claims abstract description 21
- 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 20
- 238000000034 method Methods 0.000 claims abstract description 20
- YLZGEUWNNPEHBA-UHFFFAOYSA-N anthracene-1,8-diamine Chemical compound C1=CC(N)=C2C=C3C(N)=CC=CC3=CC2=C1 YLZGEUWNNPEHBA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000004952 Polyamide Substances 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 3
- 229920002647 polyamide Polymers 0.000 claims abstract description 3
- 238000010345 tape casting Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 45
- 239000004642 Polyimide Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 12
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000035484 reaction time Effects 0.000 claims 1
- 230000003068 static effect Effects 0.000 abstract description 18
- 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 abstract description 13
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 9
- 230000005489 elastic deformation Effects 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 17
- 239000003292 glue Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000007888 film coating Substances 0.000 description 10
- 238000009501 film coating Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- NXDMHKQJWIMEEE-UHFFFAOYSA-N 4-(4-aminophenoxy)aniline;furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1.C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O NXDMHKQJWIMEEE-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- 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
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- 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
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- 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
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Abstract
A preparation method of a bending-resistant polyimide film comprises the following steps: under the environment of protective gas, adding at least one dianhydride in the formula PMDA, BPDA and 6FDA and at least one diamine in PDA, ODA, PABZ into a polar aprotic solvent, and carrying out polymerization reaction to obtain a low-molecular-weight polyamic acid solution; adding anthracene-1, 8-diamine and at least one dianhydride in PMDA, BPDA and 6FDA into a low molecular weight polyamic acid solution, and carrying out polymerization reaction by adopting dianhydride with the same structure in the two steps to obtain a high molecular weight polyamic acid solution; and (3) coating the polyamide acid solution with high molecular weight on a glass plate by adopting a tape casting method, and drying in vacuum to obtain the bending-resistant polyimide film. According to the invention, the elastic deformation range of the polymer is improved by constructing the folding macromolecular chain segment with the spring-like structure, so that the polymer can bear larger strain under a small folding radius, thereby improving the dynamic and static folding properties of the polyimide film and simultaneously keeping the thermal stability of the polyimide film.
Description
Technical Field
The invention relates to the field of polymer flexible substrate materials, in particular to a bending-resistant polyimide film and a preparation method thereof.
Background
With the development of electronic components, a flexible, wearable, lightweight polyimide substrate (PI) is attracting attention. PI substrates have the advantage of being crimpable, wearable, stretchable, heat resistant, and the like, and can withstand at least 20 ten thousand cyclic folds. However, the flexible substrate is subjected to repeated compressive and tensile stresses and bending moments when the electronic component is folded, acting on the inner side, the outer side and the direction perpendicular to the cross-section of the folded region, respectively. These stresses can cause irreversible strain accumulation in the substrate film, eventually forming visible wrinkles, thereby affecting the reliability of the flexible electronic component. Therefore, in developing a flexible electronic component, it is necessary to consider the reliability of the substrate and take corresponding measures to reduce the influence of stress.
In order to realize a Polyimide (PI) film with high folding resistance, many studies have been made in recent years. One such method is to compound an elastomeric layer with a PI film to transfer maximum strain to an elastomer with high elasticity, thereby reducing the strain in the PI substrate and enhancing its folding resistance (Jia, y.z., et al org. Electron.2019,65, 185-192). In addition, strengthening PI films by adding ionic liquids has been shown to impart a PI substrate with a tensile strength of 48.2MPa, an elongation at break of 108.4% and an ionic liquid intercalation PI film that can be folded 4 times at a minimum folding radius of 6 microns (Li, n.b., et al polymer 2018,153,538-547). In addition, crosslinked PI films also exhibit good folding resistance due to limited chain movement. Bea et al prepared PI/silica hybrids crosslinked by silane end groups, such crosslinked PI films exhibited low coefficients of thermal expansion, high thermal stability, and could be folded 200,000 times at a 3mm folding radius (Bae, W.J, et al Polymer 2016,105,124-132). In addition, hydrogen bonding and synergistic supramolecular networks have also been reported to confer fold reliability to crosslinked PI films in excess of 200,000 times (Chanjae Ahn, et al adv. Function. Mate. 2022.). However, as flexible electronics get thinner, PI-based films need to withstand as small a folding radius as possible. While PI films embedded in ionic liquids are able to withstand smaller folding radii, but unfortunately their mechanical properties and heat resistance are greatly reduced PI films crosslinked by covalent or hydrogen bonding networks exhibit good folding resistance at folding radii of 2-3 mm, brittle crosslinked films cannot withstand increased strains and folding angles with decreasing folding radii.
Thus, there remains a great difficulty in preparing PI films with high curvature fold resistance, and new strategies are urgently needed to enhance the fold resistance of PI films at high curvatures.
Disclosure of Invention
Based on the above, the invention provides a bending-resistant polyimide film and a preparation method thereof, which are used for solving the problems that the existing polymer has insufficient bending-resistant capability and is easy to crease in the bending process of large curvature.
In order to achieve the above purpose, the invention provides a bending-resistant polyimide film, which consists of a block-copolymerized polyimide macromolecule, wherein the structural general formula of the polyimide macromolecule is shown as formula (1):
wherein: m and n are positive integers, and 0.05<m/(m+n)<0.3；R 1 A structural unit selected from any dianhydride of the following formulas (2), (3) and (4) after removing anhydride at both ends, R 2 A structural unit obtained by removing amino groups at both ends of any diamine selected from the following formulas (5), (6) and (7);
according to another aspect of the present invention, the present invention also provides a method for preparing the above-mentioned bending-resistant polyimide film, including the following steps:
s1, adding at least one dianhydride in the formulas (2), (3) and (4) and at least one diamine in the formulas (5), (6) and (7) into a polar aprotic solvent in the environment of a shielding gas, and carrying out polymerization reaction to obtain a low-molecular-weight polyamic acid solution;
s2, adding anthracene-1, 8-diamine and at least one dianhydride in formulas (2), (3) and (4) into a low molecular weight polyamic acid solution, wherein the structure of the dianhydride adopted in the steps S1 and S2 is the same, the total molar weight of diamine in the system is the same as that of the dianhydride, and carrying out polymerization reaction to obtain a high molecular weight polyamic acid solution;
s3, coating the polyamide acid solution with high molecular weight on a glass plate by adopting a tape casting method, and drying in vacuum to obtain the bending-resistant polyimide film.
As a further preferable embodiment of the present invention, the amount of anthracene-1, 8-diamine added in step S2 is 5 to 30% of the total molar amount of dianhydride added in steps S1 and S2.
As a further preferable embodiment of the present invention, the amount of anthracene-1, 8-diamine added in step S2 is 10 to 25% of the total molar amount of dianhydride added in steps S1 and S2.
As a further preferable embodiment of the present invention, in the step S2, the solid content of the high molecular weight polyamic acid is 10% to 20%.
As a further preferable embodiment of the present invention, in the step S2, the solid content of the high molecular weight polyamic acid is 12 to 18%.
As a further preferable embodiment of the present invention, in the step S3, the high molecular weight polyamic acid solution is subjected to a condensation reaction at a temperature of 0 to 30℃for a period of 6 to 24 hours by stirring before casting.
As a further preferable technical scheme of the invention, in the step S3, vacuum drying is carried out by adopting temperatures of 80 ℃,120 ℃, 220 ℃ and 350 ℃ in sequence through a vacuum oven, and the treatment time at each temperature is 30-120 minutes.
The bending-resistant polyimide film and the preparation method thereof can achieve the following beneficial effects by adopting the technical scheme:
according to the invention, the elastic deformation range of the polymer is improved by constructing the folding macromolecular chain segment with the spring-like structure, so that the polymer can bear larger strain under a small folding radius, thereby improving the dynamic and static folding properties of the polyimide film and simultaneously keeping the thermal stability of the polyimide film. The polyimide substrate is suitable for various flexible, wearable and lightweight electronic equipment, so that the electronic equipment is improved to be capable of coping with more and more complex use environments, and has high commercial application value.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a graph showing the comparison of stretching angles of the polyimide films of comparative example 1 and examples 1 to 4.
FIG. 2 is a graph showing the comparison of stretching angles of the polyimide films of comparative example 2 and examples 5 to 8.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The bending-resistant polyimide film consists of segmented polyimide macromolecules, wherein the segmented polyimide has a structural general formula shown in a formula (1):
wherein: m and n are positive integers, and 0.05< m/(m+n) <0.3;
R 1 a structural unit obtained by removing acid anhydride at both ends from any dianhydride selected from the following formulas (2), (3) and (4):
R 2 a structural unit obtained by removing amino groups at both ends of any diamine selected from the following formulas (5), (6) and (7):
specifically, R is 1 Selected from the following structures:
specifically, R is 2 Selected from the following structures:
the block copolymerized polyimide represented by the formula (1) has a folded macromolecular chain segment having a spring-like structure represented by the following structure (8).
The invention provides a method for improving the bending resistance of a PI film by constructing a folding macromolecular chain segment with a spring-like structure. Specifically, anthracene-1, 8-diamine is partially introduced into a polyimide system, so that a large molecular chain segment of a spring is formed, recoverable elastic deformation of a glassy polymer caused by a bond long bond angle is fully utilized, the bending resistance of the polyimide under the condition of extremely large curvature is effectively improved, and the polyimide has good thermal performance.
The anthracene-1, 8-diamine has the following structural formula:
in order to enable those skilled in the art to further understand the technical scheme of the present invention, the technical scheme of the present invention is described in further detail below by way of examples.
What should be stated here is:
(1) In the static bending resistance test, a polyimide film was subjected to 180 ° folding (folding radius=0.5 mm) between two planes of 1mm, and heat-treated at 80 ℃ for 1 hour to accelerate the accumulation of plastic deformation. After cooling, the folded polyimide film was detached, and the open angle was measured to evaluate the static fracture resistance. Since the stretching angle of the polyimide film is the complement of the folding angle, resulting from plastic deformation, whereas the stretching angle of the PI film without folding is 180 °, it is considered that the polyimide film having a larger stretching angle exhibits better static bending resistance.
(2) Dynamic bending resistance was evaluated by a U-shaped dynamic bending test. The folding radius is fixed, so that the film is repeatedly folded and stretched, and the folding times of the folds are observed.
In the following examples and comparative examples, the structural formulae of the dianhydrides (PMDA, BPDA, 6 FDA) used are shown as formulae (2), (3) and (4), respectively, and the structural formulae of the diamines (PDA, ODA, PABZ) are shown as formulae (5), (6) and (7), respectively.
Comparative example 1
Argon is continuously introduced into a 100mL three-necked flask to maintain an anaerobic environment, 40mL of anhydrous N-methylpyrrolidone and 3.473g of ODA (17.34 mmol) are added, 3.783g of PMDA (17.34 mmol) are added after diamine is sufficiently dissolved by stirring by a stirring rod, stirring is continued for 3 hours to obtain a high molecular weight polyamic acid, the gum solution at this time has a certain viscosity, but a small amount of residual monomer remains on the wall of the flask, the flask is brought into the colloid by shaking, stirring and polymerization are continued for 6 hours, and the solid content of the gum solution at this time is 15% wt. Casting the polyamic acid solution on a clean glass plate substrate by adopting an automatic film coating machine, and placing the substrate in a vacuum oven for heating to remove the solvent and imidize to obtain a polyimide film, wherein the heating procedure is as follows in sequence: 80 ℃ for 1h, 120 ℃ for 1h, 220 ℃ for 1h, and 350 ℃ for 1h. Obtaining the polyimide film of the PMDA-ODA system.
The static bending-resistant lower stretching angle is 102 degrees; in the dynamic bending resistance test, when the bending radius is 0.5mm, folds appear after 1000 times of bending; when the bending radius is 0.25mm, folds appear after 1000 times of bending.
Comparative example 2
Argon was continuously introduced into a 100mL three-necked flask to maintain an anaerobic condition, 56mL of anhydrous N-methylpyrrolidone and 3.321g of PABZ (14.8 mmol) were added, and after the diamine was sufficiently dissolved by stirring with a stirring rod, 4.359g of BPDA (14.8 mmol) was added, and stirring was continued for 3 hours to obtain a polyamic acid having a high molecular weight, the gum solution had a certain viscosity, but a small amount of residual monomer remained on the flask wall was carried into the colloid by shaking the flask, and stirring polymerization was continued for 12 hours, at which time the solid content of the gum solution was 12% by weight. Casting the polyamic acid solution on a clean glass plate substrate by adopting an automatic film coating machine, and placing the substrate in a vacuum oven for heating to remove the solvent and imidize to obtain a polyimide film, wherein the heating procedure is as follows in sequence: 80 ℃ for 1h, 120 ℃ for 1h, 220 ℃ for 1h, 400 ℃ for 0.5h. Obtaining the polyimide film of the BPDA-PABZ system.
The static bending-resistant lower stretching angle is 120 degrees; in the dynamic bending resistance test, when the bending radius is 0.5mm, folds appear after 3000 times of bending; when the bending radius is 0.25mm, folds appear after 100 times of bending.
Example 1
Argon is continuously introduced into a 100mL three-necked flask to keep an anaerobic environment, 40mL of anhydrous N-methylpyrrolidone and 3.296g of ODA (16.46 mmol) are added, 3.402g of PMDA (15.6 mmol) is added after diamine is sufficiently dissolved by stirring by a stirring rod, low molecular weight polyamic acid with a certain molecular weight is obtained after stirring for 2 hours, at this time, 0.378g of PMDA (1.73 mmol) and 0.181g of anthracene-1, 8-diamine (0.87 mmol) are added, stirring is continued for 1 hour to obtain polyamic acid with a high molecular weight, the glue solution has a certain viscosity, but a little residual monomer remains on the wall of the flask, the flask is brought into the glue by shaking, and stirring and polymerization are continued for 6 hours, and the solid content of the glue solution is 15% wt. Casting the blending solution on a clean glass plate substrate by adopting an automatic film coating machine, and placing the glass plate substrate in a vacuum oven for heating to remove the solvent and imidize to obtain a polyimide film, wherein the heating procedure is as follows in sequence: 80 ℃ for 1h, 120 ℃ for 1h, 220 ℃ for 1h, and 350 ℃ for 1h. To obtain the copolyimide film PI-1.
The static bending-resistant lower stretching angle is 107 degrees; in the dynamic bending resistance test, when the bending radius is 0.5mm, folds appear after 1500 times of bending; when the bending radius is 0.25mm, folds appear after 10 times of bending. The depth of the cracks in the bending area is weaker than that of the bending area in comparative example 1, the number of the cracks is smaller, the dynamic bending resistance is improved, and the performance is obviously improved.
Example 2
Argon is continuously introduced into a 100mL three-necked flask to keep an anaerobic environment, 40mL of anhydrous N-methylpyrrolidone and 3.120g of ODA (15.58 mmol) are added, 3.209g of PMDA (14.71 mmol) is added after diamine is fully dissolved by stirring through a stirring rod, low molecular weight polyamic acid with a certain molecular weight is obtained after stirring for 2 hours, at this time, 0.566g of PMDA (2.6 mmol) and 0.36g of anthracene-1, 8-diamine (1.73 mmol) are added, stirring is continued for 1 hour to obtain high molecular weight polyamic acid, the glue solution at this time has a certain viscosity, but a little residual monomer remains on the wall of the flask, the flask is brought into the glue by shaking, and stirring and polymerization are continued for 6 hours, and the solid content of the glue solution at this time is 15% wt. Casting the blending solution on a clean glass plate substrate by adopting an automatic film coating machine, and placing the glass plate substrate in a vacuum oven for heating to remove the solvent and imidize to obtain a polyimide film, wherein the heating procedure is as follows in sequence: 80 ℃ for 1h, 120 ℃ for 1h, 220 ℃ for 1h, and 350 ℃ for 1h. And obtaining the copolyimide film PI-2.
The static bending-resistant lower stretching angle is 124 degrees; in the dynamic bending resistance test, when the bending radius is 0.5mm, no crease appears after 200000 times of bending; when the bending radius is 0.25mm, folds appear after 2000 times of bending.
Example 3
Argon is continuously introduced into a 100mL three-necked flask to keep an anaerobic environment, 40mL of anhydrous N-methylpyrrolidone and 2.778g of ODA (13.82 mmol) are added, 2.826g of PMDA (12.96 mmol) is added after diamine is fully dissolved by stirring through a stirring rod, low molecular weight polyamic acid with a certain molecular weight is obtained after stirring for 2 hours, 0.942g of PMDA (4.32 mmol) and 0.720g of anthracene-1, 8-diamine (3.46 mmol) are added at this time, stirring is continued for 1 hour to obtain high molecular weight polyamic acid, the glue solution at this time has a certain viscosity, but a little residual monomer remains on the wall of the flask, the flask is brought into the glue by shaking, and polymerization is continued for 6 hours with the solid content of the glue solution at this time being 15% wt. Casting the blending solution on a clean glass plate substrate by adopting an automatic film coating machine, and placing the glass plate substrate in a vacuum oven for heating to remove the solvent and imidize to obtain a polyimide film, wherein the heating procedure is as follows in sequence: 80 ℃ for 1h, 120 ℃ for 1h, 220 ℃ for 1h, and 350 ℃ for 1h. To obtain the copolyimide film PI-3.
The static bending-resistant lower stretching angle is 154 degrees; in the dynamic bending resistance test, no crease appears after the bending radius is 0.5mm and 200000 times of bending; when the bending radius is 0.25mm, folds appear after 20000 times of bending.
Example 4
Argon is continuously introduced into a 100mL three-necked flask to keep an anaerobic environment, 40mL of anhydrous N-methylpyrrolidone and 2.417g of ODA (12.07 mmol) are added, the diamine is sufficiently dissolved by stirring by a stirring rod, 2.445g of PMDA (11.21 mmol) is added, stirring is continued for 2 hours to obtain low molecular weight polyamic acid with a certain molecular weight, at this time, 1.316 of PMDA (6.03 mmol) and 1.077g of anthracene-1, 8-diamine (5.17 mmol) are added, stirring is continued for 1 hour to obtain high molecular weight polyamic acid, the glue solution at this time has a certain viscosity, but a little residual monomer remains on the wall of the flask, the flask is brought into the glue by shaking, and stirring and polymerization are continued for 6 hours, and the solid content of the glue solution at this time is 15% wt. Casting the blending solution on a clean glass plate substrate by adopting an automatic film coating machine, and placing the glass plate substrate in a vacuum oven for heating to remove the solvent and imidize to obtain a polyimide film, wherein the heating procedure is as follows in sequence: 80 ℃ for 1h, 120 ℃ for 1h, 220 ℃ for 1h, and 350 ℃ for 1h. And obtaining the copolyimide film PI-4.
The static bending-resistant lower stretching angle is 156 degrees; in the dynamic bending resistance test, no crease appears after the bending radius is 0.5mm and 200000 times of bending; when the bending radius is 0.25mm, the film breaks after 20000 times of bending.
Example 5
An oxygen-free atmosphere was maintained by continuously introducing argon gas into a 100mL three-necked flask, 50mL of anhydrous N-methylpyrrolidone and 2.885g of PABZ (12.86 mmol) were added, and after the diamine was sufficiently dissolved by stirring with a stirring rod, 3.585g of BPDA (12.18 mmol) was added, and stirring was continued for 2 hours to obtain a low molecular weight polyamic acid having a certain molecular weight, at this time, 0.398g of BPDA (1.36 mmol) and 0.141g of anthracene-1, 8-diamine (0.68 mmol) were added, and stirring polymerization was continued for 12 hours, at this time, the solid content of the dope was 12% by weight. Casting the polyamic acid solution on a clean glass plate substrate by adopting an automatic film coating machine, and placing the substrate in a vacuum oven for heating to remove the solvent and imidize to obtain a polyimide film, wherein the heating procedure is as follows in sequence: 80 ℃ for 1h, 120 ℃ for 1h, 220 ℃ for 1h, 400 ℃ for 0.5h. And obtaining the copolyimide film PI-5.
The static bending-resistant lower stretching angle is 124 degrees; in the dynamic bending resistance test, when the bending radius is 0.5mm, folds appear after 10000 times of bending; when the bending radius is 0.25mm, folds appear after 2000 times of bending.
Example 6
Argon was continuously introduced into a 100mL three-necked flask to maintain an oxygen-free atmosphere, 50mL of anhydrous N-methylpyrrolidone and 2.737g of PABZ (12.2 mmol) were added, and after the diamine was sufficiently dissolved by stirring with a stirring rod, 3.391g of BPDA (11.53 mmol) was added, and stirring was continued for 2 hours to obtain a low molecular weight polyamic acid having a certain molecular weight, at this time, 0.597g of BPDA (2.03 mmol) and 0.282g of anthracene-1, 8-diamine (1.36 mmol) were added, and stirring polymerization was continued for 12 hours, at which time the solid content of the dope was 12% wt. Casting the polyamic acid solution on a clean glass plate substrate by adopting an automatic film coating machine, and placing the substrate in a vacuum oven for heating to remove the solvent and imidize to obtain a polyimide film, wherein the heating procedure is as follows in sequence: 80 ℃ for 1h, 120 ℃ for 1h, 220 ℃ for 1h, 400 ℃ for 0.5h. To obtain the copolyimide film PI-6.
The static bending-resistant lower stretching angle is 144 degrees; in the dynamic bending resistance test, no crease appears after the bending radius is 0.5mm and 200000 times of bending; when the bending radius is 0.25mm, folds appear after 10000 times of bending.
Example 7
An oxygen-free atmosphere was maintained by continuously introducing argon gas into a 100mL three-necked flask, 50mL of anhydrous N-methylpyrrolidone and 2.441g of PABZ (10.88 mmol) were added, and after the diamine was sufficiently dissolved by stirring with a stirring rod, 3.002g of BPDA (10.2 mmol) was added, and stirring was continued for 2 hours to obtain a low molecular weight polyamic acid having a certain molecular weight, at this time, 1.001g of BPDA (3.4 mmol) and 0.567g of anthracene-1, 8-diamine (2.72 mmol) were added, and stirring polymerization was continued for 12 hours, at this time, the solid content of the dope was 12% by weight. Casting the polyamic acid solution on a clean glass plate substrate by adopting an automatic film coating machine, and placing the substrate in a vacuum oven for heating to remove the solvent and imidize to obtain a polyimide film, wherein the heating procedure is as follows in sequence: 80 ℃ for 1h, 120 ℃ for 1h, 220 ℃ for 1h, 400 ℃ for 0.5h. To obtain the copolyimide film PI-7.
The static bending-resistant lower stretching angle is 160 degrees; in the dynamic bending resistance test, no crease appears after the bending radius is 0.5mm and 200000 times of bending; crease occurred after 120,000 bends with a bend radius of 0.25 mm.
Example 8
An oxygen-free atmosphere was maintained by continuously introducing argon gas into a 100mL three-necked flask, 50mL of anhydrous N-methylpyrrolidone and 2.142g of PABZ (9.55 mmol) were added, and after the diamine was sufficiently dissolved by stirring with a stirring rod, 2.61g of BPDA (8.87 mmol) was added, and stirring was continued for 2 hours to obtain a low molecular weight polyamic acid having a certain molecular weight, at this time 1.405g of BPDA (4.78 mmol) and 0.853g of anthracene-1, 8-diamine (4.1 mmol) were added, and stirring polymerization was continued for 12 hours, at which time the solid content of the dope was 12% wt. Casting the polyamic acid solution on a clean glass plate substrate by adopting an automatic film coating machine, and placing the substrate in a vacuum oven for heating to remove the solvent and imidize to obtain a polyimide film, wherein the heating procedure is as follows in sequence: 80 ℃ for 1h, 120 ℃ for 1h, 220 ℃ for 1h, 400 ℃ for 0.5h. To obtain the copolyimide film PI-8.
The static bending-resistant lower stretching angle is 163 degrees; in the dynamic bending resistance test, no crease appears after the bending radius is 0.5mm and 200000 times of bending; when the bending radius is 0.25mm, the film breaks after 10000 times of bending.
In order to conveniently examine the performance improvement of the film material of the embodiment, the invention carries out statistics on dynamic bending resistance and static bending resistance tests, and compares comparative example 1 with examples 1,2,3 and 4; comparative example 2 and examples 5,6,7,8 are compared. The results are shown in Table 1, table 2, FIGS. 1 and 2.
Table 1: comparative example 1 Each example of the system and comparative example polyimide film dynamic bending resistance
Note that: for the dynamic folding test, "++" indicates that no crease was observed in the polyimide film and the number indicates the number of folds that have crease at the current bend radius. The film of example 4 was broken after 20000 folds with a folding radius of 0.25 mm.
Table 2: basic Properties and dynamic bending resistance of polyimide films obtained in examples of comparative example 2 System
Note that: for the dynamic folding test, "++" indicates that no crease was observed in the polyimide film and the number indicates the number of folds that have crease at the current bend radius. The film of example 8 was broken after 10000 folds with a folding radius of 0.25 mm.
The static bending-resistant lower stretching angle is 154 degrees; in the dynamic bending resistance test, no crease appears after the bending radius is 0.5mm and 200000 times of bending; when the bending radius is 0.25mm, folds appear after 20000 times of bending.
To further investigate the beneficial technical effects of the present invention, the same preparation method as in example 3 was used, with the anthracene-1, 8-diamine remaining unchanged in the material system, replacing only the dianhydride or combination of the remaining diamines, i.e. the dianhydride used BPDA or 6FDA, or the remaining diamines used PDA or PABZ. Experiments prove that the combined systems can introduce a spring-like structure into a molecular chain, and the elastic deformation range is enlarged, so that the bending resistance is stronger than that of an original system without adopting anthracene-1, 8-diamine copolymerization, the system has the same material properties in the system, and the obtained copolyimide film has the similar dynamic bending resistance and static bending resistance as those of the embodiment 3, and can achieve the technical effects of the application.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (8)
1. The bending-resistant polyimide film is characterized by comprising segmented polyimide macromolecules, wherein the structural general formula of the polyimide macromolecules is shown as formula (1):
wherein: m and n are positive integers, and 0.05<m/(m+n)<0.3；R 1 A structural unit selected from any dianhydride of the following formulas (2), (3) and (4) after removing anhydride at both ends, R 2 A structural unit obtained by removing amino groups at both ends of any diamine selected from the following formulas (5), (6) and (7);
2. a method for preparing the bending-resistant polyimide film according to claim 1, which is characterized by comprising the following steps:
s1, adding at least one dianhydride in the formulas (2), (3) and (4) and at least one diamine in the formulas (5), (6) and (7) into a polar aprotic solvent in the environment of a shielding gas, and carrying out polymerization reaction to obtain a low-molecular-weight polyamic acid solution;
s2, adding anthracene-1, 8-diamine and at least one dianhydride in formulas (2), (3) and (4) into a low molecular weight polyamic acid solution, wherein the structure of the dianhydride adopted in the steps S1 and S2 is the same, the total molar weight of diamine in the system is the same as that of the dianhydride, and carrying out polymerization reaction to obtain a high molecular weight polyamic acid solution;
s3, coating the polyamide acid solution with high molecular weight on a glass plate by adopting a tape casting method, and drying in vacuum to obtain the bending-resistant polyimide film.
3. The method for preparing a bending-resistant polyimide film according to claim 2, wherein the amount of anthracene-1, 8-diamine added in the step S2 is 5 to 30% of the total molar amount of dianhydride added in the steps S1 and S2.
4. The method for preparing a bending-resistant polyimide film according to claim 2, wherein the amount of anthracene-1, 8-diamine added in the step S2 is 10 to 25% of the total molar amount of dianhydride added in the steps S1 and S2.
5. The method for producing a bending-resistant polyimide film according to claim 2, wherein the solid content of the high molecular weight polyamic acid in step S2 is 10% to 20%.
6. The method for producing a bending-resistant polyimide film according to claim 2, wherein the solid content of the high molecular weight polyamic acid in step S2 is 12 to 18%.
7. The method for producing a bending-resistant polyimide film according to claim 2, wherein in step S3, the high molecular weight polyamic acid solution is subjected to a condensation reaction at a temperature of 0 to 30 ℃ for a reaction time of 6 to 24 hours by stirring before casting.
8. The method for producing a bending-resistant polyimide film according to claim 2, wherein in step S3, vacuum drying is performed by a vacuum oven at 80 ℃,120 ℃, 220 ℃ and 350 ℃ in this order, and the treatment time at each temperature is 30 to 120 minutes.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050196605A1 (en) * | 2004-03-08 | 2005-09-08 | Ecology Coatings, Inc. | Environmentally friendly coating compositions for coating metal objects, coated objects therefrom, and methods, processes and assemblages for coating thereof |
| US20060041047A1 (en) * | 2004-03-08 | 2006-02-23 | Ecology Coatings, Inc. | Environmentally friendly coating compositions for coating metal objects, coated objects therefrom and methods, processes and assemblages for coating thereof |
| WO2019060169A1 (en) * | 2017-09-19 | 2019-03-28 | E. I. Du Pont De Nemours And Company | Low-color polymers for use in electronic devices |
| US20200207915A1 (en) * | 2017-09-07 | 2020-07-02 | Toray Industries, Inc. | Resin composition, method of producing resin film, and method of producing electronic device |
| CN111647157A (en) * | 2020-05-27 | 2020-09-11 | 广州星晰材料有限公司 | Method for preparing transparent polyimide by block copolymerization composite decoloring |
| CN114085378A (en) * | 2021-11-16 | 2022-02-25 | 吉林奥来德光电材料股份有限公司 | Polyamide acid solution and preparation method thereof, polyimide film and preparation method and application thereof |
| CN114621436A (en) * | 2022-03-29 | 2022-06-14 | 深圳瑞华泰薄膜科技股份有限公司 | High heat-resistant transparent polyimide film, preparation method and application |
| WO2022125839A1 (en) * | 2020-12-11 | 2022-06-16 | Aspen Aerogels, Inc. | Water co-catalyst for polyimide process |
-
2023
- 2023-03-03 CN CN202310195866.1A patent/CN116162244B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050196605A1 (en) * | 2004-03-08 | 2005-09-08 | Ecology Coatings, Inc. | Environmentally friendly coating compositions for coating metal objects, coated objects therefrom, and methods, processes and assemblages for coating thereof |
| US20060041047A1 (en) * | 2004-03-08 | 2006-02-23 | Ecology Coatings, Inc. | Environmentally friendly coating compositions for coating metal objects, coated objects therefrom and methods, processes and assemblages for coating thereof |
| US20200207915A1 (en) * | 2017-09-07 | 2020-07-02 | Toray Industries, Inc. | Resin composition, method of producing resin film, and method of producing electronic device |
| WO2019060169A1 (en) * | 2017-09-19 | 2019-03-28 | E. I. Du Pont De Nemours And Company | Low-color polymers for use in electronic devices |
| CN111647157A (en) * | 2020-05-27 | 2020-09-11 | 广州星晰材料有限公司 | Method for preparing transparent polyimide by block copolymerization composite decoloring |
| WO2022125839A1 (en) * | 2020-12-11 | 2022-06-16 | Aspen Aerogels, Inc. | Water co-catalyst for polyimide process |
| CN114085378A (en) * | 2021-11-16 | 2022-02-25 | 吉林奥来德光电材料股份有限公司 | Polyamide acid solution and preparation method thereof, polyimide film and preparation method and application thereof |
| CN114621436A (en) * | 2022-03-29 | 2022-06-14 | 深圳瑞华泰薄膜科技股份有限公司 | High heat-resistant transparent polyimide film, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| WEI, Y: "Ultralarge Curvature Folding Resistance of Polyimide Films Based on Spring-Like Folding Segments", ACS MACRO LETTERS, vol. 12, no. 6, 17 May 2023 (2023-05-17), pages 703 - 709 * |
| 鲁云华;王永飞;肖国勇;迟海军;胡知之;李论;: "无色透明耐高温聚酰亚胺膜材料的研究进展", 化工新型材料, no. 08, 15 August 2009 (2009-08-15), pages 8 - 10 * |
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