CN114835899A - High-temperature-resistant shape memory transparent polyimide film and shape memory electrode prepared from same - Google Patents
High-temperature-resistant shape memory transparent polyimide film and shape memory electrode prepared from same Download PDFInfo
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a high-temperature-resistant shape memory transparent polyimide film and a shape memory electrode prepared from the same. The high-temperature-resistant shape memory transparent polyimide film is prepared by taking 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl as a diamine monomer and taking hexafluoro dianhydride and cyclopentanone bis-spironorbornane tetracarboxylic dianhydride as dianhydride monomers through a one-step polycondensation reaction. The transparent polyimide film prepared by the invention has the advantages of 90.9-91.8 percent of visible light transmittance at 550nm, 16.73-20.67ppm/K of thermal expansion coefficient, 356 ℃ of glass transition temperature and 370 ℃ of shape recovery rate, 97-98 percent of excellent performance and suitability for being used as a substrate of a shape memory flexible electronic device.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-temperature-resistant shape memory transparent polyimide film and a shape memory electrode prepared from the same.
Background
In recent years, along with the trend of light weight, miniaturization, ultra-thinning and flexibility of photoelectric devices, the CPI film has been widely applied to the manufacture of photoelectric devices such as touch screens, flexible printed circuit boards, flexible solar cells and flexible displays due to the good colorless transparency, heat resistance and insulation, and has great market potential. In the field of electronic product display screens, OLEDs replace LCDs and are developed towards curved surfaces, folding and curling, the market permeability of flexible OLEDs is continuously improved, the application range is expanded from mobile phones to products such as televisions, and the development of the CPI film industry for flexible display is promoted. However, with the improvement of the technical level of flexible light/electronics, a single flexible substrate which is extensible, foldable and bendable cannot meet the requirements of people on the preparation of flexible photoelectric devices with specific functions and structures, and the use of the flexible substrate with the shape memory effect as the substrate of the flexible photoelectric device can not only realize the controllability of the macroscopic structure of the device, but also endow the photoelectric device with the shape memory function, so as to be applied to high-end application scenes such as robots, medical instruments, aerospace and the like.
The material of the flexible substrate with the shape memory effect is a shape memory material. The shape memory material is an intelligent material which has an initial shape, can sense and respond to external change stimulation to recover the initial state after being deformed and fixed under a certain condition. The shape memory material mainly comprises Shape Memory Alloy (SMA), Shape Memory Ceramic (SMC) and Shape Memory Polymer (SMP), and compared with the shape memory alloy and the shape memory ceramic, the shape memory polymer has the advantages of small density, large strain, wide corresponding range of stimulation, good processing performance, high chemical stability and the like, and the shape memory CPI also has good transparency and wider application prospect in the field of flexible photoelectric devices. However, the manufacturing process of the flexible device is often required to be carried out at a higher temperature, so that the requirement on the high-temperature resistance of the flexible substrate is higher, the glass transition temperature of the conventional shape memory CPI is lower, and the requirement on high-temperature processing cannot be met.
Disclosure of Invention
In order to solve the problems, the invention provides a high-temperature-resistant shape memory transparent polyimide film and a shape memory electrode prepared from the same, and solves the problem that the high-temperature processing of a flexible electronic device cannot be met due to the low glass transition temperature of shape memory polyimide in the prior art.
The invention provides a high-temperature-resistant shape memory transparent polyimide film, which is prepared by taking 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl as a diamine monomer and hexafluoro dianhydride and cyclopentanone bis-spironorbornane tetracarboxylic dianhydride as dianhydride monomers through one-step polycondensation reaction.
In some of these embodiments, the molar ratio of the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, the hexafluoro dianhydride, and the cyclopentanone bis-spironorbomane tetracarboxylic dianhydride is 5: (5-A): a, wherein 1. ltoreq. A.ltoreq.4, preferably 2. ltoreq. A.ltoreq.3.
Specifically, the structure of the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl is as follows:
the structure of the hexafluorodianhydride is as follows:
the structure of the cyclopentanone spiro-norbornane tetracarboxylic dianhydride is as follows:
in some of these embodiments, the structure of the transparent polyimide film is as follows:
wherein:
x, y and z are independently selected from any number between 0.2 and 0.8.
The polyimide has a shape memory function, namely when the temperature reaches the glass transition temperature of the polyimide, because the chain segments obtain enough energy and free volume, the chain segments of macromolecules and the motion capability of long chains are improved, the polymer generates large strain due to the motion of the chain segments under the stretching action of external force, and when the temperature is reduced to be below the glass transition temperature, the motion capability of the chain segments is frozen, the stored elastic strain energy in the stretching process cannot be released and is stored in the polymer, at the moment, only the bond angles, the bond lengths and the side group units move, and as a result of the motion of the units, a small part of elastic energy can be slowly relaxed in a long time, and most of the elastic strain energy can be completely stored in the polymer, so that the polyimide is endowed with high shape fixing rate. When the polyimide is heated again to the glass transition temperature, the chain segment begins to move violently because the chain segment obtains enough energy and free volume, so that the elastic strain energy stored in the chain segment is gradually released, and the shape is promoted to return to the original state. The invention adopts 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl and cyclopentanone bisspironorbornane tetracarboxylic dianhydride as composite dianhydride, the fluorine-containing 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl monomer has excellent performance and can endow transparent polyimide with better optical performance, but the use of the monomer can reduce the adhesiveness of the polyimide and increase the thermal expansion coefficient of the material; the cyclic acid dianhydride cyclopentanone bis-spironorbornane tetracarboxylic dianhydride diester has a rigid (hard) spiro structure, has better heat resistance than a common alicyclic monomer, can enable the transparent polyimide to have lower thermal expansion coefficient and good dielectric property, and utilizes the complementary advantages of the two to prepare the polyimide with excellent optical and mechanical properties.
In some of the embodiments, the method for preparing the transparent polyimide film comprises the following steps:
(1) sequentially adding a reaction solvent, 4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, hexafluoro dianhydride, cyclopentanone bis-spironorbornane tetracarboxylic dianhydride, a crosslinking monomer, a catalyst and a molecular weight control agent into a reaction kettle in a nitrogen atmosphere to obtain a reaction precursor solution;
(2) heating the reaction precursor solution to react;
(3) after the reaction is finished, adding a diluent into the reaction solution, and uniformly stirring to obtain polyimide slurry;
(4) and coating the polyimide slurry on a base material, heating and drying by adopting a program, and demolding to obtain the transparent polyimide film with the shape memory function.
In some of these embodiments, the crosslinking monomer is tris (4-aminophenyl) amine, having the structure:
in some embodiments, the heating temperature in step (2) is 135-; preferably, the heating temperature is 145-155 ℃, and the heating time is 5-6 h.
In some of these embodiments, the polyimide slurry has a solids content of 20-30%.
The general high polymer glass transition temperature has a direct relation with the flexibility of a molecular chain, and the higher the flexibility of the molecular chain is, the lower the glass transition temperature is; the molecular chain has high rigidity and the glass transition temperature is high. In the invention, dianhydride monomers with large volume, high rigidity structure and high melting point such as benzene ring and spiro ring are selected as reaction dianhydride, so that the flexibility of molecules is limited; meanwhile, a crosslinking monomer tri (4-aminophenyl) amine is added into a polycondensation reaction system to improve the crosslinking degree of the polyimide, so that the flexibility of a molecular chain is further limited, a product is endowed with firm physical crosslinking points, and the product is further endowed with higher dimensional stability, shape recovery rate and creep resistance.
The first aspect of the invention provides a shape memory electrode, which comprises a nano silver protective layer, a nano silver conductive layer and the transparent polyimide film from top to bottom in sequence.
In some embodiments, the thickness of the nano silver protective layer is 2-20 μm, and the thickness of the nano silver conductive layer is 90-200 nm; the thickness of the transparent polyimide film is 50-120 mu m.
In some embodiments, the electrode is prepared by coating nano silver conductive ink on the surface of a transparent polyimide film, drying to obtain a nano silver conductive layer, coating nano silver protective slurry on the surface of the nano silver conductive layer, and drying again.
Specifically, the coating manner is wet coating, and the coating process includes, but is not limited to, electrostatic spraying, screen printing, wire bar coating, dip coating, blade coating, curtain coating, slide coating, slot die coating, roll coating, gravure coating, or extrusion coating.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a high-temperature-resistant shape memory transparent polyimide film, which is prepared by taking 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl as a diamine monomer and hexafluoro dianhydride and cyclopentanone bis-spironorbornane tetracarboxylic dianhydride as dianhydride monomers as reaction units, wherein the visible light transmittance of the polyimide film at 550nm is 89-93%, the thermal expansion coefficient is 8-40ppm/K, the glass transition temperature is 330-.
(2) According to the invention, hexafluoro dianhydride and cyclopentanone double-spiro norbornane tetracarboxylic dianhydride are used as composite dianhydride, fluorine-containing monomers are utilized to endow the transparent polyimide with better optical performance, meanwhile, the cyclic acid dianhydride with a rigid structure is utilized to improve the thermal expansion performance and the dielectric property of the transparent polyimide, and the two dianhydrides act synergistically, so that the polyimide with excellent optical and mechanical properties is prepared. .
(3) The invention also provides a preparation method of the high-temperature-resistant shape memory transparent polyimide film, wherein the polycondensation reaction is completed through a one-step method, the preparation process is simple, the requirement on conditions is low, the reaction auxiliary agent is conventional, and the method is suitable for industrial production.
(4) The high-temperature-resistant shape memory transparent polyimide film is used as a substrate to prepare the electrode, so that the electrode is endowed with a shape memory function, and the prepared electrode has excellent bending resistance and is suitable for popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural view of a shape memory electrode prepared in example 1 of the present invention;
FIG. 2 is a thermal stability curve of a transparent shape memory transparent polyimide film prepared in example 1 of the present invention;
FIG. 3 is a schematic view showing the shape recovery of the transparent shape-memory transparent polyimide film prepared in example 1 of the present invention.
Reference numerals: 1. a nano silver protective layer; 2. a nano-silver conductive layer; 3. a transparent polyimide film.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood 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
(1) Preparation of high-temperature-resistant shape memory transparent polyimide film
Introducing N2 into an empty reaction kettle, then adding 1100g N, N-dimethylacetamide, starting stirring at the stirring speed of 100r/min, and starting a temperature controller to set the temperature at 100 ℃; keeping nitrogen flow, adding 160.12g (0.5mol) of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, cleaning a charging hole by using 50g N, N-dimethylacetamide, and stirring for 30 min; placing a nitrogen pipe orifice above the liquid level, continuously keeping ventilation, then sequentially adding 133.27g (0.3mol) of hexafluoro dianhydride, 76.87g (0.2mol) of cyclopentanone bis-spironorbomane tetracarboxylic dianhydride and 4.70g of tris (4-aminophenyl) amine, cleaning a feeding port with 50g of gamma-butyrolactone/N, N-dimethylacetamide, stirring at room temperature for 30min, then adding 3.81g of isoquinoline, and stirring for 2 h; then 70g of trimellitic anhydride is dripped in 3h, the temperature is raised to 150 ℃ after the dripping is finished, the stirring speed is set to be 300r/min, and the reaction lasts for 6 h; and finally, 600g N, N-dimethylacetamide is added for dilution, the mixture is stirred for 1 hour, and the polyimide slurry is obtained. Coating the prepared polyimide slurry on a clean glass plate by using a coating machine, setting the film thickness to be 150 mu m, putting the coated wet film into a drying oven, drying the wet film into a film by using a temperature-rising program of 80 ℃/0.5h-120 ℃/0.5h-150 ℃/0.5h-200 ℃/0.5h-250 ℃/1h, demoulding by using pure water at the temperature of 80 ℃, and finally drying at the temperature of 120 ℃/10min to obtain the transparent polyimide film.
(2) Preparation of shape memory electrode
Coating the nano silver wire conductive ink on the transparent polyimide film in a slit coating mode, and drying at 70 ℃/80 ℃/90 ℃/100 ℃/120 ℃/100 ℃/80 ℃ by a drying process on a coating line to obtain a nano silver conductive layer; and then coating nano-silver protective slurry on the surface of the nano-silver conductive layer, and drying again to obtain the shape memory electrode. The electrode structure is shown in fig. 1.
Example 2
(1) Preparation of high-temperature-resistant shape memory transparent polyimide film
Introducing N into the empty reaction kettle 2 Then 1100g N, N-dimethylacetamide was added and the reaction was startedStirring at a stirring speed of 100r/min, and starting a temperature controller to set the temperature at 100 ℃; keeping nitrogen flow, adding 160.12g (0.5mol) of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, cleaning a charging hole by using 50g N, N-dimethylacetamide, and stirring for 30 min; placing a nitrogen pipe orifice above the liquid level, continuously keeping ventilation, then sequentially adding 177.70g (0.4mol) of hexafluoro dianhydride, 38.43g (0.1mol) of cyclopentanone bis-spironorbomane tetracarboxylic dianhydride and 4.70g of tris (4-aminophenyl) amine, cleaning a feeding port by using 50g of gamma-butyrolactone/N, N-dimethylacetamide, stirring at room temperature for 30min, then adding 3.81g of isoquinoline, and stirring for 2 h; then 70g of trimellitic anhydride is dripped in 3h, the temperature is raised to 135 ℃ after the dripping is finished, the stirring speed is set to 300r/min, and the reaction lasts for 8 h; and finally, 600g N, N-dimethylacetamide is added for dilution, the mixture is stirred for 1 hour, and the polyimide slurry is obtained.
Coating the prepared polyimide slurry on a clean glass plate by using a coating machine, setting the film thickness to be 150 mu m, putting the coated wet film into a drying oven, drying the wet film into a film by using a temperature-rising program of 80 ℃/0.5h-120 ℃/0.5h-150 ℃/0.5h-200 ℃/0.5h-250 ℃/1h, demoulding by using pure water at the temperature of 80 ℃, and finally drying at the temperature of 120 ℃/10min to obtain the transparent polyimide film.
(2) Preparation of shape memory electrode
Coating the nano silver wire conductive ink on the transparent polyimide film in a slit coating mode, and drying at 70 ℃/80 ℃/90 ℃/100 ℃/120 ℃/100 ℃/80 ℃ by a drying process on a coating line to obtain a nano silver conductive layer; and then coating nano-silver protective slurry on the surface of the nano-silver conductive layer, and drying again to obtain the shape memory electrode.
Example 3
(1) Preparation of high-temperature-resistant shape memory transparent polyimide film
Introducing N into the empty reaction kettle 2 Then adding 1100g N, N-dimethylacetamide, starting stirring at a stirring speed of 100r/min, and starting a temperature controller to set the temperature at 100 ℃; keeping nitrogen flow, adding 160.12g (0.5mol) of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, cleaning a charging hole by using 50g N, N-dimethylacetamide, and stirring for 30 min; placing the nitrogen nozzle into the liquidKeeping the above, keeping the aeration, then adding 44.42g (0.1mol) of hexafluoro dianhydride, 157.74g (0.4mol) of cyclopentanone bis-spironorbomane tetracarboxylic dianhydride and 4.70g of tris (4-aminophenyl) amine in sequence, cleaning a feeding port with 50g of gamma-butyrolactone/N, N-dimethylacetamide, stirring at room temperature for 30min, then adding 3.81g of isoquinoline, and stirring for 2 h; then 70g of trimellitic anhydride is dripped in 3h, the temperature is raised to 155 ℃ after the dripping is finished, the stirring speed is set to 300r/min, and the reaction lasts for 5 h; and finally, 600g N, N-dimethylacetamide is added for dilution, the mixture is stirred for 1 hour, and the polyimide slurry is obtained.
Coating the prepared polyimide slurry on a clean glass plate by using a coating machine, setting the film thickness to be 150 mu m, putting the coated wet film into a drying oven, drying the wet film into a film by using a temperature-rising program of 80 ℃/0.5h-120 ℃/0.5h-150 ℃/0.5h-200 ℃/0.5h-250 ℃/1h, demoulding by using pure water at the temperature of 80 ℃, and finally drying at the temperature of 120 ℃/10min to obtain the transparent polyimide film.
(2) Preparation of shape memory electrodes
Coating the nano silver wire conductive ink on the transparent polyimide film in a slit coating mode, and drying at 70 ℃/80 ℃/90 ℃/100 ℃/120 ℃/100 ℃/80 ℃ by a drying process on a coating line to obtain a nano silver conductive layer; and then coating nano silver protective slurry on the surface of the nano silver conductive layer, and drying again to obtain the shape memory electrode.
Comparative example 1
This comparative example includes most of the procedure of example 1 except that the dianhydride monomers cyclopentanone bis-spironorbornane tetracarboxylic dianhydride were formulated differently. The preparation method comprises the following steps:
introducing N2 into an empty reaction kettle, then adding 1100g N, N-dimethylacetamide, starting stirring at the stirring speed of 100r/min, and starting a temperature controller to set the temperature at 100 ℃; keeping nitrogen flow, adding 160.12g (0.1mol) of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, cleaning a charging hole by 50g N, N-dimethylacetamide, and stirring for 30 min; placing a nitrogen pipe orifice above the liquid level, continuously keeping ventilation, then sequentially adding 21.21g (0.05mol) of hexafluoro dianhydride, 172.95g (0.45mol) of cyclopentanone bis-spironorbornane tetracarboxylic dianhydride and 4.70g of tris (4-aminophenyl) amine, cleaning a feeding port by using 50g of gamma-butyrolactone/N, N-dimethylacetamide, stirring at room temperature for 30min, then adding 3.81g of isoquinoline, and stirring for 2 h; then 70g of trimellitic anhydride is dripped in 3h, the temperature is raised to 150 ℃ after the dripping is finished, the stirring speed is set to be 300r/min, and the reaction lasts for 6 h; and finally, 600g N, N-dimethylacetamide is added for dilution, the mixture is stirred for 1 hour, and the polyimide slurry is obtained. Coating the prepared polyimide slurry on a clean glass plate by using a coating machine, setting the film thickness to be 150 mu m, putting the coated wet film into a drying oven, drying the wet film into a film by using a temperature-rising program of 80 ℃/0.5h-120 ℃/0.5h-150 ℃/0.5h-200 ℃/0.5h-250 ℃/1h, demoulding by using pure water at the temperature of 80 ℃, and finally drying at the temperature of 120 ℃/10min to obtain the transparent polyimide film.
Example 5
This example includes most of the steps of example 1, except that the ratio of cyclopentanone bis-spironorbornane tetracarboxylic dianhydride in the dianhydride monomer is varied. The preparation method comprises the following steps:
introducing N2 into an empty reaction kettle, then adding 1100g N, N-dimethylacetamide, starting stirring at the stirring speed of 100r/min, and starting a temperature controller to set the temperature at 100 ℃; keeping nitrogen flow, adding 160.12g (0.5mol) of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, cleaning a charging hole by using 50g N, N-dimethylacetamide, and stirring for 30 min; placing a nitrogen pipe orifice above the liquid level, continuously keeping ventilation, then sequentially adding 199.91g (0.45mol) of hexafluoro dianhydride, 192.20g (0.05mol) of cyclopentanone bis-spironorbomane tetracarboxylic dianhydride and 4.70g of tris (4-aminophenyl) amine, cleaning a feeding port with 50g of gamma-butyrolactone/N, N-dimethylacetamide, stirring at room temperature for 30min, then adding 3.81g of isoquinoline, and stirring for 2 h; then 70g of trimellitic anhydride is dripped in 3h, the temperature is raised to 150 ℃ after the dripping is finished, the stirring speed is set to be 300r/min, and the reaction lasts for 6 h; and finally, 600g N, N-dimethylacetamide is added for dilution, the mixture is stirred for 1 hour, and the polyimide slurry is obtained. Coating the prepared polyimide slurry on a clean glass plate by using a coating machine, setting the film thickness to be 150 mu m, putting the coated wet film into a drying oven, drying the wet film into a film by using a temperature-rising program of 80 ℃/0.5h-120 ℃/0.5h-150 ℃/0.5h-200 ℃/0.5h-250 ℃/1h, demoulding by using pure water at the temperature of 80 ℃, and finally drying at the temperature of 120 ℃/10min to obtain the transparent polyimide film.
Comparative example 3
This comparative example includes most of the procedure of example 1 except that the dianhydride monomer contains only hexafluorodianhydride. The preparation method comprises the following steps:
introducing N2 into an empty reaction kettle, then adding 1100g N, N-dimethylacetamide, starting stirring at the stirring speed of 100r/min, and starting a temperature controller to set the temperature at 100 ℃; keeping nitrogen flow, adding 160.12g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, cleaning a charging hole with 50g N, N-dimethylacetamide, and stirring for 30 min; placing a nitrogen pipe orifice above the liquid level, continuously keeping ventilation, then adding 222.12g of hexafluoro dianhydride and 4.70g of tris (4-aminophenyl) amine in sequence, cleaning a charging hole by using 50g of gamma-butyrolactone/N, N-dimethylacetamide, stirring at room temperature for 30min, then adding 3.81g of isoquinoline, and stirring for 2 h; then 70g of trimellitic anhydride is dripped in 3h, the temperature is raised to 150 ℃ after the dripping is finished, the stirring speed is set to be 300r/min, and the reaction lasts for 6 h; and finally, 600g N, N-dimethylacetamide is added for dilution, the mixture is stirred for 1 hour, and the polyimide slurry is obtained. Coating the prepared polyimide slurry on a clean glass plate by using a coating machine, setting the film thickness to be 150 mu m, putting the coated wet film into a drying oven, drying the wet film into a film by using a temperature-rising program of 80 ℃/0.5h-120 ℃/0.5h-150 ℃/0.5h-200 ℃/0.5h-250 ℃/1h, demoulding by using pure water at the temperature of 80 ℃, and finally drying at the temperature of 120 ℃/10min to obtain the polyimide film.
Comparative example 4
This comparative example includes most of the procedure of example 1 except that the dianhydride monomer contains only cyclopentanone bis-spironorbornane tetracarboxylic dianhydride. The preparation method comprises the following steps:
introducing N2 into an empty reaction kettle, then adding 1100g N, N-dimethylacetamide, starting stirring at the stirring speed of 100r/min, and starting a temperature controller to set the temperature at 100 ℃; keeping nitrogen flow, adding 160.12g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, cleaning a charging hole with 50g N, N-dimethylacetamide, and stirring for 30 min; placing a nitrogen pipe orifice above the liquid level, continuously keeping ventilation, then sequentially adding 192.17g of cyclopentanone bis-spironorbornane tetracarboxylic dianhydride and 4.70g of tris (4-aminophenyl) amine, cleaning a feeding port by using 50g of gamma-butyrolactone/N, N-dimethylacetamide, stirring at room temperature for 30min, then adding 3.81g of isoquinoline, and stirring for 2 h; then 70g of trimellitic anhydride is dripped in 3h, the temperature is raised to 150 ℃ after the dripping is finished, the stirring speed is set to 300r/min, and the reaction lasts for 6 h; and finally, 600g N, N-dimethylacetamide is added for dilution, the mixture is stirred for 1 hour, and the polyimide slurry is obtained. Coating the prepared polyimide slurry on a clean glass plate by using a coating machine, setting the film thickness to be 150 mu m, putting the coated wet film into a drying oven, drying the wet film into a film by using a temperature-rising program of 80 ℃/0.5h-120 ℃/0.5h-150 ℃/0.5h-200 ℃/0.5h-250 ℃/1h, demoulding by using pure water at the temperature of 80 ℃, and finally drying at the temperature of 120 ℃/10min to obtain the polyimide film.
Comparative example 5
This comparative example includes most of the procedure of example 1 except that no crosslinking monomer is included. The preparation method comprises the following steps:
introducing N2 into an empty reaction kettle, then adding 1100g N, N-dimethylacetamide, starting stirring at the stirring speed of 100r/min, and starting a temperature controller to set the temperature at 100 ℃; keeping nitrogen flow, adding 160.12g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, cleaning a charging hole with 50g N, N-dimethylacetamide, and stirring for 30 min; placing a nitrogen pipe orifice above the liquid level, continuously keeping ventilation, then sequentially adding 133.27g of hexafluoro dianhydride and 76.87g of cyclopentanone bis-spironorbornane tetracarboxylic dianhydride, cleaning a feeding port by using 50g of gamma-butyrolactone/N, N-dimethylacetamide, stirring at room temperature for 30min, then adding 3.81g of isoquinoline, and stirring for 2 h; then 70g of trimellitic anhydride is dripped in 3h, the temperature is raised to 150 ℃ after the dripping is finished, the stirring speed is set to be 300r/min, and the reaction lasts for 6 h; and finally, 600g N, N-dimethylacetamide is added for dilution, the mixture is stirred for 1 hour, and the polyimide slurry is obtained. Coating the prepared polyimide slurry on a clean glass plate by using a coating machine, setting the film thickness to be 150 mu m, putting the coated wet film into a drying oven, drying the wet film into a film by using a temperature-rising program of 80 ℃/0.5h-120 ℃/0.5h-150 ℃/0.5h-200 ℃/0.5h-250 ℃/1h, demoulding by using pure water at the temperature of 80 ℃, and finally drying at the temperature of 120 ℃/10min to obtain the polyimide film.
Comparative example 6
This comparative example includes most of the operating steps of example 1, with the difference that the reaction temperature is different. The preparation method comprises the following steps:
introducing N2 into an empty reaction kettle, then adding 1100g N, N-dimethylacetamide, starting stirring at the stirring speed of 100r/min, and starting a temperature controller to set the temperature at 100 ℃; keeping nitrogen flow, adding 160.12g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, cleaning a charging hole with 50g N, N-dimethylacetamide, and stirring for 30 min; placing a nitrogen pipe orifice above the liquid level, continuously keeping ventilation, then sequentially adding 133.27g of hexafluoro dianhydride, 76.87g of cyclopentanone double-spiro norbornane tetracarboxylic dianhydride and 4.70g of tri (4-aminophenyl) amine, cleaning a feeding port by using 50g of gamma-butyrolactone/N, N-dimethylacetamide, stirring at room temperature for 30min, then adding 3.81g of isoquinoline, and stirring for 2 h; then 70g of trimellitic anhydride is dripped in 3h, the temperature is raised to 100 ℃ after the dripping is finished, the stirring speed is set to 300r/min, and the reaction lasts for 6 h; and finally, adding 600g of N, N-dimethylacetamide to dilute, stirring for 1h, and collecting to obtain the polyimide slurry. Coating the prepared polyimide slurry on a clean glass plate by using a coating machine, setting the film thickness to be 150 mu m, putting the coated wet film into a drying oven, drying the wet film into a film by using a temperature-rising program of 80 ℃/0.5h-120 ℃/0.5h-150 ℃/0.5h-200 ℃/0.5h-250 ℃/1h, demoulding by using pure water at the temperature of 80 ℃, and finally drying at the temperature of 120 ℃/10min to obtain the polyimide film.
Comparative example 7
This comparative example includes most of the operating steps of example 1, with the exception of the reaction temperature. The preparation method comprises the following steps:
introducing N2 into an empty reaction kettle, then adding 1100g N, N-dimethylacetamide, starting stirring at the stirring speed of 100r/min, and starting a temperature controller to set the temperature at 100 ℃; keeping nitrogen flow, adding 160.12g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, cleaning a charging hole with 50g N, N-dimethylacetamide, and stirring for 30 min; placing a nitrogen pipe orifice above the liquid level, continuously keeping ventilation, then sequentially adding 133.27g of hexafluoro dianhydride, 76.87g of cyclopentanone bis-spironorbomane tetracarboxylic dianhydride and 4.70g of tris (4-aminophenyl) amine, cleaning a feeding port by using 50g of gamma-butyrolactone/N, N-dimethylacetamide, stirring at room temperature for 30min, then adding 3.81g of isoquinoline, and stirring for 2 h; then 70g of trimellitic anhydride is dripped in 3h, the temperature is raised to 180 ℃ after the dripping is finished, the stirring speed is set to be 300r/min, and the reaction lasts for 6 h; and finally, adding 600g of N, N-dimethylacetamide to dilute, stirring for 1h, and collecting to obtain the polyimide slurry. Coating the prepared polyimide slurry on a clean glass plate by using a coating machine, setting the film thickness to be 150 mu m, putting the coated wet film into a drying oven, drying the wet film into a film by using a temperature-rising program of 80 ℃/0.5h-120 ℃/0.5h-150 ℃/0.5h-200 ℃/0.5h-250 ℃/1h, demoulding by using pure water at the temperature of 80 ℃, and finally drying at the temperature of 120 ℃/10min to obtain the polyimide film.
Test example 1
The optical properties of the polyimide films obtained in examples 1 to 3 and comparative examples 1 to 7 were measured using an ultraviolet spectrophotometer. The test results are shown in table 1.
TABLE 1
| Item | T | H | L * | a * | b * |
| Example 1 | 91.8 | 0.20 | 95.42 | -0.85 | 0.30 |
| Example 2 | 91.6 | 0.21 | 94.51 | -0.96 | 0.26 |
| Example 3 | 90.9 | 0.30 | 92.56 | -0.87 | 0.31 |
| Comparative example 1 | 90.7 | 0.45 | 94.59 | -0.86 | 0.65 |
| Comparative example 2 | 91.2 | 0.23 | 92.13 | -0.83 | 0.85 |
| Comparative example 3 | 91.4 | 0.48 | 95.89 | -0.71 | 0.35 |
| Comparative example 4 | 90.3 | 0.30 | 92.87 | -0.81 | 0.77 |
| Comparative example 5 | 90.7 | 0.79 | 93.16 | -0.85 | 0.65 |
| Comparative example 6 | 90.5 | 0.57 | 96.01 | -0.94 | 0.41 |
| Comparative example 7 | 90.1 | 0.88 | 95.11 | -0.76 | 0.59 |
Test example 2
The thermal properties of the polyimide films obtained in examples 1 to 3 and comparative examples 1 to 7 were measured using a scanning thermal difference analyzer. The test results are shown in table 2, in which the thermal stability curve of the polyimide film obtained in example 1 is shown in fig. 2, and the shape recovery diagram of the polyimide film obtained in example 1 is shown in fig. 3.
TABLE 2
| Item | CTE(ppm/k) | Tg(℃) | Shape fixation Rate (%) | Shape recovery rate/%) |
| Example 1 | 18.86 | 370 | 97 | 98 |
| Example 2 | 16.73 | 367 | 98 | 98 |
| Example 3 | 20.67 | 356 | 96 | 97 |
| Comparative example 1 | 38.13 | 331 | 95 | 97 |
| Comparative example 2 | 41.81 | 334 | 96 | 96 |
| Comparative example 3 | 45.12 | 351 | 94 | 96 |
| Comparative example 4 | 39.58 | 356 | 95 | 97 |
| Comparative example 5 | 37.13 | 361 | 94 | 96 |
| Comparative example 6 | 37.18 | 363 | 97 | 97 |
| Comparative example 7 | 42.71 | 331 | 93 | 95 |
As can be seen from tables 1-2 and FIGS. 2-3, in the high temperature resistant shape memory transparent polyimide films prepared by the present invention in examples 1-3, the visible light transmittance at 550nm is 90.9-91.8%, the thermal expansion coefficient is 16.73-20.67ppm/K, the glass transition temperature is 356-370 ℃, the shape recovery rate is 97-98%, and the film has excellent properties and is suitable for being used as a substrate of a shape memory flexible electronic device. Comparative examples 1 to 7 are comparative experiments on selection, proportion and reaction conditions of raw material monomers in example 1 of the present invention, wherein the effects of different proportions of cyclopentanone bis-spironorbornane tetracarboxylic dianhydride in the composite dianhydride monomer of the present invention on the polyimide performance are verified in example 1 and comparative examples 1 to 2, and the results show that the polyimide prepared from the composite dianhydride monomer in which cyclopentanone bis-spironorbornane tetracarboxylic dianhydride accounts for 20 to 80% has better high temperature resistance and optical properties. Compared with the composite dianhydride monomer, the prepared polyimide has a relatively single cross-linking structure, the number of cross-linking sites is reduced, the rigidity and toughness of a molecular chain cannot be coordinated, the glass transition temperature of the prepared polyimide is reduced, the reversible transformation capacity is weakened, and meanwhile, the polyimide has a higher yellowness value and is yellow; comparative example 5 no crosslinking agent was added, and the prepared polyimide could not form a chemical crosslinking network, and the degree of crosslinking was weak and various properties were poor; comparative examples 6 to 7 were respectively polycondensation at lower and higher temperatures, too low a temperature to start and advance the polycondensation, and too high a temperature caused energy waste due to exothermic polycondensation, and also affected the final product performance.
Test example 3
The bending resistance of the electrodes obtained in examples 1 to 3 was measured, and the test results are shown in Table 3.
TABLE 1
As can be seen from Table 3, the sheet resistance change rate of the shape memory electrode prepared by using the high temperature resistant shape memory transparent polyimide is only 1.60-2.72% after bending 100000 times, and the bending resistance is good.
In conclusion, the high-temperature-resistant shape memory transparent polyimide prepared by the method has good performances, and the prepared shape memory electrode has stable mechanical properties and good application value.
The present invention has been further described with reference to specific embodiments, but it should be understood that the detailed description should not be construed as limiting the spirit and scope of the present invention, and various modifications made to the above-described embodiments by those of ordinary skill in the art after reading this specification are within the scope of the present invention.
Claims (10)
1. The high-temperature-resistant shape memory transparent polyimide film is characterized in that the transparent polyimide film is prepared by taking 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl as a diamine monomer and hexafluoro dianhydride and cyclopentanone bis-spironorbornane tetracarboxylic dianhydride as dianhydride monomers through one-step polycondensation reaction.
2. The transparent polyimide film according to claim 1, wherein the molar ratio of the 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, the hexafluoro dianhydride and the cyclopentanone bis-spironorbornane tetracarboxylic dianhydride is 5: (5-A): a is more than or equal to 1 and less than or equal to 4.
3. The transparent polyimide film according to claim 1, wherein the structure of the transparent polyimide film is as follows:
wherein:
x, y and z are independently selected from any number between 0.2 and 0.8.
4. The transparent polyimide film according to any one of claims 1 to 3, wherein the method for producing the transparent polyimide film comprises the steps of:
(1) sequentially adding a reaction solvent, 4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, hexafluoro dianhydride, cyclopentanone bis-spironorbornane tetracarboxylic dianhydride, a crosslinking monomer, a catalyst and a molecular weight control agent into a reaction kettle in a nitrogen atmosphere to obtain a reaction precursor solution;
(2) heating the reaction precursor solution to react;
(3) after the reaction is finished, adding a diluent into the reaction solution, and uniformly stirring to obtain polyimide slurry;
(4) and coating the polyimide slurry on a base material, heating and drying by adopting a program, and demolding to obtain the transparent polyimide film with the shape memory function.
5. The transparent polyimide film according to claim 4, wherein the crosslinking monomer is tris (4-aminophenyl) amine.
6. The transparent polyimide film as claimed in claim 4, wherein the heating temperature in step (2) is 135-155 ℃ and the heating time is 5-8 h.
7. The transparent polyimide film according to claim 4, wherein the polyimide paste has a solid content of 20 to 30%.
8. A shape memory electrode, comprising a nano silver protective layer, a nano silver conductive layer and the transparent polyimide film according to any one of claims 1 to 7 in this order from top to bottom.
9. The electrode according to claim 8, wherein the nano silver protective layer has a thickness of 2-20 μm, and the nano silver conductive layer has a thickness of 90-200 nm; the thickness of the transparent polyimide film is 50-120 mu m.
10. The electrode according to claim 8, wherein the electrode is prepared by coating nano silver conductive ink on the surface of a transparent polyimide film, drying to obtain a nano silver conductive layer, coating nano silver protective slurry on the surface of the nano silver conductive layer, and drying again.
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