CN112691621B - Preparation method of hollow porous microspheres - Google Patents
Preparation method of hollow porous microspheres Download PDFInfo
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- CN112691621B CN112691621B CN201911011917.0A CN201911011917A CN112691621B CN 112691621 B CN112691621 B CN 112691621B CN 201911011917 A CN201911011917 A CN 201911011917A CN 112691621 B CN112691621 B CN 112691621B
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Abstract
The invention provides a preparation method of hollow porous microspheres, belonging to the technical field of materials. The preparation method of the hollow porous microspheres comprises the following steps: the sulfonic polystyrene cation exchange resin particles are used as raw materials, and are cracked for 1-60min at the temperature of 350-550 ℃ in the nitrogen or nitrogen-oxygen atmosphere to obtain the hollow porous microspheres. The prepared product has a complete shell, a hollow interior and a uniformly distributed hole structure. The number and the distribution of the holes in the formed hollow porous polymer microsphere can be effectively regulated and controlled by changing the cracking reaction conditions, so that the method is suitable for different application fields.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of hollow porous microspheres.
Background
The hollow porous polymer microsphere has the characteristics of high specific surface area, low density, adjustable pore diameter and the like due to the special structure of hollow inside, uniform hole arrangement and stable shell, and has wide application in the fields of catalyst loading, nano material preparation, ion exchange, electrochemistry, adsorption separation, radioactive waste resin treatment and the like. At present, the preparation of porous polymer microspheres is mainly divided into two categories, one is an in-situ polymerization preparation method with an initiator and a pore-forming agent added, and the preparation method comprises suspension polymerization, precipitation polymerization, multi-step emulsion polymerization, dispersion polymerization, microfluid polymerization and the like; the other is a modified preparation method for promoting the polymer to form a porous structure through the change of environmental conditions, and mainly comprises acid-base swelling, distillation precipitation, a self-assembly method and the like. The in-situ polymerization preparation method has the problems of complex operation, high difficulty in product separation and purification, low yield, high time cost and difficult regulation and control of a porous structure. The existing modification preparation method usually needs to combine subsequent treatment processes such as extraction, solvent evaporation, etching, dialysis and the like, and has the disadvantages of complex process, long time and low yield. Therefore, it is necessary to provide a method for preparing hollow porous polymer microspheres with simple operation, short time, high yield and adjustable porous structure.
Disclosure of Invention
Aiming at the problems of the existing preparation method, the invention aims to provide a preparation method of hollow porous microspheres. The preparation method of the hollow porous microspheres provided by the invention is simple to operate, short in reaction time, large in porous microsphere yield and adjustable in pore structure.
The invention provides a preparation method of hollow porous microspheres, which specifically comprises the following steps: the sulfonic polystyrene cation exchange resin particles are used as raw materials, and are cracked for 1-60min at the temperature of 350-550 ℃ in the nitrogen or nitrogen-oxygen atmosphere to obtain the hollow porous microspheres. The sulfonic polystyrene cation exchange resin particle has a temperature difference of 1-200 ℃ between the inside and the outside surface of the particle in the cracking process.
The shell of the hollow porous microsphere particle is kept complete, and compared with the sulfonic acid polystyrene cation exchange resin particle, the particle size is increased and the volume is expanded.
The size and distribution of the holes in the hollow porous microspheres can be regulated and controlled by regulating the cracking temperature, the cracking atmosphere and the cracking time.
The diameter of the inner hole of the hollow porous microsphere is 1-1000 μm.
The holes in the hollow porous microspheres are in centralized distribution or uniform distribution at the particle centers.
The cracking atmosphere is nitrogen or nitrogen-oxygen mixed gas with the oxygen concentration lower than 10vt percent.
The particle size of the sulfonic polystyrene cation exchange resin is 0.02-2 mm.
The crosslinking degree of the sulfonic acid polystyrene cation exchange resin is more than 1 percent.
The sulfonic acid polystyrene cation exchange resin is gel type or macroporous type.
The sulfonic polystyrene cation exchange resin can be prepared by sulfonation of polystyrene-divinylbenzene copolymer.
Compared with the prior art, the invention has the following characteristics:
(1) the preparation method is simple, and the polymer microspheres with hollow interiors and porous structures can be prepared in a large scale in a short time only by adjusting the cracking temperature and the cracking atmosphere;
(2) the surface of the prepared hollow porous microsphere has better thermal stability due to the formation of a cross-linked structure of a monothio bond and a polystyrene-divinylbenzene matrix;
(3) the preparation method can regulate the number and distribution of the holes in the hollow porous microspheres by regulating the cracking time, the cracking atmosphere and the cracking temperature, so as to form a structure with uniformly distributed holes.
Drawings
FIG. 1 is an electron microscope schematic view of a hollow porous microsphere prepared in example 1 of the present invention;
FIG. 2 is a schematic electron microscope view of a hollow porous microsphere prepared in example 2 of the present invention;
FIG. 3 is an electron microscope schematic view of a hollow porous microsphere prepared in example 3 of the present invention.
Detailed Description
The invention provides a preparation method of hollow porous microspheres, which specifically comprises the following steps: the sulfonic polystyrene cation exchange resin particles are used as raw materials, and are cracked for 1-60min at the temperature of 350-550 ℃ in the nitrogen or nitrogen-oxygen atmosphere to obtain the hollow porous microspheres. It should be noted that the reactor for cracking the resin particles is a common electric heating device, and can be a muffle furnace or a tube furnace.
The sulfonic polystyrene cation exchange resin particle has a temperature difference of 1-200 ℃ between the inside and the outside surface of the particle in the cracking process. Under the temperature difference, sulfonic groups are removed from the interior of the resin particles to form sulfur dioxide, and the exposed polystyrene-divinyl phenyl body is cracked to form holes; sulfonic groups on the surfaces of the particles are converted into monothio bonds to be crosslinked with polystyrene-divinyl phenyl bodies to form stable structures.
The sulfonic acid polystyrene cation exchange resin is gel type or macroporous type.
The shell of the hollow porous microsphere particle is kept complete, and compared with the sulfonic acid polystyrene cation exchange resin particle, the particle size is increased and the volume is expanded. For the gel type particles, the surface of the formed hollow porous microsphere is compact, and the cracking of the polystyrene-divinylbenzene matrix in the hollow porous microsphere can generate gaseous hydrocarbon which is remained in the particles, so that the volume of the particles is expanded, and the particle size is increased. For macroporous resin, the surface of the formed hollow porous microsphere has a pore channel structure.
The size and distribution of the holes in the hollow porous microspheres can be regulated and controlled by regulating the cracking temperature, the cracking atmosphere and the cracking time. The diameter of the holes in the hollow porous microspheres can be reduced by reducing the cracking temperature, reducing the oxygen concentration in the cracking atmosphere or reducing the cracking time, and the holes are distributed in a particle center concentrated manner. The diameter of the holes in the hollow porous microspheres can be increased by increasing the cracking temperature, increasing the oxygen concentration in the cracking atmosphere or increasing the cracking time, and the holes are uniformly distributed.
The diameter of the inner hole of the hollow porous microsphere is 1-1000 μm. The diameter of the holes increases along with the increase of the cracking temperature, the increase of the oxygen concentration in the cracking atmosphere and the increase of the cracking time.
The holes in the hollow porous microspheres are in centralized distribution or uniform distribution at the particle centers.
The cracking temperature is 350-550 ℃, and preferably 380-480 ℃; more preferably 400-450 ℃.
The cracking time is 1-60min, preferably 5-45min, and more preferably 5-30 min. The length of the reaction time affects the number of pores formed.
The cracking atmosphere is nitrogen or a nitrogen-oxygen mixed gas with oxygen concentration lower than 10 vt%, preferably the nitrogen-oxygen mixed gas with oxygen concentration lower than 8 vt%, more preferably the nitrogen-oxygen mixed gas with oxygen concentration lower than 5 vt%. The oxygen concentration affects the cracking degree of the polystyrene-divinyl benzene and further affects the size of the formed hole.
The particle size of the sulfonic acid polystyrene cation exchange resin is 0.02-2mm, preferably 0.05-0.8mm, and more preferably 0.1-0.6 mm. Too large or too small particle size increases the difficulty of controlling the pore structure.
The crosslinking degree of the sulfonic polystyrene cation exchange resin is more than 1%, preferably 4-12%, and more preferably 6-10%. The higher the crosslinking degree is, the more stable the structure obtained by crosslinking the polystyrene-divinylbenzene matrix and the monosulfur bond is, and the higher the shell integrity of the formed hollow porous microsphere particles is. However, too high a degree of crosslinking results in a decrease in the rate of formation of pores inside the particles.
The sulfonic acid polystyrene cation exchange resin particles need to be dried before cracking, and adsorption water is removed. The drying temperature is 80-105 deg.C, and the drying mode can be vacuum drying.
The sulfonic polystyrene cation exchange resin can be prepared by sulfonation of polystyrene-divinylbenzene copolymer, the sulfonation reagent is concentrated sulfuric acid, chlorosulfonic acid, sulfur trioxide or fuming sulfuric acid, the sulfonation temperature is 70-90 ℃, and the sulfonation time is 1-8 h.
In order to further illustrate the present invention, the following describes the preparation method of the hollow porous microspheres provided by the present invention in detail with reference to the accompanying drawings and examples.
Example 1
A preparation method of hollow porous microspheres comprises the following specific steps: amberlite IRN-97H sulfonic acid type cation exchange resin with crosslinking degree of 8% and average particle diameter of 0.5mm is used as raw material, and vacuum drying is carried out at 105 ℃ for 4H. And (3) putting the dried resin particles into a tubular furnace for cracking, wherein the cracking temperature is 450 ℃, the cracking time is 20min, and the cracking atmosphere is nitrogen-oxygen mixed gas with the oxygen concentration of 3 vt%. Under this condition, the temperature difference between the inside and the outside surface of the resin particle was 110 ℃. And after the reaction is finished, taking the product, and naturally cooling to obtain the hollow porous microspheres.
The product was sliced and the structure of the cut surface of the product was observed using a scanning electron microscope, as shown in FIG. 1. The shell of the prepared product is kept to be in a complete spherical shape, and the interior of the product is in a hollow hole structure which is symmetrical about the center of the particle and is uniformly distributed. Compared with the raw materials, the particle size of the prepared hollow porous microsphere product is increased by 10%.
Example 2
A preparation method of hollow porous microspheres comprises the following specific steps: amberlite IRN-97H sulfonic acid type cation exchange resin with crosslinking degree of 8% and average particle diameter of 0.5mm is used as raw material, and vacuum drying is carried out at 105 ℃ for 4H. And (3) putting the dried resin particles into a tubular furnace for cracking, wherein the cracking temperature is 450 ℃, the cracking time is 30min, and the cracking atmosphere is nitrogen-oxygen mixed gas with the oxygen concentration of 5 vt%. Under this condition, the temperature difference between the inside and the outside surface of the resin particle was 80 ℃. And after the reaction is finished, taking the product, and naturally cooling to obtain the hollow porous microspheres.
The product was sliced and the structure of the cut surface of the product was observed using a scanning electron microscope, as shown in FIG. 2. The shell of the prepared product is kept in a complete spherical shape, the interior of the product is hollow, and the product is in a porous uniform arrangement structure. Compared with the raw material, the particle size of the prepared hollow porous microsphere product is increased by 15%.
Compared with example 1, in this example, the cracking time of the resin particles is longer, and the oxygen concentration in the cracking atmosphere is higher, resulting in a higher cracking degree of the polystyrene-divinylbenzene matrix inside the resin particles, thereby forming a structure with a higher hollow degree and a larger number of holes. The higher the degree of cracking inside the resin particles, the more gaseous hydrocarbons are produced, the larger the volume of the product particles, and the larger the particle size, consistent with the test results.
Example 3
A preparation method of hollow porous microspheres comprises the following specific steps: amberlite IRN-97H sulfonic acid type cation exchange resin with crosslinking degree of 8% and average particle diameter of 0.5mm is used as raw material, and vacuum drying is carried out at 105 ℃ for 4H. And (3) putting the dried resin particles into a tubular furnace for cracking, wherein the cracking temperature is 400 ℃, the cracking time is 5min, and the cracking atmosphere is nitrogen. Under this condition, the temperature difference between the inside and the outside surface of the resin particle was 130 ℃. And after the reaction is finished, taking the product, and naturally cooling to obtain the hollow porous microspheres.
The product was sliced and the structure of the cut surface of the product was observed using a scanning electron microscope, as shown in FIG. 3. The shell of the prepared product is kept in a complete sphere shape, and a single hole is formed in the center of the particle. Compared with the raw materials, the particle size of the prepared hollow porous microsphere product has no obvious change.
Compared with the example 1 and the example 2, the cracking temperature of the resin particles is lower, the cracking time is shorter, and the reaction is performed in the inert atmosphere, so that the cracking degree of the polystyrene-divinylbenzene matrix in the resin particles is lower, a single pore structure is formed only in the center, the particle size of the product is not obviously changed, and the result is consistent with the test result.
The comparison of the three examples shows that the number and distribution of the pores inside the formed hollow porous microspheres can be effectively controlled by changing the cracking temperature, the cracking time and the cracking atmosphere of the ion exchange resin, so that the hollow porous microspheres are suitable for different application fields.
Claims (9)
1. The preparation method of the hollow porous microspheres is characterized by comprising the following steps of: cracking sulfonic polystyrene cation exchange resin particles serving as a raw material for 1-60min in a nitrogen or nitrogen-oxygen atmosphere at the temperature of 350-550 ℃ to obtain hollow porous microspheres; the sulfonic polystyrene cation exchange resin particle has a temperature difference of 1-200 ℃ between the inside and the outside surface of the particle in the cracking process.
2. The method for producing hollow porous microspheres according to claim 1, wherein: the shell of the hollow porous microsphere particle is kept complete, and compared with the sulfonic acid polystyrene cation exchange resin particle, the particle size is increased and the volume is expanded.
3. The method for producing hollow porous microspheres according to claim 1, wherein: the size and distribution of the holes in the hollow porous microspheres are regulated and controlled by regulating the cracking temperature, the cracking atmosphere and the cracking time.
4. The method for producing hollow porous microspheres according to claim 3, wherein: the diameter of the inner hole of the hollow porous microsphere is 1-1000 μm.
5. The method for producing hollow porous microspheres according to claim 3, wherein: the holes in the hollow porous microspheres are in centralized distribution or uniform distribution at the particle centers.
6. The method for producing hollow porous microspheres according to claim 1, wherein: the particle size of the sulfonic polystyrene cation exchange resin is 0.02-2 mm.
7. The method for producing hollow porous microspheres according to claim 1, wherein: the crosslinking degree of the sulfonic acid polystyrene cation exchange resin is more than 1 percent.
8. The method for producing hollow porous microspheres according to claim 1, wherein: the sulfonic acid polystyrene cation exchange resin is gel type or macroporous type.
9. The method for producing hollow porous microspheres according to claim 1, wherein: the sulfonic polystyrene cation exchange resin is prepared by sulfonating polystyrene-divinylbenzene copolymer.
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Citations (4)
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|---|---|---|---|---|
| CN1986401A (en) * | 2007-01-10 | 2007-06-27 | 华东理工大学 | Improved process for preparing porous microsphere active carbon |
| CN101259403A (en) * | 2004-11-11 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing hollow ball with polymer complex structure by swelling polymerization |
| WO2010070987A1 (en) * | 2008-12-18 | 2010-06-24 | 株式会社クレハ | Process for producing hollow microspheres and process for producing porous molded ceramic |
| CN108164631A (en) * | 2018-01-12 | 2018-06-15 | 东华大学 | Styrene-bifunctionality monomer copolymer hollow porous micro sphere and preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259403A (en) * | 2004-11-11 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing hollow ball with polymer complex structure by swelling polymerization |
| CN1986401A (en) * | 2007-01-10 | 2007-06-27 | 华东理工大学 | Improved process for preparing porous microsphere active carbon |
| WO2010070987A1 (en) * | 2008-12-18 | 2010-06-24 | 株式会社クレハ | Process for producing hollow microspheres and process for producing porous molded ceramic |
| CN108164631A (en) * | 2018-01-12 | 2018-06-15 | 东华大学 | Styrene-bifunctionality monomer copolymer hollow porous micro sphere and preparation method |
Non-Patent Citations (1)
| Title |
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| 模拟放射性废树脂与纯树脂裂解行为对比研究;姚兵等;《化学反应工程与工艺》;20190430;第35卷(第2期);152-159 * |
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