CN109337646B - Magnetic porous carbon microsphere and method for preparing same by utilizing hydroxymethyl ferrocene - Google Patents
Magnetic porous carbon microsphere and method for preparing same by utilizing hydroxymethyl ferrocene Download PDFInfo
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- CN109337646B CN109337646B CN201811305323.6A CN201811305323A CN109337646B CN 109337646 B CN109337646 B CN 109337646B CN 201811305323 A CN201811305323 A CN 201811305323A CN 109337646 B CN109337646 B CN 109337646B
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Abstract
The invention relates to a magnetic porous carbon microsphere and a method for preparing the same by utilizing hydroxymethyl ferrocene. The magnetic porous carbon microsphere is expected to be widely applied to the aspect of electromagnetic wave absorption due to the rich pore passages, the large specific surface area, the light weight, the good magnetic performance and the sufficient composite form of the magnetic nano particles and the carbon material.
Description
Technical Field
The invention belongs to the field of wave-absorbing materials, and relates to a magnetic porous carbon microsphere and a method for preparing the same by utilizing hydroxymethyl ferrocene.
Background
Hypercrosslinked polymers are a class of porous materials based on friedel-crafts alkylation reactions, which are the polymerization products of irreversible reactions under kinetic control, the channels of which are formed by the prevention of inter-chain close packing through hyperbranched polymer chains. At present, the research on the hypercrosslinked polymer mainly designs a special structural monomer and adjusts the structure of a pore channel. Magnetic hypercrosslinked polymers have also been relatively less studied as a branch thereof. The magnetic super-crosslinked polymer has both pore performance and magnetic performance, and has more advantages in application. Liu and the like prepare a hypercrosslinked precursor by an external crosslinking ferrocene method, and obtain a magnetic hypercrosslinked polymer by hydrothermal conversion, but the magnetic hypercrosslinked polymer has no regular morphology (ACS Sustainable Chemistry & Engineering,2018.6: 210). Zhang Bao Liang and the like utilize a double-oil phase system to prepare magnetic super-crosslinked polymer microspheres (ZL201510787092.7, ZL201510789213.1) and magnetic nano fibers (CN201711039190.8, CN 201711053683.7).
Ferrocene is taken as a hypercrosslinked polymer monomer, and an external cross-linking agent is necessarily used for synthesizing the magnetic hypercrosslinked material. Unlike functionalized monomers, such as 1, 4-p-dichlorobenzyl, p-xylylene glycol, and the like, can be directly self-condensed to obtain a hypercrosslinked polymer. Reports that a hypercrosslinked polymer is prepared by utilizing a self-shrinkable ferrocene monomer and is converted to obtain a hypercrosslinked magnetic material are not found yet.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a magnetic porous carbon microsphere and a method for preparing the magnetic porous carbon microsphere by utilizing hydroxymethyl ferrocene.
Technical scheme
A magnetic porous carbon microsphere is characterized in that: the ratio of the magnetic nano particles to the carbon is not lower than 1:2, the microsphere has rich pore channels, magnetic responsiveness and high specific surface area; the magnetic nano particles are simple substance iron, iron oxide or mixed in any ratio.
A method for preparing the magnetic porous carbon microsphere by utilizing hydroxymethyl ferrocene is characterized by comprising the following steps:
step 1: dissolving hydroxymethyl ferrocene in 1, 2-dichloroethane to obtain a dispersed phase; wherein the mass fraction of the hydroxymethyl ferrocene is 15-30%;
step 2: adding the dispersed phase into silicone oil, stirring and adding 1, 2-dichloroethane dissolved with anhydrous aluminum trichloride; wherein the volume ratio of the dispersed phase to the silicone oil is 1: 5-10; the mass ratio of the anhydrous aluminum trichloride to the hydroxymethyl ferrocene is 2-3: 1; the mass fraction of the anhydrous aluminum trichloride is 60-80%;
and step 3: reacting the system at the temperature of 75-85 ℃ for 12-24 h, cooling to room temperature, performing suction filtration and cleaning with 1, 2-dichloroethane until the filtrate is colorless and transparent to obtain a black solid;
and 4, step 4: tightly wrapping the obtained black solid with filter paper, and performing Soxhlet extraction and vacuum drying treatment by using absolute ethyl alcohol to obtain precursor microspheres;
and 5: calcining the obtained precursor microsphere for 3-5 h at 500-700 ℃ under a vacuum condition, and cooling along with a furnace to obtain the magnetic porous carbon microsphere.
The silicone oil is methyl silicone oil, ethyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil or ethyl hydrogen-containing silicone oil, and the viscosity is 5-100cps at 25 ℃.
Advantageous effects
The invention provides a magnetic porous carbon microsphere and a method for preparing the same by utilizing hydroxymethyl ferrocene. The magnetic porous carbon microsphere is expected to be widely applied to the aspect of electromagnetic wave absorption due to the rich pore passages, the large specific surface area, the light weight, the good magnetic performance and the sufficient composite form of the magnetic nano particles and the carbon material.
The invention selects hydroxymethyl ferrocene as a hypercrosslinked monomer, uses anhydrous aluminum trichloride as a catalyst in a two-oil phase system, prepares a hypercrosslinked hydroxymethyl ferrocene polymer by self-polycondensation, and synthesizes a class of magnetic porous carbon microspheres by vacuum carbonization. The compatibility of the hydroxymethyl ferrocene and the silicone oil is worse, and microsphere morphology particles can be obtained; the activity of the hydroxymethyl ferrocene is relatively low, so that water vapor is isolated in a double oil phase, anhydrous aluminum trichloride is only used for catalysis, and anhydrous ferric trichloride serving as a general side-gram alkylation reaction catalyst is difficult to catalyze the hydroxymethyl ferrocene to generate a hypercrosslinking reaction; the vacuum carbonization can improve the pore performance of the material and improve the magnetic responsiveness of the material.
Drawings
FIG. 1 is a schematic diagram of the preparation process of magnetic porous carbon microspheres
FIG. 2 is an SEM photograph of magnetic porous carbon microspheres
FIG. 3 shows a BET curve (A) and a pore size distribution curve (B) of a magnetic porous carbon microsphere
FIG. 4 is a graph showing the magnetic responsiveness of the magnetic porous carbon microspheres
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1: preparation of magnetic porous carbon microspheres
0.50g of hydroxymethyl ferrocene is dissolved in 2.00g of 1, 2-dichloroethane to obtain a dispersion, which is added to a three-necked flask containing 12mL of methyl silicone oil (25 ℃, 5cps), stirred, and 0.60g of 1, 2-dichloroethane solution containing 1.00g of anhydrous aluminum trichloride is added thereto. Reacting the system at the temperature of 75 ℃ for 24h, cooling to room temperature, performing suction filtration, washing with 1, 2-dichloroethane until the filtrate is colorless and transparent to obtain a black solid, wrapping the black solid with filter paper, performing Soxhlet extraction with absolute ethyl alcohol, and performing vacuum drying to obtain the precursor microsphere. Calcining the precursor microsphere for 3h at 550 ℃ under a vacuum condition, and cooling along with a furnace to obtain the magnetic porous carbon microsphere.
Example 2: preparation of magnetic porous carbon microspheres
1.00g of hydroxymethyl ferrocene was dissolved in 2.35g of 1, 2-dichloroethane to obtain a dispersion, which was put into a three-necked flask containing 14mL of ethyl silicone oil (25 ℃, 100cps), and stirred, to which 1.07g of 1, 2-dichloroethane solution containing 2.50g of anhydrous aluminum trichloride was added. Reacting the system at 78 ℃ for 20h, cooling to room temperature, performing suction filtration, washing with 1, 2-dichloroethane until the filtrate is colorless and transparent to obtain a black solid, wrapping the black solid with filter paper, performing Soxhlet extraction with absolute ethyl alcohol, and vacuum drying to obtain the precursor microsphere. Calcining the precursor microsphere for 5h at 500 ℃ under a vacuum condition, and cooling along with a furnace to obtain the magnetic porous carbon microsphere.
Example 3: preparation of magnetic porous carbon microspheres
2.00g of hydroxymethyl ferrocene was dissolved in 6.00g of 1, 2-dichloroethane to obtain a dispersion, which was put into a three-necked flask containing 40mL of methyl hydrogen-containing silicone oil (25 ℃, 50cps), and then stirred, 4.00g of 1, 2-dichloroethane solution containing 6.00g of anhydrous aluminum trichloride was added thereto. Reacting the system at the temperature of 80 ℃ for 16h, cooling to room temperature, performing suction filtration, washing with 1, 2-dichloroethane until the filtrate is colorless and transparent to obtain a black solid, wrapping the black solid with filter paper, performing Soxhlet extraction with absolute ethyl alcohol, and performing vacuum drying to obtain the precursor microsphere. Calcining the precursor microsphere for 3h at 700 ℃ under a vacuum condition, and cooling along with a furnace to obtain the magnetic porous carbon microsphere.
Example 4: preparation of magnetic porous carbon microspheres
1.80g of hydroxymethyl ferrocene is dissolved in 8.79g of 1, 2-dichloroethane to obtain a dispersion, which is added to a three-necked flask containing 60mL of methylphenyl silicone oil (25 ℃, 50cps), stirring is started, and 1.50g of 1, 2-dichloroethane solution containing 4.50g of anhydrous aluminum trichloride is added thereto. Reacting the system at 85 ℃ for 12h, cooling to room temperature, performing suction filtration, washing with 1, 2-dichloroethane until the filtrate is colorless and transparent to obtain a black solid, wrapping the black solid with filter paper, performing Soxhlet extraction with absolute ethyl alcohol, and vacuum drying to obtain the precursor microsphere. Calcining the precursor microsphere for 5h at 600 ℃ under a vacuum condition, and cooling along with a furnace to obtain the magnetic porous carbon microsphere.
Example 5: preparation of magnetic porous carbon microspheres
0.70g of hydroxymethyl ferrocene was dissolved in 3.20g of 1, 2-dichloroethane to obtain a dispersion, which was put into a three-necked flask containing 19mL of ethyl hydrogen-containing silicone oil (25 ℃, 10cps), and then stirred, and 0.90g of 1, 2-dichloroethane solution containing 1.68g of anhydrous aluminum trichloride was added thereto. Reacting the system at the temperature of 80 ℃ for 20h, cooling to room temperature, performing suction filtration, washing with 1, 2-dichloroethane until the filtrate is colorless and transparent to obtain a black solid, wrapping the black solid with filter paper, performing Soxhlet extraction with absolute ethyl alcohol, and performing vacuum drying to obtain the precursor microsphere. Calcining the precursor microsphere for 3h at 650 ℃ under a vacuum condition, and cooling along with a furnace to obtain the magnetic porous carbon microsphere.
Example 6: preparation of magnetic porous carbon microspheres
1.50g of hydroxymethyl ferrocene is dissolved in 5.64g of 1, 2-dichloroethane to obtain a dispersion, which is added into a three-necked flask containing 30mL of methyl silicone oil (25 ℃, 50cps), stirring is started, and 0.85g of 1, 2-dichloroethane solution containing 3.30g of anhydrous aluminum trichloride is added thereto. Reacting the system at 82 ℃ for 19h, cooling to room temperature, performing suction filtration, washing with 1, 2-dichloroethane until the filtrate is colorless and transparent to obtain a black solid, wrapping the black solid with filter paper, performing Soxhlet extraction with absolute ethyl alcohol, and vacuum drying to obtain the precursor microsphere. Calcining the precursor microsphere for 4h at 700 ℃ under a vacuum condition, and cooling along with a furnace to obtain the magnetic porous carbon microsphere.
Claims (2)
1. A method for preparing magnetic porous carbon microspheres by utilizing hydroxymethyl ferrocene is characterized by comprising the following steps: in the magnetic porous carbon microsphere, the ratio of magnetic nanoparticles to carbon is not less than 1:2, the microsphere has rich pore channels, and has magnetic responsiveness and high specific surface area; the magnetic nano particles are simple substance iron, iron oxide or mixed according to any ratio;
the method comprises the following specific steps:
step 1: dissolving hydroxymethyl ferrocene in 1, 2-dichloroethane to obtain a dispersed phase; wherein the mass fraction of the hydroxymethyl ferrocene is 15-30%;
step 2: adding the dispersed phase into silicone oil, stirring and adding 1, 2-dichloroethane dissolved with anhydrous aluminum trichloride; wherein the volume ratio of the dispersed phase to the silicone oil is 1: 5-10; the mass ratio of the anhydrous aluminum trichloride to the hydroxymethyl ferrocene is 2-3: 1; the mass fraction of the anhydrous aluminum trichloride is 60-80%;
and step 3: reacting the system at the temperature of 75-85 ℃ for 12-24 h, cooling to room temperature, performing suction filtration and cleaning with 1, 2-dichloroethane until the filtrate is colorless and transparent to obtain a black solid;
and 4, step 4: tightly wrapping the obtained black solid with filter paper, and performing Soxhlet extraction and vacuum drying treatment by using absolute ethyl alcohol to obtain precursor microspheres;
and 5: calcining the obtained precursor microsphere for 3-5 h at 500-700 ℃ under a vacuum condition, and cooling along with a furnace to obtain the magnetic porous carbon microsphere.
2. The method of claim 1, wherein: the silicone oil is methyl silicone oil, ethyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil or ethyl hydrogen-containing silicone oil, and the viscosity is 5-100cps at 25 ℃.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MXPA06013291A (en) * | 2006-11-16 | 2008-10-08 | Frugosa S A De C V | Process for the production of carbon submicronic structures having a tubular morphology, using metallic or ceramic substrates which have been subjected to thermal and/or thermo chemical treatments. |
| CN101284223A (en) * | 2007-04-13 | 2008-10-15 | 中国科学院金属研究所 | Magnetic porous carbon adsorbent and preparation method thereof |
| CN102110506A (en) * | 2010-11-17 | 2011-06-29 | 安徽工业大学 | Carbon-based magnetic mesoporous composite microsphere and preparation method thereof |
| CN103318973A (en) * | 2013-06-26 | 2013-09-25 | 哈尔滨工业大学 | Preparation method of carbon-cladding Fe3O4 microsphere wave-absorbing material |
| CN104117329A (en) * | 2014-07-21 | 2014-10-29 | 太原理工大学 | Preparation method of carbon-coated ferroferric oxide magnetic microspheres |
| CN105312034A (en) * | 2015-11-17 | 2016-02-10 | 西北工业大学 | Preparation method for high-specific-surface magnetic resin ball |
| CN105435754A (en) * | 2015-11-17 | 2016-03-30 | 西北工业大学 | Preparation method for micropore high specific surface magnetic macromolecule composite microsphere |
| CN105896099A (en) * | 2016-04-25 | 2016-08-24 | 中国科学院西安光学精密机械研究所 | Method for preparing porous carbon ball composite absorbing material loaded with magnetic metal element |
| CN108641781A (en) * | 2018-04-25 | 2018-10-12 | 青岛大学 | A kind of preparation method of the porous Nano carbon balls magnetorheological fluid of embedded ferroso-ferric oxide |
| CN109095450A (en) * | 2018-11-05 | 2018-12-28 | 西北工业大学 | A kind of magnetic porous carbon particle of high-ratio surface and preparation method |
-
2018
- 2018-11-05 CN CN201811305323.6A patent/CN109337646B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MXPA06013291A (en) * | 2006-11-16 | 2008-10-08 | Frugosa S A De C V | Process for the production of carbon submicronic structures having a tubular morphology, using metallic or ceramic substrates which have been subjected to thermal and/or thermo chemical treatments. |
| CN101284223A (en) * | 2007-04-13 | 2008-10-15 | 中国科学院金属研究所 | Magnetic porous carbon adsorbent and preparation method thereof |
| CN102110506A (en) * | 2010-11-17 | 2011-06-29 | 安徽工业大学 | Carbon-based magnetic mesoporous composite microsphere and preparation method thereof |
| CN103318973A (en) * | 2013-06-26 | 2013-09-25 | 哈尔滨工业大学 | Preparation method of carbon-cladding Fe3O4 microsphere wave-absorbing material |
| CN104117329A (en) * | 2014-07-21 | 2014-10-29 | 太原理工大学 | Preparation method of carbon-coated ferroferric oxide magnetic microspheres |
| CN105312034A (en) * | 2015-11-17 | 2016-02-10 | 西北工业大学 | Preparation method for high-specific-surface magnetic resin ball |
| CN105435754A (en) * | 2015-11-17 | 2016-03-30 | 西北工业大学 | Preparation method for micropore high specific surface magnetic macromolecule composite microsphere |
| CN105896099A (en) * | 2016-04-25 | 2016-08-24 | 中国科学院西安光学精密机械研究所 | Method for preparing porous carbon ball composite absorbing material loaded with magnetic metal element |
| CN108641781A (en) * | 2018-04-25 | 2018-10-12 | 青岛大学 | A kind of preparation method of the porous Nano carbon balls magnetorheological fluid of embedded ferroso-ferric oxide |
| CN109095450A (en) * | 2018-11-05 | 2018-12-28 | 西北工业大学 | A kind of magnetic porous carbon particle of high-ratio surface and preparation method |
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