CN115386130B - Preparation method of multistage foam pore material - Google Patents

Preparation method of multistage foam pore material Download PDF

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CN115386130B
CN115386130B CN202210133425.4A CN202210133425A CN115386130B CN 115386130 B CN115386130 B CN 115386130B CN 202210133425 A CN202210133425 A CN 202210133425A CN 115386130 B CN115386130 B CN 115386130B
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孙辉
许磊
于斌
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Zhejiang Sci Tech University ZSTU
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    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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Abstract

The invention provides a preparation method of a multi-stage foam pore material, which comprises the following steps: drying polyethersulfone ketone resin and polyetherimide; adding aerogel containing Y-type carbon nano tubes and N-methyl pyrrolidone and stirring; ultrasonic dispersion; casting on horizontal glass, and drying; taking down, washing with cold water, and drying to obtain a mixed film; by supercritical N 2 Preparing micropores of the mixed membrane by reaction; obtaining a microcellular foam material; by supercritical CO 2 Reacting the nanopores of the microcellular foam material; rapidly decompressing, carrying out glycerol bath, taking out, quenching in distilled water at room temperature, and carrying out vacuum drying to obtain the multi-stage foam pore material. The invention adopts a two-step method, wherein micropores are prepared in the first step, nanopores are prepared in the second step, and finally the multi-level foam pore material is obtained; the existence of the foam holes can squeeze the Y-shaped carbon nano tube to the foam walls, and the foam walls are connected to form a passage, so that the dielectric constant of the material is improved, the better the appearance of the foam holes is, the higher the hole density is, and the more conductive passages are formed, the better the conductivity is.

Description

Preparation method of multistage foam pore material
Technical Field
The invention relates to the field of foam materials, in particular to a preparation method of a multistage foam pore material.
Background
Typically, a porous material refers to a material in which the interior of the material is composed of a plurality of pores, each of which may be interconnected or closed. Since 1756 natural zeolite was found by humans, porous materials have been under the attention and research of researchers, and the use of porous materials has also been rapidly developed. Porous materials possess many advantages such as large specific surface area, complex pores, lower density, etc. Therefore, the porous material plays an important role in various aspects such as environmental management, biological medicine, energy storage and the like.
In the last few years, nano-scale particles have been of interest and research into nanoporous foamed materials has been conducted due to their specific properties. Similarly, the method of grafting mesoporous materials to macroporous materials is widely used, and the method can neutralize the advantages of the two materials to achieve better effect.
Disclosure of Invention
The technical problems to be solved are as follows: the invention adopts a two-step method, wherein micropores are prepared in the first step, nanopores are prepared in the second step, and finally the multi-level foam pore material is obtained; the Y-shaped carbon nano tube is extruded to the bubble walls by the existence of the bubble holes in the multi-stage foam pore material, and the bubble walls are connected to form a passage, so that the dielectric constant of the material is improved, the better the appearance of the bubble holes is, the smaller the size is, the larger the pore density is, and the more conductive passages are formed and the better the conductivity is.
The technical scheme is as follows: the preparation method of the multi-stage foam pore material comprises the following steps in parts by weight:
(1) Drying 1-2 parts of polyethersulfone ketone resin and 0.2-0.5 part of polyetherimide;
(2) Adding 0.1-0.3 part of aerogel containing Y-type carbon nano tubes, adding 15 parts of N-methyl pyrrolidone, and stirring for 2-3 hours at 230 ℃;
(3) Ultrasonic dispersion is carried out for 20-30 min;
(4) Casting on horizontal glass, and drying at 200 ℃ for 12h;
(5) Taking down, washing with cold water, and vacuum drying in an oven at 80 ℃ to obtain a mixed film;
(6) At low pressure N 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the kettle into a mixed membrane, and reacting for 2-12 hours at the saturation temperature of 20-45 ℃ and the saturation pressure of 5-30 MPa to prepare micropores of the mixed membrane;
(7) Rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 50-200 ℃ for 60s within 20-40 s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the microporous foam material;
(8) At low pressure CO 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the microporous foam material into the kettle, and reacting for 2-8 hours at the saturation temperature of 150 ℃ and the saturation pressure of 25MPa to prepare the nanopores of the microporous foam material;
(9) Rapidly decompressing, placing the sample in a glycerol bath with a preset temperature of 150-200 ℃ for 60s within 20s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the multi-stage foam pore material.
Preferably, the thickness of the mixed film in the step (5) is 100 to 150. Mu.m.
Preferably, the micropores in the step (6) have a diameter of 1 to 8 μm.
Preferably, the diameter of the nano-pores in the step (8) is 200-500 nm.
Preferably, the preparation method of the aerogel containing the Y-type carbon nano tubes comprises the following steps:
(1) Dissolving 20g of nano cellulose powder in 100mL of deionized water, adding Y-type carbon nanotubes, and performing ultrasonic treatment in an ice-water bath until gelation;
(2) Placing the mixture in a beaker, slowly adding 400mL of tertiary butanol along the wall of the beaker, and replacing once every 12 hours until the refractive index at the sol-gel interface is no longer changed;
(3) Freezing in liquid nitrogen for 1h;
(4) Drying in vacuum freeze dryer for 36 hr.
Preferably, the diameter of the nanocellulose is 1-100nm.
Preferably, the mass ratio of the nanocellulose to the Y-shaped carbon nano tube is 10 (1-2).
Preferably, the ultrasonic dispersion power in the step (1) is 600W.
Preferably, the outer diameter of the Y-shaped carbon nano tube is 60-70 nm, and the inner diameter is 30-40 nm.
The beneficial effects are that:
1. the Y-shaped carbon nano tube is extruded to the bubble walls by the existence of the bubble holes in the multi-stage foam pore material, and the bubble walls are connected to form a passage, so that the dielectric constant of the material is improved, the better the appearance of the bubble holes is, the smaller the size is, the larger the pore density is, and the more conductive passages are formed and the better the conductivity is.
2. The invention adopts a two-step method, wherein micropores are prepared in the first step, nanopores are prepared in the second step, and finally the multi-stage foam pore material is obtained.
3. The invention adopts the aerogel loaded Y-shaped carbon nano tube, the aerogel has high specific surface area and firm three-dimensional skeleton structure, and the invention is also greatly helpful for improving the mechanical property of the foam material.
4. The multi-stage foam pore material has good mechanical property and good conductivity.
Detailed Description
Example 1
The preparation method of the multi-stage foam pore material comprises the following steps in parts by weight:
(1) Drying 1 part of polyethersulfone ketone resin and 0.2 part of polyetherimide;
(2) Adding 0.1 part of aerogel containing Y-type carbon nano tubes, adding 15 parts of N-methyl pyrrolidone, and stirring for 2 hours at 230 ℃;
(3) Dispersing by ultrasonic for 20min;
(4) Casting on horizontal glass, and drying at 200 ℃ for 12h;
(5) Taking down, washing with cold water, and vacuum drying in an oven at 80deg.C to obtain a mixed film with a film thickness of 100 μm;
(6) At low pressure N 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the kettle into a mixed membrane, and reacting for 12 hours at the saturation temperature of 20 ℃ and the saturation pressure of 5MPa to prepare micropores of the mixed membrane, wherein the diameters of the micropores are 3-8 mu m;
(7) Rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 50 ℃ for 60s within 20s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain a microporous foam material;
(8) At low pressure CO 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the microporous foam material into the kettle, and reacting for 8 hours at the saturation temperature of 150 ℃ and the saturation pressure of 25MPa to prepare nano holes of the microporous foam material, wherein the diameter of the nano holes is 350-500 nm;
(9) And rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 150 ℃ for 60 seconds within 20 seconds, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the multi-stage foam pore material.
The preparation method of the aerogel containing the Y-type carbon nano tubes comprises the following steps:
(1) Dissolving 20g of nano cellulose powder with the diameter of 1-100nm in 100mL of deionized water, adding Y-type carbon nanotubes, performing ultrasonic treatment in an ice-water bath, and performing ultrasonic dispersion until gelation; the mass ratio of the nano cellulose to the Y-type carbon nano tube is 10:1; the outer diameter of the Y-shaped carbon nano tube is 60-70 nm, and the inner diameter is 30-40 nm;
(2) Placing the mixture in a beaker, slowly adding 400mL of tertiary butanol along the wall of the beaker, and replacing once every 12 hours until the refractive index at the sol-gel interface is no longer changed;
(3) Freezing in liquid nitrogen for 1h;
(4) Drying in vacuum freeze dryer for 36 hr.
Example 2
The preparation method of the multi-stage foam pore material comprises the following steps in parts by weight:
(1) Drying 1 part of polyethersulfone ketone resin and 0.3 part of polyetherimide;
(2) Adding 0.2 part of aerogel containing Y-type carbon nano tubes, adding 15 parts of N-methyl pyrrolidone, and stirring for 2 hours at 230 ℃;
(3) Ultrasonic dispersion for 25min;
(4) Casting on horizontal glass, and drying at 200 ℃ for 12h;
(5) Taking off, washing with cold water, vacuum drying at 80deg.C in oven to obtain mixed film with a film thickness of 110 μm
(6) At low pressure N 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the kettle into a mixed membrane, and reacting for 10 hours at the saturation temperature of 25 ℃ and the saturation pressure of 10MPa to prepare micropores of the mixed membrane; the diameter of the micropores is 3-7 mu m;
(7) Rapidly decompressing, placing the sample in a glycerol bath with a preset temperature of 100 ℃ for 60s within 25s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain a microporous foam material;
(8) At low pressure CO 2 Washing supercritical reaction kettle for several times to remove air, adding microporous foam material, and saturating at 150deg.C and 25MReacting for 3h under Pa to prepare the nano holes of the microporous foam material; the diameter of the nano hole is 350-450 nm;
(9) And rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 160 ℃ for 60 seconds within 20 seconds, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the multi-stage foam pore material.
The preparation method of the aerogel containing the Y-type carbon nano tubes comprises the following steps:
(1) Dissolving 20g of nano cellulose powder with the diameter of 1-100nm in 100mL of deionized water, adding Y-type carbon nanotubes, performing ultrasonic treatment in an ice-water bath, and performing ultrasonic dispersion until gelation; the mass ratio of the nano cellulose to the Y-type carbon nano tube is 10:1; the outer diameter of the Y-shaped carbon nano tube is 60-70 nm, and the inner diameter is 30-40 nm;
(2) Placing the mixture in a beaker, slowly adding 400mL of tertiary butanol along the wall of the beaker, and replacing once every 12 hours until the refractive index at the sol-gel interface is no longer changed;
(3) Freezing in liquid nitrogen for 1h;
(4) Drying in vacuum freeze dryer for 36 hr.
Example 3
The preparation method of the multi-stage foam pore material comprises the following steps in parts by weight:
(1) Drying 1 part of polyethersulfone ketone resin and 0.4 part of polyetherimide;
(2) Adding 0.2 part of aerogel containing Y-type carbon nano tubes, adding 15 parts of N-methyl pyrrolidone, and stirring for 2.5 hours at 230 ℃;
(3) Ultrasonic dispersion for 25min;
(4) Casting on horizontal glass, and drying at 200 ℃ for 12h;
(5) Taking off, washing with cold water, vacuum drying at 80deg.C in oven to obtain mixed film with a film thickness of 120 μm
(6) At low pressure N 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the kettle into a mixed membrane, and reacting for 8 hours at the saturation temperature of 30 ℃ and the saturation pressure of 15MPa to prepare micropores of the mixed membrane, wherein the diameters of the micropores are 3-6 mu m;
(7) Rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 100 ℃ for 60s within 30s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain a microporous foam material;
(8) At low pressure CO 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the microporous foam material into the kettle, and reacting for 5 hours at the saturation temperature of 150 ℃ and the saturation pressure of 25MPa to prepare nano holes of the microporous foam material, wherein the diameter of the nano holes is 300-400 nm;
(9) And rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 170 ℃ for 60 seconds within 20 seconds, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the multi-stage foam pore material.
The preparation method of the aerogel containing the Y-type carbon nano tubes comprises the following steps:
(1) Dissolving 20g of nano cellulose powder with the diameter of 1-100nm in 100mL of deionized water, adding Y-type carbon nanotubes, performing ultrasonic treatment in an ice-water bath, and performing ultrasonic dispersion until gelation; the mass ratio of the nano cellulose to the Y-type carbon nano tube is 10:1.5; the outer diameter of the Y-shaped carbon nano tube is 60-70 nm, and the inner diameter is 30-40 nm
(2) Placing the mixture in a beaker, slowly adding 400mL of tertiary butanol along the wall of the beaker, and replacing once every 12 hours until the refractive index at the sol-gel interface is no longer changed;
(3) Freezing in liquid nitrogen for 1h;
(4) Drying in vacuum freeze dryer for 36 hr.
Example 4
The preparation method of the multi-stage foam pore material comprises the following steps in parts by weight:
(1) Drying 1 part of polyethersulfone ketone resin and 0.5 part of polyetherimide;
(2) Adding 0.3 part of aerogel containing Y-type carbon nano tubes, adding 15 parts of N-methyl pyrrolidone, and stirring for 2.5 hours at 230 ℃;
(3) Ultrasonic dispersion for 25min;
(4) Casting on horizontal glass, and drying at 200 ℃ for 12h;
(5) Taking down, washing with cold water, and vacuum drying in an oven at 80 ℃ to obtain a mixed film; the film thickness of the mixed film was 130. Mu.m
(6) At low pressure N 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the kettle into a mixed membrane, and reacting for 6 hours at the saturation temperature of 35 ℃ and the saturation pressure of 20MPa to prepare micropores of the mixed membrane; the diameter of the micropores is 1-6 mu m;
(7) Rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 100 ℃ for 60s within 30s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain a microporous foam material;
(8) At low pressure CO 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the microporous foam material into the kettle, and reacting for 4 hours at the saturation temperature of 150 ℃ and the saturation pressure of 25MPa to prepare nanopores of the microporous foam material; the diameter of the nano hole is 200-350 nm;
(9) Rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 180 ℃ for 60s within 20s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the multi-stage foam pore material.
The preparation method of the aerogel containing the Y-type carbon nano tubes comprises the following steps:
(1) Dissolving 20g of nano cellulose powder with the diameter of 1-100nm in 100mL of deionized water, adding Y-type carbon nanotubes, performing ultrasonic treatment in an ice-water bath, and performing ultrasonic dispersion until gelation; the mass ratio of the nano cellulose to the Y-type carbon nano tube is 10:1.5; the outer diameter of the Y-shaped carbon nano tube is 60-70 nm, and the inner diameter is 30-40 nm;
(2) Placing the mixture in a beaker, slowly adding 400mL of tertiary butanol along the wall of the beaker, and replacing once every 12 hours until the refractive index at the sol-gel interface is no longer changed;
(3) Freezing in liquid nitrogen for 1h;
(4) Drying in vacuum freeze dryer for 36 hr.
Example 5
The preparation method of the multi-stage foam pore material comprises the following steps in parts by weight:
(1) Drying 1.5 parts of polyethersulfone ketone resin and 0.5 part of polyetherimide;
(2) Adding 0.2 part of aerogel containing Y-type carbon nano tubes, adding 15 parts of N-methyl pyrrolidone, and stirring for 2.5 hours at 230 ℃;
(3) Ultrasonic dispersion for 25min;
(4) Casting on horizontal glass, and drying at 200 ℃ for 12h;
(5) Taking down, washing with cold water, and vacuum drying in an oven at 80 ℃ to obtain a mixed film; the film thickness of the mixed film was 140. Mu.m;
(6) At low pressure N 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the kettle into a mixed membrane, and reacting for 4 hours at the saturation temperature of 40 ℃ and the saturation pressure of 25MPa to prepare micropores of the mixed membrane; the diameter of the micropores is 1-6 mu m;
(7) Rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 200 ℃ for 60 seconds within 40 seconds, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain a microporous foam material;
(8) At low pressure CO 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the microporous foam material into the kettle, and reacting for 3 hours at the saturation temperature of 150 ℃ and the saturation pressure of 25MPa to prepare nanopores of the microporous foam material; the diameter of the nano hole is 200-350 nm;
(9) And rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 200 ℃ for 60s within 20s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the multi-stage foam pore material.
The preparation method of the aerogel containing the Y-type carbon nano tubes comprises the following steps:
(1) Dissolving 20g of nano cellulose powder with the diameter of 1-100nm in 100mL of deionized water, adding Y-type carbon nanotubes, performing ultrasonic treatment in an ice-water bath, and performing ultrasonic dispersion until gelation; the mass ratio of the nano cellulose to the Y-type carbon nano tube is 10:2; the outer diameter of the Y-shaped carbon nano tube is 60-70 nm, and the inner diameter is 30-40 nm;
(2) Placing the mixture in a beaker, slowly adding 400mL of tertiary butanol along the wall of the beaker, and replacing once every 12 hours until the refractive index at the sol-gel interface is no longer changed;
(3) Freezing in liquid nitrogen for 1h;
(4) Drying in vacuum freeze dryer for 36 hr.
Example 6
The preparation method of the multi-stage foam pore material comprises the following steps in parts by weight:
(1) Drying 2 parts of polyethersulfone ketone resin and 0.5 part of polyetherimide;
(2) Adding 0.3 part of aerogel containing Y-type carbon nano tubes, adding 15 parts of N-methyl pyrrolidone, and stirring for 3 hours at 230 ℃;
(3) Dispersing for 30min by ultrasonic;
(4) Casting on horizontal glass, and drying at 200 ℃ for 12h;
(5) Taking down, washing with cold water, and vacuum drying in an oven at 80 ℃ to obtain a mixed film; the film thickness of the mixed film was 150. Mu.m;
(6) At low pressure N 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the kettle into a mixed membrane, and reacting for 2 hours at the saturation temperature of 45 ℃ and the saturation pressure of 30MPa to prepare micropores of the mixed membrane; the diameter of the micropores is 1-5 mu m;
(7) Rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 200 ℃ for 60 seconds within 40 seconds, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain a microporous foam material;
(8) At low pressure CO 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the microporous foam material into the kettle, and reacting for 2 hours at the saturation temperature of 150 ℃ and the saturation pressure of 25MPa to prepare nanopores of the microporous foam material; the diameter of the nano hole is 200-350 nm;
(9) And rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 200 ℃ for 60s within 20s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the multi-stage foam pore material.
The preparation method of the aerogel containing the Y-type carbon nano tubes comprises the following steps:
(1) Dissolving 20g of nano cellulose powder with the diameter of 1-100nm in 100mL of deionized water, adding Y-type carbon nanotubes, performing ultrasonic treatment in an ice-water bath, and performing ultrasonic dispersion until gelation; the mass ratio of the nano cellulose to the Y-type carbon nano tube is 10:2; the outer diameter of the Y-shaped carbon nano tube is 60-70 nm, and the inner diameter is 30-40 nm;
(2) Placing the mixture in a beaker, slowly adding 400mL of tertiary butanol along the wall of the beaker, and replacing once every 12 hours until the refractive index at the sol-gel interface is no longer changed;
(3) Freezing in liquid nitrogen for 1h;
(4) Drying in vacuum freeze dryer for 36 hr.
Comparative example 1
The difference between this example and example 6 is that the aerogel containing no Y-type carbon nanotubes, in particular:
a preparation method of a multi-stage foam pore material comprises the following steps:
(1) Drying 2 parts of polyethersulfone ketone resin and 0.5 part of polyetherimide;
(2) 15 parts of N-methylpyrrolidone are added and stirred for 3 hours at 230 ℃;
(3) Dispersing for 30min by ultrasonic;
(4) Casting on horizontal glass, and drying at 200 ℃ for 12h;
(5) Taking down, washing with cold water, and vacuum drying in an oven at 80 ℃ to obtain a mixed film; the film thickness of the mixed film was 150. Mu.m;
(6) At low pressure N 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the kettle into a mixed membrane, and reacting for 2 hours at the saturation temperature of 45 ℃ and the saturation pressure of 30MPa to prepare micropores of the mixed membrane; the diameter of the micropores is 1-5 mu m;
(7) Rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 200 ℃ for 60 seconds within 40 seconds, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain a microporous foam material;
(8) At low pressure CO 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the microporous foam material into the kettle, and reacting for 2 hours at the saturation temperature of 150 ℃ and the saturation pressure of 25MPa to prepare nanopores of the microporous foam material; the diameter of the nano hole is 200-350 nm；
(9) And rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 200 ℃ for 60s within 20s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the multi-stage foam pore material.
Comparative example 2
The difference between this example and example 6 is that the Y-carbon nanotubes are directly added in the same amount as in example 6, instead of the aerogel containing Y-carbon nanotubes, specifically:
the preparation method of the multi-stage foam pore material comprises the following steps in parts by weight:
(1) Drying 2 parts of polyethersulfone ketone resin and 0.5 part of polyetherimide;
(2) Adding 0.05 part of Y-type carbon nano tube, adding 15 parts of N-methyl pyrrolidone, and stirring for 3 hours at 230 ℃, wherein the outer diameter of the Y-type carbon nano tube is 60-70 nm, and the inner diameter of the Y-type carbon nano tube is 30-40 nm;
(3) Dispersing for 30min by ultrasonic;
(4) Casting on horizontal glass, and drying at 200 ℃ for 12h;
(5) Taking down, washing with cold water, and vacuum drying in an oven at 80 ℃ to obtain a mixed film; the film thickness of the mixed film was 150. Mu.m;
(6) At low pressure N 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the kettle into a mixed membrane, and reacting for 2 hours at the saturation temperature of 45 ℃ and the saturation pressure of 30MPa to prepare micropores of the mixed membrane; the diameter of the micropores is 1-5 mu m;
(7) Rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 200 ℃ for 60 seconds within 40 seconds, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain a microporous foam material;
(8) At low pressure CO 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the microporous foam material into the kettle, and reacting for 2 hours at the saturation temperature of 150 ℃ and the saturation pressure of 25MPa to prepare nanopores of the microporous foam material; the diameter of the nano hole is 200-350 nm;
(9) And rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 200 ℃ for 60s within 20s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the multi-stage foam pore material.
The tensile and flexural properties of the samples were characterized using a material testing machine, with standards ISO527-5-2009 and ISO178-2019, respectively. The sample sizes for tensile and flexural performance testing were 80mm by 10mm by 4mm, with a tensile rate of 5mm/min. Impact performance testing was performed with a plastic pendulum impact tester, standard ISO179-2010. The ambient temperature for all experiments was 25 ℃, and the results of the experiments were the average of the results of six experiments.
TABLE 1 mechanical Properties of the different examples
Tensile Strength (MPa) Flexural Strength (MPa) Impact Strength (KJ/m) 2 ）
Example 1 78.3 118.3 7.8
Example 2 81.1 122.4 8.0
Example 3 83.5 126.7 8.4
Example 4 82.2 124.9 8.3
Example 5 83.2 126.1 8.3
Example 6 79.9 120.8 7.9
Comparative example 1 63.4 105.2 7.2
Comparative example 2 71.0 101.3 6.9
Table 2 conductivity of different examples
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 2
Dielectric constant 214 349 331 444 238 275 232
Dielectric loss 122 163 141 231 134 145 127
As can be seen from tables 1 and 2, the addition of the Y-type carbon nanotubes greatly increases the dielectric constant, but the direct addition of the Y-type carbon nanotubes greatly decreases the mechanical properties of the foam material, and the aerogel containing the Y-type carbon nanotubes reduces the influence of the Y-type carbon nanotubes on the mechanical energy absorption of the foam material on the basis of maintaining the dielectric constant of the material.

Claims (7)

1. The preparation method of the multi-stage foam pore material is characterized by comprising the following steps of:
(1) Drying 1-2 parts of polyethersulfone ketone resin and 0.2-0.5 part of polyetherimide;
(2) Adding 0.1-0.3 part of aerogel containing Y-type carbon nano tubes, adding 15 parts of N-methyl pyrrolidone, and stirring for 2-3 hours at 230 ℃; wherein the outer diameter of the Y-shaped carbon nano tube is 60-70 nm, and the inner diameter is 30-40 nm;
(3) Ultrasonic dispersion is carried out for 20-30 min;
(4) Casting on horizontal glass, and drying at 200 ℃ for 12h;
(5) Taking down, flushing with cold water, and vacuum drying in an oven at 80 ℃ to obtain a mixed film with the film thickness of 100-150 mu m;
(6) At low pressure N 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the kettle into a mixed membrane, and reacting for 2-12 hours at the saturation temperature of 20-45 ℃ and the saturation pressure of 5-30 MPa to prepare micropores of the mixed membrane;
(7) Rapidly decompressing, placing the sample in a glycerol bath with the preset temperature of 50-200 ℃ for 60s within 20-40 s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the microporous foam material;
(8) At low pressure CO 2 Washing the supercritical reaction kettle for several times to remove air in the kettle, putting the microporous foam material into the kettle, and reacting for 2-8 hours at the saturation temperature of 150 ℃ and the saturation pressure of 25MPa to prepare the nanopores of the microporous foam material;
(9) Rapidly decompressing, placing the sample in a glycerol bath with a preset temperature of 150-200 ℃ for 60s within 20s, taking out, quenching in distilled water at room temperature, and vacuum drying to obtain the multi-stage foam pore material.
2. The method for preparing the multi-stage foam cellular material according to claim 1, wherein: the diameter of the micropores in the step (6) is 1-8 mu m.
3. The method for preparing the multi-stage foam cellular material according to claim 1, wherein: the diameter of the nano hole in the step (8) is 200-500 nm.
4. The method for preparing the multi-stage foam cellular material according to claim 1, wherein: the preparation method of the aerogel containing the Y-type carbon nano tubes comprises the following steps:
(1) Dissolving 20g of nano cellulose powder in 100mL of deionized water, adding Y-type carbon nanotubes, and performing ultrasonic treatment in an ice-water bath until gelation;
(2) Placing the mixture in a beaker, slowly adding 400mL of tertiary butanol along the wall of the beaker, and replacing once every 12 hours until the refractive index at the sol-gel interface is no longer changed;
(3) Freezing in liquid nitrogen for 1h;
(4) Drying in vacuum freeze dryer for 36 hr.
5. The method for preparing the multi-stage foam cellular material according to claim 4, wherein: the diameter of the nanocellulose is 1-100nm.
6. The method for preparing the multi-stage foam cellular material according to claim 4, wherein: the mass ratio of the nano cellulose to the Y-type carbon nano tube is 10 (1-2).
7. The method for preparing the multi-stage foam cellular material according to claim 4, wherein: the ultrasonic dispersion power in the step (1) is 600W.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN103382262A (en) * 2013-07-24 2013-11-06 大连工业大学 Method for preparing PPESK through super-critical CO2 foaming
CN112934129A (en) * 2021-01-28 2021-06-11 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 Efficient photo-thermal water evaporation carbon nanotube hydrogel and preparation method and application thereof

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CA2891378C (en) * 2012-11-15 2020-11-10 Cytec Industries Inc. Thermoset resin composite materials comprising inter-laminar toughening particles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103382262A (en) * 2013-07-24 2013-11-06 大连工业大学 Method for preparing PPESK through super-critical CO2 foaming
CN112934129A (en) * 2021-01-28 2021-06-11 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 Efficient photo-thermal water evaporation carbon nanotube hydrogel and preparation method and application thereof

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