CN112552553A - Composite foam porous material and preparation method and application thereof - Google Patents
Composite foam porous material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112552553A CN112552553A CN202011445800.6A CN202011445800A CN112552553A CN 112552553 A CN112552553 A CN 112552553A CN 202011445800 A CN202011445800 A CN 202011445800A CN 112552553 A CN112552553 A CN 112552553A
- Authority
- CN
- China
- Prior art keywords
- composite foam
- cellulose
- paraffin
- porous material
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
Abstract
The invention relates to the technical field of foam porous material preparation, and particularly discloses a composite foam porous material and a preparation method and application thereof. The composite foam porous material takes a nano cellulose-based foam material as a base material, ferroferric oxide is doped in the base material, paraffin is embedded in the base material, and polypyrrole is polymerized; the preparation method comprises the steps of firstly, stabilizing paraffin emulsion drops by utilizing nano-cellulose, carrying out ultrasonic emulsification to form stable Pickering emulsion, then combining a freeze drying technology to obtain nano-cellulose/paraffin composite foam, and then polymerizing polypyrrole in a nano-cellulose/paraffin composite foam structure by using a simple in-situ polymerization method to obtain the multifunctional composite foam porous material. The preparation process is simple, and the prepared composite foam porous material has good microwave absorption performance, energy storage function and hydrophobicity, and has good application prospects in the aspects of microwave absorption, energy storage and self-cleaning.
Description
Technical Field
The invention relates to the technical field of preparation of foam porous materials, in particular to a composite foam porous material and a preparation method and application thereof.
Background
With the advent of the 5G era, electromagnetic waves bring great convenience to human life, and electromagnetic radiation can cause considerable harm (such as electromagnetic interference between electronic devices, information leakage, radiation of electromagnetic waves to human bodies, and the like), so that development of materials capable of effectively absorbing electromagnetic waves is urgently needed, and the materials can be applied to more complicated fields. The nano cellulose porous material is a natural biodegradable material, and has wide application prospects in the fields of energy storage, electromagnetic wave absorption and sensors by virtue of low density, high porosity and three-dimensional structure.
The electromagnetic wave absorbing material converts the absorbed electromagnetic energy into heat energy, thereby effectively shielding the electromagnetic wave; if the generated joule heat can be stored or the solar energy can be stored through the photo-thermal conversion, the electromagnetic wave absorbing material has further potential to solve the problems of environmental pollution and energy shortage. And a special three-dimensional porous material is constructed, so that the transmission path of incident electromagnetic waves can be increased, multiple scattering and refraction can be generated, and the absorption capacity of the electromagnetic waves can be further enhanced. In order to meet the requirement of actual complex environment, the advanced electromagnetic wave absorbing material which has a special three-dimensional porous structure and multiple functions and is prepared by a simple and low-cost method is a key problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a composite foam porous material, a preparation method and application thereof, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the first technical scheme is as follows:
the invention provides a composite foam porous material, which takes a nanocellulose-based foam material as a base material, ferroferric oxide is uniformly doped in the base material, paraffin microspheres are embedded in the hole walls of the base material, and polypyrrole uniformly grows on the hole walls of the base material and the exposed surfaces embedded with the paraffin microspheres.
The second technical scheme is as follows:
the invention provides a preparation method of a composite foam porous material, which comprises the steps of forming Pickering emulsion by using paraffin droplets in a nano-cellulose stable ferroferric oxide solution, then carrying out freeze drying to obtain nano-cellulose/paraffin composite foam, and polymerizing polypyrrole into a nano-cellulose/paraffin composite foam structure by using an in-situ polymerization method to obtain the composite foam porous material.
As a further optimization of the invention, the method comprises the following steps:
(1) adding paraffin into a ferroferric oxide solution, then carrying out water bath ultrasonic mixing, continuously adding a nano-cellulose aqueous dispersion, and continuously carrying out ultrasonic mixing to obtain a stable Pickering emulsion;
(2) freezing and preserving the Pickering emulsion obtained in the step (1), and then carrying out vacuum freeze drying to obtain the nano-cellulose/paraffin composite foam;
(3) preparing a pyrrole monomer solution, soaking the nano-cellulose/paraffin composite foam obtained in the step (2) in the pyrrole monomer solution, transferring the solution into a ferric trichloride solution, soaking in an ice water bath, taking out, washing with deionized water, and finally freeze-drying to obtain the nano-cellulose/paraffin/polypyrrole composite foam porous material.
As a further optimization of the method, in the step (1), the mass concentration of the ferroferric oxide solution is 5.5%, the mass concentration of the nano-cellulose aqueous dispersion is 0.5%, and the material-liquid ratio of the paraffin, the ferroferric oxide solution and the nano-cellulose aqueous dispersion is (18-68) g to (32-80) mL to 400 mL.
As a further optimization of the invention, the nanocellulose comprises cellulose nanocrystals and cellulose nanofibers extracted from plant material.
As a further optimization of the invention, the ultrasonic mixing in the water bath in the step (1) is ultrasonic mixing in the water bath at the temperature of 60-80 ℃ for 6-9 min, preferably 8min, and the ultrasonic oscillation mixing is ultrasonic mixing in an ultrasonic instrument with the power of 380-420W and the temperature of 60-80 ℃ for 3-7 min, and is performed by hand shaking and repeated for 5-7 times, preferably 6 times.
As a further optimization of the invention, the freezing pretreatment of the step (2) is to freeze the Pickering emulsion obtained in the step (1) at-30 to-10 ℃ for 6 to 8 hours, preferably 8 hours, and the vacuum freeze drying is to freeze the product after the freezing pretreatment at-50 ℃ and 25Pa for 40 to 50 hours, preferably 48 hours, so as to obtain the nano-cellulose/paraffin composite foam.
As a further optimization of the invention, in the step (3), the pyrrole monomer solution with the molar concentration of 5-20 mmol/mL is soaked for 1-3 h, preferably 2 h; the molar concentration of the ferric trichloride solution is 400mmol/mL, and the soaking time is 7-9 h, preferably 8 h.
As a further optimization of the present invention, the polymer solution solvent comprises at least one of dichloromethane, 1, 2-dichloroethane, chloroform, n-hexane, and cyclohexane.
As a further optimization of the invention, all starting materials are of analytical purity or above.
The third technical scheme is as follows:
the invention provides an application of a composite foam porous material in the aspects of microwave absorption, energy storage or self-cleaning.
By means of a Pickering emulsion technology with stable nanocellulose, the nanocellulose/paraffin composite foam with a special three-dimensional porous structure can be simply, conveniently and quickly obtained to improve the energy storage performance of the nanocellulose/paraffin composite foam, the conductivity and the surface roughness of the nanocellulose/paraffin/polypyrrole composite foam are further improved by adopting polypyrrole with low surface energy, and the nanocellulose/paraffin/polypyrrole composite foam porous material with good hydrophobicity and electromagnetic wave absorption performance is further prepared. The method combining the Pickering emulsion technology and in-situ polymerization has simple process, low cost and practical popularization significance in the aspect of preparing the porous material with effective electromagnetic wave absorption, energy storage performance and hydrophobicity.
The ferroferric oxide has superparamagnetism, provides magnetic loss for incident electromagnetic waves, improves impedance matching, enables more electromagnetic waves to be incident into the foam porous material structure, reduces interface reflection of the electromagnetic waves, and improves the absorption capacity of the electromagnetic waves; the paraffin has high phase change enthalpy, endows the foam porous material with storage and release performances, is embedded in the foam structure, increases the pore area, and enhances multiple scattering and refraction of incident electromagnetic waves, thereby improving the dissipation capacity of the foam material to the electromagnetic waves; polypyrrole has good conductivity and conducts loss of incident electromagnetic waves. The conductive polypyrrole, the non-conductive nano-cellulose and the ferroferric oxide form a heterogeneous interface, so that a large amount of free electrons are accumulated to form a scattering center, and interface polarization is generated, thereby dissipating the electromagnetic waves. The content of ferroferric oxide in the prepared composite foam material is about 7.1 percent, and the content of the paraffin wax microspheres is about 88.0 percent.
The invention discloses the following technical effects:
(1) the method is suitable for various nanocelluloses to stabilize the solid paraffin with different chain lengths, and has universal applicability.
(2) The method has simple and quick process and is easy for large-scale production.
(3) The special three-dimensional structure foam porous material prepared by the method has the characteristics of biodegradability, hydrophobicity, energy storage, electromagnetic wave absorption and other multifunctionality; and the practical application requirements are met.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a scanning electron micrograph of a syntactic foam porous material prepared in example 1 of the present invention, wherein a is a scanning electron micrograph at a size of 250 μm and b is a scanning electron micrograph at a size of 1 μm;
FIG. 2 is an electromagnetic wave absorption diagram of a composite foam cellular material prepared in example 1 of the present invention;
FIG. 3 is a contact angle test chart of the syntactic foam porous material prepared in example 1 of the present invention;
FIG. 4 is a photograph of an infrared image of photothermal conversion of a composite foam porous material prepared in example 1 of the present invention, wherein a is a photograph of an infrared image simulating irradiation under sunlight for 3min, and b is a photograph of an infrared effect after the irradiation is turned off for 5 min.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) Adding 0.387g of paraffin into 0.57mL of ferroferric oxide solution with the mass concentration of 5.5%, and ultrasonically mixing in a water bath at 60 ℃ for 8 min; adding 4mL of nano-cellulose aqueous dispersion with the mass concentration of 0.5%, carrying out ultrasonic treatment on the mixed solution in an ultrasonic instrument with the power of 400W and the temperature of 60 ℃ for 5min, shaking by hand, and repeating for 6 times to obtain the nano-cellulose stable oil-in-water Pickering emulsion.
(2) And (2) freezing the Pickering emulsion prepared in the step (1) at-10 ℃ for 8h, and then freezing the Pickering emulsion in a freeze dryer at-50 ℃ and the vacuum degree of 25Pa for 48h to obtain the nano-cellulose/paraffin composite foam.
(3) Preparing 20mL of pyrrole monomer solution with the molar concentration of 5mmol/mL, and soaking the nano-cellulose/paraffin composite foam obtained in the step (2) in the pyrrole monomer solution for 2 hours; then transferring the mixture into 50mL of ferric trichloride solution with the molar concentration of 400mmol/mL, carrying out in-situ polymerization in ice water bath for 8h, and washing out unreacted pyrrole monomer and ferric trichloride solution by deionized water. Finally, freeze drying to obtain the nano-cellulose/paraffin/polypyrrole composite foam porous material.
The ferroferric oxide solution in the embodiment is prepared by adding ferroferric oxide into a dichloromethane solvent.
The scanning electron microscope image of the composite foam porous material prepared in the embodiment is shown in fig. 1, and it can be seen from fig. 1 that paraffin microspheres with uneven sizes are embedded in the structure, so that the pore area of the three-dimensional porous structure is effectively increased; the surface of the pore wall is covered with compact polypyrrole nano-particles. As can be seen from fig. 2, the absorption and reflection loss of the composite foam porous material prepared in this embodiment to electromagnetic waves reaches-27.60 dB, the efficiency reaches 99%, and the effective absorption bandwidth reaches 6.6GHz, where the electromagnetic wave absorption diagram of the composite foam porous material prepared in this embodiment is shown in fig. 2, the left side of fig. 2 is an electromagnetic wave absorption plan view, and the right side is an electromagnetic wave absorption 3D diagram.
The syntactic foam porous material prepared in the embodiment is subjected to a hydrophobic property test by light, a contact angle test chart is shown in figure 3, the syntactic foam porous material has good hydrophobic property, and the measured contact angle is 106.5 degrees (shown in figure 3), so that the syntactic foam porous material is endowed with long-term stability and durability in the practical application process and has self-cleaning capability.
The photothermal conversion performance of the composite foam porous material prepared in the embodiment under the simulated sunlight irradiation environment is shown in fig. 4. As can be seen from fig. 4, after irradiation for 3min under simulated sunlight, the surface temperature can reach 98 ℃ (see fig. 4a), indicating excellent light-heat conversion; and after the illumination is turned off for 5min, the surface temperature thereof can still reach 44.2 ℃ (see fig. 4b), which proves that the energy storage performance is excellent.
Example 2
(1) Adding 0.68g of paraffin into 0.8mL of ferroferric oxide solution with the mass concentration of 5.5%, and then ultrasonically mixing in a water bath at 60 ℃ for 6 min; adding 4mL of nano-cellulose aqueous dispersion with the mass concentration of 0.5%, carrying out ultrasonic treatment on the mixed solution in an ultrasonic instrument with the power of 380W and the temperature of 60 ℃ for 7min, shaking by hand, and repeating for 5 times to obtain the nano-cellulose stable oil-in-water Pickering emulsion.
(2) And (2) freezing the Pickering emulsion prepared in the step (1) at-30 ℃ for 6h, and then putting the Pickering emulsion into a freeze dryer at-50 ℃ and the vacuum degree of 25Pa for freezing for 50h to obtain the nano-cellulose/paraffin composite foam.
(3) Preparing 20mL of pyrrole monomer solution with the molar concentration of 20mmol/mL, and soaking the nano-cellulose/paraffin composite foam obtained in the step (2) in the pyrrole monomer solution for 3 hours; then transferring the mixture into 50mL of ferric trichloride solution with the molar concentration of 400mmol/mL, carrying out in-situ polymerization in ice water bath for 7h, and washing out unreacted pyrrole monomer and ferric trichloride solution by deionized water. Finally, freeze drying to obtain the nano-cellulose/paraffin/polypyrrole composite foam porous material.
The ferroferric oxide solution in the embodiment is prepared by adding ferroferric oxide into a 1, 2-dichloroethane solvent.
Example 3
(1) Adding 0.30g of paraffin into 0.32mL of ferroferric oxide solution with the mass concentration of 5.5%, and then ultrasonically mixing in a water bath at the temperature of 80 ℃ for 9 min; adding 4mL of nano-cellulose aqueous dispersion with the mass concentration of 0.5%, carrying out ultrasonic treatment on the mixed solution in an ultrasonic instrument with the power of 420W and the temperature of 80 ℃ for 3min, shaking by hand, and repeating for 6 times to obtain the nano-cellulose stable oil-in-water Pickering emulsion.
(2) And (2) freezing the Pickering emulsion prepared in the step (1) at-20 ℃ for 8h, and then freezing the Pickering emulsion in a freeze dryer at-50 ℃ and the vacuum degree of 25Pa for 40h to obtain the nano-cellulose/paraffin composite foam.
(3) Preparing 20mL of pyrrole monomer solution with the molar concentration of 10mmol/mL, and soaking the nano-cellulose/paraffin composite foam obtained in the step (2) in the pyrrole monomer solution for 1 h; then transferring the mixture into 50mL of ferric trichloride solution with the molar concentration of 400mmol/mL, carrying out in-situ polymerization in an ice water bath for 9 hours, and washing out unreacted pyrrole monomer and ferric trichloride solution by using deionized water. Finally, freeze drying to obtain the nano-cellulose/paraffin/polypyrrole composite foam porous material.
The ferroferric oxide solution in the embodiment is prepared by adding ferroferric oxide into a chloroform solvent.
Example 4
(1) Adding 0.18g of paraffin into 0.32mL of ferroferric oxide solution with the mass concentration of 5.5%, and then ultrasonically mixing in a water bath at 65 ℃ for 7 min; adding 4mL of nano-cellulose aqueous dispersion with the mass concentration of 0.5%, carrying out ultrasonic treatment on the mixed solution in an ultrasonic instrument with the power of 400W and the temperature of 70 ℃ for 5min, shaking by hand, and repeating for 7 times to obtain the nano-cellulose stable oil-in-water Pickering emulsion.
(2) And (2) freezing the Pickering emulsion prepared in the step (1) at-25 ℃ for 7h, and then freezing the Pickering emulsion in a freeze dryer at-50 ℃ and the vacuum degree of 25Pa for 45h to obtain the nano-cellulose/paraffin composite foam.
(3) Preparing 20mL of pyrrole monomer solution with the molar concentration of 15mmol/mL, and soaking the nano-cellulose/paraffin composite foam obtained in the step (2) in the pyrrole monomer solution for 2 hours; then transferring the mixture into 50mL of ferric trichloride solution with the molar concentration of 400mmol/mL, carrying out in-situ polymerization in ice water bath for 7h, and washing out unreacted pyrrole monomer and ferric trichloride solution by deionized water. Finally, freeze drying to obtain the nano-cellulose/paraffin/polypyrrole composite foam porous material.
The ferroferric oxide solution in the embodiment is prepared by adding ferroferric oxide into a mixed solvent of normal hexane and cyclohexane, wherein the volume ratio of the normal hexane to the cyclohexane is 1: 1.
Comparative example 1
In the prior art, polypyrrole/cellulose aerogel with microwave absorption performance is synthesized mainly by in-situ polymerization and freeze drying technology. The method comprises the following steps:
dissolving 7g of NaOH and 12g of urea in 81mL of deionized water, and precooling to-12 ℃; 4g of cotton pulp was further added to the above-mentioned precooled solution, followed by centrifugation at 8000rpm for 10 minutes to obtain a cellulose solution. Next, 2mL of epichlorohydrin was added to 20mL of the above cellulose solution and stirred for 30min, and then left to stand at room temperature for 24 hours to form a cellulose hydrogel; the porous cellulose aerogel was obtained by purification and freeze-drying. The obtained porous cellulose aerogel was cut into a rectangular block (size 2.3 cm. times.1.2 cm), and placed in deionized water to be saturated with water to obtain a wet cellulose block. Next, 500. mu.L of pyrrole monomer was added to 5mL of anhydrous ethanol at room temperature to obtain solution A (pyrrole solution). 1.2g of anhydrous FeCl3Dissolved in 5mL of deionized water to form solution B. Then, mixing the solution A and the solution B, putting the wet cellulose block into the mixed solution until the mixed solution is saturated, and carrying out in-situ polymerization for 12 hours at room temperature; finally, the polypyrrole/cellulose aerogel composite is obtained by purification and freeze drying.
However, it shows that the reflection loss value of electromagnetic wave absorption reaches only-12.24 dB; and it does not have the ability to store and release energy.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The composite foam porous material is characterized in that a nanocellulose-based foam material is used as a base material, ferroferric oxide is uniformly doped in the base material, paraffin microspheres are embedded in the hole walls of the base material, and polypyrrole uniformly grows on the hole walls of the base material and the surfaces of the paraffin microspheres.
2. The preparation method of the composite foam porous material as claimed in claim 1, wherein the composite foam porous material is obtained by forming Pickering emulsion by using paraffin droplets in a nano-cellulose-stabilized ferroferric oxide solution, then performing freeze drying to obtain nano-cellulose/paraffin-based composite foam, and polymerizing polypyrrole into a nano-cellulose/paraffin composite foam structure by using an in-situ polymerization method.
3. The method of preparing a syntactic foam cellular material according to claim 2, comprising the steps of:
(1) adding paraffin into a ferroferric oxide solution, then carrying out water bath ultrasonic mixing, continuously adding a nano-cellulose aqueous dispersion, and carrying out ultrasonic mixing to obtain a Pickering emulsion;
(2) freezing pretreatment is carried out on the Pickering emulsion obtained in the step (1), and then vacuum freeze drying is carried out to obtain nano-cellulose/paraffin composite foam;
(3) preparing a pyrrole monomer solution, soaking the nano-cellulose/paraffin composite foam obtained in the step (2) in the pyrrole monomer solution, transferring the solution into a ferric trichloride solution, soaking in an ice water bath, taking out, washing with deionized water, and finally freeze-drying to obtain the composite foam porous material.
4. The preparation method of the composite foam porous material as claimed in claim 3, wherein the feed-liquid ratio of the paraffin, the ferroferric oxide solution and the nano-cellulose aqueous dispersion in the step (1) is (18-68) g to (32-80) mL to 400 mL.
5. The method of preparing a composite foam porous material according to any one of claims 2 to 4, wherein the nanocellulose comprises cellulose nanocrystals and cellulose nanofibers extracted from a plant material.
6. The preparation method of the composite foam porous material according to claim 3, wherein the water bath ultrasonic mixing in the step (1) is ultrasonic mixing in a water bath at 60-80 ℃ for 6-9 min, and the ultrasonic oscillation mixing is ultrasonic mixing in an ultrasonic instrument with power of 380-420W and temperature of 60-80 ℃ for 3-7 min, and the steps of shaking by hand and repeating for 5-7 times.
7. The preparation method of the composite foam porous material as claimed in claim 3, wherein the freezing pretreatment in the step (2) is to freeze the Pickering emulsion obtained in the step (1) at-30 to-10 ℃ for 6 to 8 hours, and the vacuum freeze drying is to freeze the product after the freezing pretreatment in an environment with-50 ℃ and a vacuum degree of 25Pa for 40 to 50 hours, so as to obtain the nano-cellulose/paraffin composite foam.
8. The preparation method of the composite foam porous material according to claim 3, wherein in the step (3), the pyrrole monomer solution with the molar concentration of 5-20 mmol/mL is soaked for 1-3 h; the molar concentration of the ferric trichloride solution is 400mmol/mL, and the soaking time is 7-9 h.
9. The method for preparing the composite foam porous material as claimed in claim 3, wherein the solvent of the ferroferric oxide solution comprises at least one of dichloromethane, 1, 2-dichloroethane, chloroform, n-hexane and cyclohexane.
10. Use of the syntactic foam cellular material of claim 1 in microwave absorption, energy storage or self-cleaning.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011445800.6A CN112552553B (en) | 2020-12-09 | 2020-12-09 | Composite foam porous material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011445800.6A CN112552553B (en) | 2020-12-09 | 2020-12-09 | Composite foam porous material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112552553A true CN112552553A (en) | 2021-03-26 |
| CN112552553B CN112552553B (en) | 2022-06-17 |
Family
ID=75061161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011445800.6A Active CN112552553B (en) | 2020-12-09 | 2020-12-09 | Composite foam porous material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112552553B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113120879A (en) * | 2021-04-25 | 2021-07-16 | 桂林理工大学 | Carbon aerogel material and preparation method and application thereof |
| CN113415800A (en) * | 2021-06-23 | 2021-09-21 | 桂林理工大学 | Carbon foam material and preparation method and application thereof |
| CN113860411A (en) * | 2021-10-14 | 2021-12-31 | 吉林农业大学 | Oil body-polypyrrole solar energy absorbing material and photo-thermal evaporation water purifier |
| CN114377188A (en) * | 2022-01-14 | 2022-04-22 | 宋金华 | Super-absorbent bio-based foam material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010058148A1 (en) * | 2008-10-08 | 2010-05-27 | Imperial Innovations Ltd | Hydrophobized organic particle stabilized emulsions |
| CN104650353A (en) * | 2015-03-19 | 2015-05-27 | 桂林理工大学 | Method for preparing conductive polymer microsphere by stabilizing Pickering emulsion through nanocellulose |
| CN110205101A (en) * | 2019-06-28 | 2019-09-06 | 西安工程大学 | A kind of phase-change accumulation energy porous material and preparation method thereof |
| CN110330944A (en) * | 2019-07-02 | 2019-10-15 | 同济大学 | Derivative composite phase change energy-storing conductive material of natural timber and preparation method thereof |
| CN110746938A (en) * | 2019-10-17 | 2020-02-04 | 东华大学 | Cellulose/polypyrrole supported composite phase change heat storage material and preparation method thereof |
| CN110819311A (en) * | 2019-11-15 | 2020-02-21 | 东华大学 | Method for preparing hydrated salt/paraffin/cellulose sponge composite phase change material by inverse emulsion method |
| CN111363188A (en) * | 2019-12-17 | 2020-07-03 | 华东理工大学 | Preparation method of ultralight cellulose nanocrystal aerogel material |
-
2020
- 2020-12-09 CN CN202011445800.6A patent/CN112552553B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010058148A1 (en) * | 2008-10-08 | 2010-05-27 | Imperial Innovations Ltd | Hydrophobized organic particle stabilized emulsions |
| CN104650353A (en) * | 2015-03-19 | 2015-05-27 | 桂林理工大学 | Method for preparing conductive polymer microsphere by stabilizing Pickering emulsion through nanocellulose |
| CN110205101A (en) * | 2019-06-28 | 2019-09-06 | 西安工程大学 | A kind of phase-change accumulation energy porous material and preparation method thereof |
| CN110330944A (en) * | 2019-07-02 | 2019-10-15 | 同济大学 | Derivative composite phase change energy-storing conductive material of natural timber and preparation method thereof |
| CN110746938A (en) * | 2019-10-17 | 2020-02-04 | 东华大学 | Cellulose/polypyrrole supported composite phase change heat storage material and preparation method thereof |
| CN110819311A (en) * | 2019-11-15 | 2020-02-21 | 东华大学 | Method for preparing hydrated salt/paraffin/cellulose sponge composite phase change material by inverse emulsion method |
| CN111363188A (en) * | 2019-12-17 | 2020-07-03 | 华东理工大学 | Preparation method of ultralight cellulose nanocrystal aerogel material |
Non-Patent Citations (3)
| Title |
|---|
| YINGYING HE等: "Cellulose nanofibrils-based hybrid foam generated from Pickering emulsion toward high-performance microwave absorption", 《CARBOHYDRATE POLYMERS》 * |
| 刘刚等: "纳米技术在相变蓄能材料中的应用", 《化工新型材料》 * |
| 陈玉等: "蒙脱土稳定石蜡基Pickering乳液处理材的性能研究", 《林业工程学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113120879A (en) * | 2021-04-25 | 2021-07-16 | 桂林理工大学 | Carbon aerogel material and preparation method and application thereof |
| CN113415800A (en) * | 2021-06-23 | 2021-09-21 | 桂林理工大学 | Carbon foam material and preparation method and application thereof |
| CN113860411A (en) * | 2021-10-14 | 2021-12-31 | 吉林农业大学 | Oil body-polypyrrole solar energy absorbing material and photo-thermal evaporation water purifier |
| CN113860411B (en) * | 2021-10-14 | 2023-03-14 | 吉林农业大学 | Oil body-polypyrrole solar energy absorbing material and photo-thermal evaporation water purifier |
| CN114377188A (en) * | 2022-01-14 | 2022-04-22 | 宋金华 | Super-absorbent bio-based foam material and preparation method and application thereof |
| CN114377188B (en) * | 2022-01-14 | 2023-01-10 | 宋金华 | Super-absorbent bio-based foam material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112552553B (en) | 2022-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112552553B (en) | Composite foam porous material and preparation method and application thereof | |
| Inagaki et al. | Templated mesoporous carbons: Synthesis and applications | |
| Zhao et al. | Excellent electromagnetic absorption capability of Ni/carbon based conductive and magnetic foams synthesized via a green one pot route | |
| CN111171340A (en) | Photo-thermal evaporation material based on PVA hydrogel and preparation and application thereof | |
| Gai et al. | Versatile bimetal sulfides nanoparticles-embedded N-doped hierarchical carbonaceous aerogels (N-NixSy/CoxSy@ C) for excellent supercapacitors and microwave absorption | |
| CN107934937B (en) | A kind of carbon material-black phosphorus alkene composite aerogel and preparation method thereof | |
| CN107286491A (en) | A kind of high conductivity carbon nano tube/graphene aeroge/poly styrene composite material and preparation method thereof | |
| CN102432720B (en) | Preparation method for graphene based compound hydrogel modified with poly (N-isopropylacrylamide) | |
| CN110734575A (en) | Preparation method and application of aerogel-polypyrrole photothermal conversion materials | |
| Song et al. | Applications of cellulose-based composites and their derivatives for microwave absorption and electromagnetic shielding | |
| Chen et al. | State-of-the-art synthesis strategy for nitrogen-doped carbon-based electromagnetic wave absorbers: from the perspective of nitrogen source | |
| CN107161979B (en) | Carbon-based nanobelt porous material, and preparation method and application thereof | |
| CN114350159B (en) | Multifunctional wave-absorbing aerogel and preparation method thereof | |
| CN106672935A (en) | Preparation method of nitrogen-doped hollow porous carbon | |
| CN103897390A (en) | Graphene/polyaniline spherical composite material and preparation method thereof | |
| Zhou et al. | Biomass porous carbon/polyethylene glycol shape-stable phase change composites for multi-source driven thermal energy conversion and storage | |
| CN108752905B (en) | Preparation method of composite wave-absorbing material based on silver @ polypyrrole core-shell nanofibers | |
| Pai et al. | Nanocellulose-based sustainable microwave absorbers to stifle electromagnetic pollution | |
| CN113845690A (en) | Chitosan/montmorillonite aerogel and preparation method thereof | |
| CN114890770A (en) | Preparation method of porous silicon carbide/carbon composite aerogel | |
| CN114030046B (en) | Preparation method of isotropic conductive paper | |
| Yuan et al. | Carbon-coated Mn4N nanowires with abundant internal voids for microwave absorption | |
| Lu et al. | Construction of chitosan-derived porous nest-like C/SnO2 materials for microwave absorption | |
| CN113415800B (en) | Carbon foam material and preparation method and application thereof | |
| Pekala et al. | Carbon aerogels: an update on structure, properties, and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |