CN113698763B - ZIF-8 carbon nanotube polyimide porous film and preparation method thereof - Google Patents

ZIF-8 carbon nanotube polyimide porous film and preparation method thereof Download PDF

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CN113698763B
CN113698763B CN202111019500.6A CN202111019500A CN113698763B CN 113698763 B CN113698763 B CN 113698763B CN 202111019500 A CN202111019500 A CN 202111019500A CN 113698763 B CN113698763 B CN 113698763B
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周雨薇
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Datong Copolymerization Xi'an Technology Co ltd
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    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract

The invention relates to a ZIF-8 carbon nano tube polyimide porous film and a preparation method thereof. The ZIF-8 carbon nanotube polyimide porous film consists of ZIF-8, carbon nanotubes and polyimide, wherein the film is provided with honeycomb micropores, the ZIF-8 and the carbon nanotubes are uniformly dispersed in a polyimide porous framework, the size of the honeycomb micropores is adjustable, and the density of the porous film is lower than 0.35g/cm 3 The porosity is more than 60%, the conductivity is more than 0.10S/cm, the electromagnetic shielding performance is more than 20dB, the ratio of the electromagnetic absorption performance to the total shielding performance is more than 80%, the tensile strength is more than 10MPa, and the elongation at break is more than 100%. The ZIF-8 carbon nanotube polyimide porous film is prepared by mixing polyimide, carbon nanotubes and zinc nitrate, dissolving the mixture into a polar solvent, and carrying out phase inversion on the mixture in a dimethylimidazole/ethanol mixture. The ZIF-8 carbon nano tube polyimide porous film belongs to the field of polymer composite material manufacturing, and can be used as an electromagnetic shielding material to be applied to the field of remote communication.

Description

ZIF-8 carbon nanotube polyimide porous film and preparation method thereof
Technical Field
The invention relates to a ZIF-8 carbon nanotube polyimide porous film and a preparation method thereof, belonging to the field of polymer composite material manufacture. The carbon nano tube and polyimide porous film can be used as electromagnetic shielding materials in the field of remote communication.
Background
The rapid development of communication technology and electronics has resulted in a large amount of electromagnetic radiation that adversely affects human health and electronics. In order to solve the problem of electromagnetic wave pollution, a great deal of research has been conducted to develop an electromagnetic shielding material with high efficiency. So far, metals and alloys are common materials for electromagnetic shielding, but they still have the disadvantages of high weight density, poor flexibility, poor scratch resistance, high processing cost, and the like. (As the common material used for electromagnetic shielding, metals and alloys still have the defects of high weight density, poor flexibility, poor scratch resistance, high processing cost and the like.) meanwhile, the shielding effect of the electromagnetic shielding material is mainly electromagnetic reflection, and secondary pollution of electromagnetic waves is often caused. To solve this problem, a conductive filler is generally used as an electromagnetic shielding material by adding to a polymer. In recent years, in the practical application of electromagnetic shielding materials, especially in the fields of aerospace, automobiles, etc., light weight is a very critical technical requirement, because it means energy and material saving. The introduction of porous structures into barrier material systems is often used to reduce the density of the composite material, wherein phase inversion is considered to be a more efficient way of introducing porous structures. Compared with the traditional supercritical carbon dioxide foaming, freeze drying and other methods, the phase inversion method is simple, controllable and easy to operate, and is suitable for large-scale preparation. In addition to the important advantage of light weight, the introduction of the porous structure helps to tailor the conductivity and electromagnetic shielding properties of the polymer composite. The microporous structure in the porous conductive polymer composite material is beneficial to uniformly dispersing the conductive filler in the polymer matrix, and a continuous 3D conductive interconnection network can be constructed without high-content conductive filler, so that the conductivity of the porous conductive polymer composite material is effectively improved, good electromagnetic shielding performance is obtained, in addition, the reduction of mechanical performance caused by severe agglomeration of high-load conductive filler is avoided, and the flexibility of the composite material is effectively improved.
Carbon Nanotubes (CNTs) can provide an effective solution in designing lightweight high performance polymeric electromagnetic shielding materials due to their unique tubular structure, light weight, specific surface area, and excellent electrical properties. The conductive network can be built in the polymer matrix by virtue of the higher aspect ratio of the carbon nanotubes, which helps to make electron transitions in more directions and enhance dielectric loss, enhancing electromagnetic shielding performance. The construction of the porous structure is beneficial to obtaining excellent electromagnetic shielding materials with strong impedance matching and high attenuation capability. The porous structure may facilitate a match with air, which may facilitate more electromagnetic waves from the air into the electromagnetic shielding material. Therefore, it is an important research topic to prepare a porous composite structure based on carbon nanotubes to enhance electromagnetic shielding performance. The ZIF-8 serving as a porous material can effectively improve reflection loss due to higher porosity, and accelerates the entry of electromagnetic waves due to better impedance matching with air. Therefore, the construction of the ZIF-8CNT polymer porous electromagnetic shield is a feasible method for overcoming the poor impedance matching. In addition, the air contained in the micropores in the light ZIF-8CNT polymer composite material can also effectively reduce the reflection loss of electromagnetic waves on the surface of the material, so that the composite material is mainly based on an absorption mechanism. Compared with the common electromagnetic shielding material, the light conductive polymer composite material mainly based on absorption has wider application prospect. According to the invention, the high-performance polyimide material is mixed with the carbon nano tube, a porous structure is introduced into the polyimide matrix through phase inversion, so that the carbon nano tube is uniformly dispersed on the honeycomb hole wall of the system, a continuous 3D conductive network structure can be formed by only a small amount of carbon nano tube, the conductivity of the material is effectively improved, good electromagnetic shielding performance is obtained, in addition, the reduction of mechanical performance caused by severe agglomeration of high-load conductive filler is avoided, the flexibility of the polyimide composite film is improved, and the light high-performance electromagnetic shielding polyimide composite film is obtained.
Disclosure of Invention
The invention aims to overcome the defects of the existing electromagnetic shielding material such as higher electromagnetic reflection, high density, serious agglomeration of conductive fillers, poor mechanical property and the like, and provides a ZIF-8 carbon nanotube polyimide porous film and a preparation method thereof. The preparation method comprises the steps of mixing polyimide, carbon nano-tube and zinc nitrate, dissolving the mixture into a polar solvent to obtain a mixed solution, pouring the mixed solution on a glass plate, soaking the glass plate and the mixed solution on the surface of the glass plate in an ethanol solution of dimethylimidazole, enabling the zinc nitrate and the dimethylimidazole to react in situ to grow on the surface of the carbon tube in the film forming process, enabling the ZIF-8 carbon nano-tube polyimide mixed solution to be converted into a porous film wet film in the dimethylimidazole/ethanol mixed solution through phase conversion, and drying in vacuum to obtain the ZIF-8 carbon nano-tube polyimide porous film.
The ZIF-8 carbon nano tube polyimide porous film is characterized in that: the porous film consists of ZIF-8, carbon nano tubes and polyimide, wherein honeycomb micropores are formed in the film, the honeycomb micropores are helpful for promoting the ZIF-8 and the carbon nano tubes to be uniformly dispersed in a polyimide porous framework, the size of the honeycomb micropores is adjustable, a continuous conductive network structure can be formed only by a small amount of carbon nano tubes, and the density of the porous film is lower than 0.35g/cm 3 The composite film has the advantages that the porosity is more than 60%, the conductivity is more than 0.10S/cm, the electromagnetic shielding performance is more than 20dB, the electromagnetic absorption performance is more than 80% of the total shielding performance, the tensile strength is more than 10MPa, the elongation at break is more than 100%, the excellent flexibility and stability are shown under a bending cycle, and the electromagnetic shielding performance reduction rate of the composite film is 3.0% even after 2000 bending release cycles.
The preparation method of the ZIF-8 carbon nano tube polyimide porous film is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) Adding carbon nano tube and zinc nitrate into polar solvent, ultrasonic treating for 20-90 min to obtain suspension with carbon nano tube concentration of 1-3 wt% and zinc nitrate concentration of 1-30 wt%, adding polyimide into the suspension, and mechanically stirring for 1-3 hr at 100-300 r/min to obtain mixed solution of polyimide, carbon nano tube and zinc nitrate, wherein the concentration of polyimide is 10-20 wt%, and the polar solvent is one of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
(2) Pouring the polyimide, carbon nano tube and zinc nitrate mixed solution obtained in the step (1) onto a glass plate, scraping a liquid film of 100-1000 mu m by a wet film preparation device, then soaking the glass plate and the liquid film on the surface of the glass plate together in ethanol solution of dimethyl imidazole for 0.5-3 h, peeling the obtained film from the glass plate, and then continuously soaking in deionized water for 1-3 days to obtain a composite film wet film, wherein the concentration of the dimethyl imidazole is 0.1-1 wt%;
(3) Placing the composite film wet film prepared in the step (2) on an ultra-clean workbench for 1-4 h, draining water on the surface of the composite film wet film, then placing the composite film wet film in a vacuum oven at 80-150 ℃ for vacuum drying for 5-24 h, and naturally cooling to room temperature to obtain the ZIF-8 carbon nano tube polyimide porous film.
The invention has the beneficial effects that: the ZIF-8 carbon nano tube polyimide porous film prepared by adopting the simple and environmentally-friendly phase inversion processing technology has a large number of micropore structures, effectively reduces the density of a system, and uniformly disperses the ZIF-8 and the carbon nano tube on a polyimide framework to form a continuous structureThe continuous 3D conductive network structure is beneficial to improving the electromagnetic shielding capability, and simultaneously the electromagnetic absorption performance is obviously enhanced, in addition, the reduction of the mechanical performance caused by carbon nano tube aggregation is avoided, and the flexibility of the composite film is improved. The density of the light polyimide composite film can be adjusted by the content of zinc nitrate, and the density is lower than 0.35g/cm 3 The porous film has excellent mechanical properties, tensile strength higher than 10MPa, elongation at break higher than 100%, excellent flexibility and stability under bending cycle, and the electromagnetic shielding performance decline rate of the light polyimide composite film is lower than 3.0% even after 2000 bending release cycles. The preparation method of the ZIF-8/carbon nano tube/polyimide porous film is simple, easy to operate and easy to realize industrialization.
Drawings
FIG. 1 is a cross-sectional SEM view of a ZIF-8 carbon nanotube polyimide porous film
Detailed Description
The following examples of the preparation method of the present invention are presented for illustration of the present invention and are not to be construed as limiting the scope of the claims.
Example 1
(1) Adding 1g of carbon nano tube and 1g of zinc nitrate into 90g of N, N-dimethylformamide, carrying out ultrasonic treatment for 30min to obtain uniform zinc nitrate/carbon nano tube suspension, adding 8g of polyimide into the suspension, and mechanically stirring for 2h at 300r/min until the polyimide is completely dissolved to obtain a polyimide, carbon nano tube and zinc nitrate mixed solution;
(2) Pouring the polyimide, carbon nano tube and zinc nitrate mixed solution obtained in the step (1) onto a glass plate, scraping a 200 mu m liquid film by a wet film preparation device, adding 4g of dimethyl imidazole into 200mL of ethanol, soaking the glass plate and the liquid film on the surface of the glass plate together in dimethyl imidazole/ethanol solution for 0.5h, stripping the obtained film from the glass plate, and then continuously soaking in deionized water for 2 days to obtain a composite film wet film;
(3) And (3) placing the light polyimide composite film prepared in the step (2) on an ultra-clean workbench for 4 hours to drain water on the surface of the light polyimide composite film, then placing the light polyimide composite film in a vacuum oven at 100 ℃ for vacuum drying for 12 hours, and naturally cooling to room temperature to obtain the ZIF-8 carbon nano tube polyimide porous film.
The density of the ZIF-8 carbon nano tube polyimide porous film is 0.235g/cm 3 The porosity is 71%, the SEM (scanning electron microscope) graph of the section of the light polyimide composite film is shown in figure 1, the conductivity is 0.15S/cm, the electromagnetic shielding performance is 28dB, the electromagnetic absorption performance accounts for 80% of the total shielding performance, the tensile strength of the ZIF-8 carbon nanotube polyimide porous film is 12MPa, the elongation at break is 105%, and the electromagnetic shielding performance of the ZIF-8 carbon nanotube polyimide porous film is reduced by 2.6% after 2000 bending release cycles.
Example 2
(1) Adding 2g of carbon nano tube and 1g of zinc nitrate into 90g of N, N-dimethylformamide, carrying out ultrasonic treatment for 20min to obtain uniform zinc nitrate/carbon nano tube suspension, adding 7g of polyimide into the suspension, and mechanically stirring for 2h at 300r/min until the polyimide is completely dissolved to obtain a polyimide, carbon nano tube and zinc nitrate mixed solution;
(2) Consistent with step (2) procedure in example 1;
(3) Consistent with step (3) procedure in example 1;
the density of the ZIF-8 carbon nano tube polyimide porous film is 0.229g/cm 3 The ZIF-8 carbon nano tube polyimide porous film has the advantages that the porosity is 73%, the conductivity is 0.21S/cm, the electromagnetic shielding performance is 32dB, the electromagnetic absorption performance accounts for 81% of the total shielding performance, the tensile strength is 13MPa, the elongation at break is 112%, and the electromagnetic shielding performance of the ZIF-8 carbon nano tube polyimide porous film is reduced by 2.1% after 2000 bending release cycles.
Example 3
(1) Adding 3g of carbon nano tube and 1g of zinc nitrate into 90g of N, N-dimethylformamide, carrying out ultrasonic treatment for 20min to obtain uniform zinc nitrate/carbon nano tube suspension, adding 6g of polyimide into the suspension, and mechanically stirring for 2h at 300r/min until the polyimide is completely dissolved to obtain a polyimide, carbon nano tube and zinc nitrate mixed solution;
(2) Consistent with step (2) procedure in example 1;
(3) Consistent with step (3) procedure in example 1;
the density of the ZIF-8 carbon nano tube polyimide porous film is 0.212g/cm 3 The ZIF-8 carbon nano tube polyimide porous film has the advantages that the porosity is 79%, the conductivity is 0.35S/cm, the electromagnetic shielding performance is 41dB, the electromagnetic absorption performance accounts for 83% of the total shielding performance, the tensile strength is 14MPa, the elongation at break is 121%, and the electromagnetic shielding performance of the ZIF-8 carbon nano tube polyimide porous film is reduced by 2.2% after 2000 bending release cycles.
Example 4
(1) Adding 1g of carbon nano tube and 2g of zinc nitrate into 90g of N, N-dimethylformamide, carrying out ultrasonic treatment for 20min to obtain uniform zinc nitrate/carbon nano tube suspension, adding 7g of polyimide into the suspension, and mechanically stirring for 2h at 300r/min until the polyimide is completely dissolved to obtain a polyimide, carbon nano tube and zinc nitrate mixed solution;
(2) Pouring the polyimide, carbon nano tube and zinc nitrate mixed solution obtained in the step (1) onto a glass plate, scraping a 200 mu m liquid film by a wet film preparation device, adding 8g of dimethyl imidazole into 200mL of ethanol at the same time, soaking the glass plate and the liquid film on the surface of the glass plate together in dimethyl imidazole/ethanol solution for 0.5h, stripping the obtained film from the glass plate, and then continuously soaking in deionized water for 2 days to obtain a composite film wet film;
(3) Consistent with step (3) procedure in example 1;
the density of the ZIF-8 carbon nano tube polyimide porous film is 0.227g/cm 3 The ZIF-8 carbon nano tube polyimide porous film has a porosity of 85%, an electrical conductivity of 0.17S/cm, an electromagnetic shielding performance of 31dB, an electromagnetic absorption performance with a total shielding performance ratio of 81%, a tensile strength of 11MPa, an elongation at break of 110%, and an electromagnetic shielding performance of 2000 bending release cyclesThe performance is reduced by 2.3%.
Example 5
(1) Adding 1g of carbon nano tube and 3g of zinc nitrate into 90g of N, N-dimethylformamide, carrying out ultrasonic treatment for 20min to obtain uniform zinc nitrate/carbon nano tube suspension, adding 6g of polyimide into the suspension, and mechanically stirring for 2h at 300r/min until the polyimide is completely dissolved to obtain a polyimide, carbon nano tube and zinc nitrate mixed solution;
(2) Pouring the polyimide obtained in the step (1), carbon nano tube and zinc nitrate mixed solution on a glass plate, scraping a 200 mu m liquid film by a wet film preparation device, adding 12g of dimethyl imidazole into 200mL of ethanol at the same time, then soaking the glass plate and the liquid film on the surface thereof together in dimethyl imidazole/ethanol solution for 0.5h, stripping the obtained film from the glass plate, and then continuously soaking in deionized water for 2 days to obtain a composite film wet film;
(3) Consistent with step (3) procedure in example 1;
the density of the ZIF-8 carbon nano tube polyimide porous film is 0.220g/cm 3 The ZIF-8 carbon nano tube polyimide porous film has the advantages that the porosity is 87%, the conductivity is 0.12S/cm, the electromagnetic shielding performance is 25dB, the electromagnetic absorption performance accounts for 81% of the total shielding performance, the tensile strength is 10MPa, the elongation at break is 114%, and the electromagnetic shielding performance of the ZIF-8 carbon nano tube polyimide porous film is reduced by 2.4% after 2000 bending release cycles.

Claims (2)

1. A ZIF-8 carbon nano tube polyimide porous film is characterized in that: the porous film consists of ZIF-8, carbon nano tubes and polyimide, wherein the film is provided with honeycomb micropores, the ZIF-8 and the carbon nano tubes are uniformly dispersed in a polyimide porous framework, the size of the honeycomb micropores is adjustable, and the density of the porous film is lower than 0.35g/cm 3 The porosity is more than 60%, the conductivity is more than 0.10S/cm, the electromagnetic shielding performance is more than 20dB, the ratio of the electromagnetic absorption performance to the total shielding performance is more than 80%, the tensile strength is more than 10MPa, and the elongation at break is more than 100%.
2. The ZIF-8 carbon nanotube polyimide porous film according to claim 1, wherein: the preparation method comprises the following steps:
(1) Adding carbon nano tube and zinc nitrate into polar solvent, ultrasonic treating for 20-90 min to obtain suspension with carbon nano tube concentration of 1-3 wt% and zinc nitrate concentration of 1-30 wt%, adding polyimide into the suspension, and mechanically stirring for 1-3 hr at 100-300 r/min to obtain mixed solution of polyimide, carbon nano tube and zinc nitrate, wherein the concentration of polyimide is 10-20 wt%, and the polar solvent is one of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
(2) Pouring the polyimide, carbon nano tube and zinc nitrate mixed solution obtained in the step (1) onto a glass plate, scraping a liquid film of 100-1000 mu m by a wet film preparation device, then soaking the glass plate and the liquid film on the surface of the glass plate together in ethanol solution of dimethyl imidazole for 0.5-3 h, peeling the obtained film from the glass plate, and then continuously soaking in deionized water for 1-3 days to obtain a composite film wet film, wherein the concentration of the dimethyl imidazole is 0.1-1 wt%;
(3) Placing the composite film wet film prepared in the step (2) on an ultra-clean workbench for 1-4 h, draining water on the surface of the composite film wet film, then placing the composite film wet film in a vacuum oven at 80-150 ℃ for vacuum drying for 5-24 h, and naturally cooling to room temperature to obtain the ZIF-8 carbon nano tube polyimide porous film.
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