CN106009346B - A kind of preparation method of monodisperse silica microspheres - Google Patents
A kind of preparation method of monodisperse silica microspheres Download PDFInfo
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- CN106009346B CN106009346B CN201610329438.3A CN201610329438A CN106009346B CN 106009346 B CN106009346 B CN 106009346B CN 201610329438 A CN201610329438 A CN 201610329438A CN 106009346 B CN106009346 B CN 106009346B
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention discloses a kind of preparation methods of monodisperse silica microspheres, including step：Prepare that seed suspension liquid is spare, it is spare to prepare teos solution, it is spare to prepare initiator solution, teos solution and initiator solution are added to simultaneously in seed suspension liquid again, and the addition constant airspeed of teos solution and initiator solution is controlled respectively, it is stood after the completion of reaction, it is centrifugally separating to obtain SiO 2 composite microsphere, further, which can calcine to obtain porous silica microballoon.The controllable silicon dioxide microsphere of grain size and aperture can be prepared using the above method, and the silicon dioxide microsphere grain size height prepared is uniform, chemical stability is high, good dispersion.
Description
Technical field
The present invention relates to a kind of preparation methods of monodisperse silica microspheres, belong to technical field of polymer materials.
Background technology
In material science, silicon dioxide microsphere often shows unique property, such as electrical properties, optical property, catalysis
Property, mechanical property etc. are widely used general, wherein the complex microsphere that silica-colloidal particle is formed not only has upper
Excellent property is stated, porous silica microballoon can also be further prepared, porous silica microballoon has larger ratio table
Area has a wide range of applications in many fields, can be used as Stationary Phase for HPLC, High-efficiency catalyst carrier, high molecular material
Reinforcing agent, adsorbent, delustering agent, filtering and separation material etc..
Currently, the preparation method of porous silicon dioxide microsphere has spray drying process, sol-gel method and LBL self-assembly
Method etc., but still there is inherent shortcoming in some aspects in existing method.For example, it is micro- to prepare porous silica by spray technique
Ball requires height to spray technique, needs special spraying apparatus；Sol-gel method hydrolytic process is not easy to control, easily leads to microballoon
Particle diameter distribution is wider, and aperture is not easy to control.LBL self-assembly method will pass through the processes such as multiple absorption and centrifuge washing, efficiency
It is relatively low.
Chinese patent (CN101804986A) disclose it is a kind of using polystyrene microsphere as template prepare wall thickness it is controllable in
The method of empty silicon dioxide microsphere, using supercritical carbon dioxide as supplementary means, using crosslinked polystyrene microsphere as template,
Using supercritical carbon dioxide to the property of the good swelling property of polymer microballoon and its carrying inorganic precursor come a step
Realize that the control of shell thickness, the reaction use supercritical reaction container, limits it and be widely used..
Chinese patent (CN104909378A) discloses a kind of preparation method of monodisperse porous silicon dioxide microsphere, be with
Ethyl orthosilicate hydrolyzes under alkaline condition generates nano level solid silicon dioxide microsphere, then carries out hydro-thermal process to it,
To realize by solid to porous transformation, but hydrothermal treatment process needs the reaction environment of high temperature and pressure.
Invention content
The technical problem to be solved by the present invention is to overcome prior art defect, a kind of monodisperse silica microspheres are provided
The main thought of preparation method, this method is that polymer seeds microballoon is swollen by ethyl orthosilicate, and it is compound micro- that silica is made
Ball, the complex microsphere pass through high-temperature calcination, can form porous silica microballoon, the silicon dioxide microsphere prepared using this method
Uniform particle diameter, grain diameter and aperture it is controllable.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of monodisperse silica microspheres, includes the following steps：
1 polymer seeds are added in the organic solvent containing ammonium hydroxide, form evenly dispersed seed suspension liquid, described kind
Polymer seeds solid content is 4-8g/L in sub- suspension；
2 are added to ethyl orthosilicate in organic solvent, stir evenly to form teos solution；
Ammonium hydroxide and ethyl alcohol are configured to initiator solution by 3 by a certain percentage；
4 teos solutions are added to the initiator solution in the seed suspension liquid simultaneously, and point
The addition constant airspeed of the teos solution and the initiator solution is not controlled, and postcooling, centrifugation point are completed in reaction
From obtaining SiO 2 composite microsphere.
Preferably, polymer seeds described in the step 1 are polystyrene seed, and the polymer seeds and institute
The weight ratio for stating ammonium hydroxide is 1:5-1:10.
Preferably, the ratio between ethyl orthosilicate described in the step 2 and the volume of the organic solvent are 1:3-1:10.
Preferably, in the step 3, the ratio between volume ammonium hydroxide：Ethyl alcohol is 1:2-1:5.
Preferably, the addition speed of teos solution described in the step 4 is 0.1-5mL/min, the initiation
The addition speed of agent solution is 0.5-2.5mL/min.
Preferably, organic solvent described in the step 1 is ethyl alcohol.
Preferably, organic solvent described in the step 2 is ethyl alcohol, ethylene glycol or tetrahydrofuran.
Preferably, the polymer seeds and the ethyl orthosilicate weight ratio are 1:5-1:30.
Preferably, following steps are specifically included：
1 polystyrene seed is added in the ethyl alcohol containing ammonium hydroxide, forms evenly dispersed seed suspension liquid, the seed
Polymer seeds solid content is 6-8g/L in suspension, and polystyrene seed and the weight ratio of ammonium hydroxide are 1:6-1:8；
2 are added to ethyl orthosilicate in tetrahydrofuran, stir evenly to form teos solution, the positive silicic acid second
The ratio between ester and the tetrahydrofuran volume are 1:6-1:10；
Ammonium hydroxide and ethyl alcohol are configured to initiator solution by 3 by a certain percentage, and the ratio between the volume of the ammonium hydroxide and ethyl alcohol is 1:
3；
4 are added to teos solution and initiator solution in seed suspension liquid with constant speed addition simultaneously, institute
The addition speed for stating teos solution is 2mL/min, and the addition speed of the initiator solution is that 1.5mL/min has reacted
At postcooling, it is centrifugally separating to obtain SiO 2 composite microsphere.
Wherein, further include following step after the step 4：
SiO 2 composite microsphere described in step 4 is carried out calcination processing by 5 at 500-800 DEG C, wherein calcination time
It is 3-6 hours, obtains porous silica microballoon.
Preferably, the calcination processing process heating rate is 2-10 DEG C/min.
Wherein, porous silica microballoon obtained is monodisperse silica microspheres.
The advantageous effect that the present invention is reached：
The method of the present invention can prepare the controllable silicon dioxide microsphere of grain size and aperture, and the silicon dioxide microsphere grain prepared
Diameter height is uniform, and chemical stability is high, good dispersion.
Specific implementation mode
With reference to specific embodiment, the invention will be further described.Following embodiment is only used for clearly illustrating
Technical scheme of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
(1) it is constant under room temperature, polystyrene seed (0.55 μm of granularity, CV=3%) is added to containing ammonia
It in the ethyl alcohol of water, is sufficiently stirred, forms that evenly dispersed seed suspension liquid is spare, and polymer seeds solid contains in seed suspension liquid
Amount is 6g/L, and polystyrene seed and the weight ratio of ammonium hydroxide (mass percentage concentration containing ammonia is 25%) are 1:6；
(2) ethyl orthosilicate is added in ethyl alcohol, stirs evenly that form teos solution spare, wherein positive silicon
The ratio between volume of acetoacetic ester and ethyl alcohol is 1:6；
(3) it is standby that ammonium hydroxide (mass percentage concentration containing ammonia be 25%) is configured to initiator solution by a certain percentage with ethyl alcohol
With, wherein the ratio between volume of ammonium hydroxide and ethyl alcohol is 1:3；
(4) teos solution and initiator solution are added to constant speed addition in seed suspension liquid simultaneously,
The addition speed for controlling teos solution is 2mL/min, and the addition speed for controlling initiator solution is 1.5mL/min, is reached
Stop that seed suspension agent and initiator solution is added after to preset microspherulite diameter, after reacting 2 hours, stands, centrifuge
To polystyrene SiO 2 composite microsphere, microballoon is washed using absolute ethyl alcohol.
Its grain size is measured using Beckman Counter and particle diameter distribution obtains：Grain size is 5 μm, CV (coefficient of
Variation it is) 2.5%.
Embodiment 2
(1) it is constant under room temperature, polystyrene seed (10 μm of granularity, CV=3%) is added to containing ammonium hydroxide
Ethyl alcohol in, be sufficiently stirred, it is spare to form evenly dispersed seed suspension liquid, polymer seeds solid content in seed suspension liquid
For 7g/L, and polystyrene seed and the weight ratio of ammonium hydroxide (mass percentage concentration containing ammonia is 25%) are 1:10；
(2) ethyl orthosilicate is added in ethyl alcohol, stirs evenly that form teos solution spare, wherein positive silicon
The ratio between volume of acetoacetic ester and ethyl alcohol is 1:4；
(3) it is standby that ammonium hydroxide (mass percentage concentration containing ammonia be 25%) is configured to initiator solution by a certain percentage with ethyl alcohol
With, wherein the ratio between volume of ammonium hydroxide and ethyl alcohol is 1:4；
(4) teos solution and initiator solution are added to constant speed addition in seed suspension liquid simultaneously,
The addition speed for controlling teos solution is 1mL/min, and the addition speed for controlling initiator solution is 1mL/min, is reached
Stop that seed suspension agent and initiator solution is added after preset microspherulite diameter, after reacting 3 hours, stands, be centrifugally separating to obtain
Polystyrene SiO 2 composite microsphere washs microballoon using absolute ethyl alcohol.
Its grain size is measured using Beckman Counter and particle diameter distribution obtains：Grain size is 50 μm, CV (coefficient
Of variation) it is 3%.
Embodiment 3
(1) it is constant under room temperature, polystyrene seed (5 μm of granularity, CV=3%) is added to containing ammonium hydroxide
It in ethyl alcohol, is sufficiently stirred, forms that evenly dispersed seed suspension liquid is spare, and polymer seeds solid content is in seed suspension liquid
6.5g/L, and polystyrene seed and the weight ratio of ammonium hydroxide (mass percentage concentration containing ammonia is 25%) they are 1:5；
(2) ethyl orthosilicate is added in tetrahydrofuran, stirs evenly that form teos solution spare, wherein
The ratio between ethyl orthosilicate and tetrahydrofuran volume are 1:5；
(3) it is standby that ammonium hydroxide (mass percentage concentration containing ammonia be 25%) is configured to initiator solution by a certain percentage with ethyl alcohol
With, wherein the ratio between volume of ammonium hydroxide and ethyl alcohol is 1:2；
(4) teos solution and initiator solution are added to constant speed addition in seed suspension liquid simultaneously,
The addition speed for controlling teos solution is 3mL/min, and the addition speed for controlling initiator solution is 1.5mL/min, is reached
Stop that seed suspension agent and initiator solution is added after to preset microspherulite diameter, after reacting 2 hours, stands, centrifuge
To polystyrene SiO 2 composite microsphere, microballoon is washed using absolute ethyl alcohol.
Its grain size is measured using Beckman Counter and particle diameter distribution obtains：Grain size is 30 μm, CV (coefficient
Of variation) it is 2.9%.
Embodiment 4
(1) it is constant under room temperature, polystyrene seed granularity (1.5 μm, CV=3%) is added to containing ammonium hydroxide
Ethyl alcohol in, be sufficiently stirred, it is spare to form evenly dispersed seed suspension liquid, polymer seeds solid content in seed suspension liquid
For 8g/L, and polystyrene seed and the weight ratio of ammonium hydroxide (mass percentage concentration containing ammonia is 25%) are 1:7；
(2) ethyl orthosilicate is added in ethylene glycol, stirs evenly that form teos solution spare, wherein just
The ratio between volume of silester and ethylene glycol is 1:3；
(3) it is standby that ammonium hydroxide (mass percentage concentration containing ammonia be 25%) is configured to initiator solution by a certain percentage with ethyl alcohol
With, wherein the ratio between volume of ammonium hydroxide and ethyl alcohol is 1:5；
(4) teos solution and initiator solution are added to constant speed addition in seed suspension liquid simultaneously,
The addition speed for controlling teos solution is 0.3mL/min, and the addition speed for controlling initiator solution is 2mL/min, is reached
Stop that seed suspension agent and initiator solution is added after to preset microspherulite diameter, after reacting 2 hours, stands, centrifuge
To polystyrene SiO 2 composite microsphere, microballoon is washed using absolute ethyl alcohol.
Its grain size is measured using Beckman Counter and particle diameter distribution obtains：Grain size is 10 μm, CV (coefficient
Of variation) it is 2.7%.
Embodiment 5
(1) it is constant under room temperature, polystyrene seed granularity (3 μm, CV=3%) is added to containing ammonium hydroxide
It in ethyl alcohol, is sufficiently stirred, forms that evenly dispersed seed suspension liquid is spare, and polymer seeds solid content is in seed suspension liquid
7.5g/L, and polystyrene seed and the weight ratio of ammonium hydroxide (mass percentage concentration containing ammonia is 25%) they are 1:8；
(2) ethyl orthosilicate is added in ethyl alcohol, stirs evenly that form teos solution spare, wherein positive silicon
The ratio between volume of acetoacetic ester and ethyl alcohol is 1:10；
(3) it is standby that ammonium hydroxide (mass percentage concentration containing ammonia be 25%) is configured to initiator solution by a certain percentage with ethyl alcohol
With, wherein the ratio between volume of ammonium hydroxide and ethyl alcohol is 1:2；
(4) teos solution and initiator solution are added to constant speed addition in seed suspension liquid simultaneously,
The addition speed for controlling teos solution is 5mL/min, and the addition speed for controlling initiator solution is 0.5mL/min, is reached
Stop that seed suspension agent and initiator solution is added after to preset microspherulite diameter, after reacting 2 hours, stands, centrifuge
To polystyrene SiO 2 composite microsphere, microballoon is washed using absolute ethyl alcohol.
(5) polystyrene SiO 2 composite microsphere of the washing after dry is subjected to calcination processing, 4 is calcined at 600 DEG C
Hour, obtain porous silica microballoon.
Its grain size is measured using Beckman Counter and particle diameter distribution obtains：Grain size is 20 μm, aperture 30nm, CV
(coefficient of variation) is 2.7%.
Embodiment 6
(1) it is constant under room temperature, polystyrene seed granularity (20 μm, CV=3%) is added to containing ammonium hydroxide
Ethyl alcohol in, be sufficiently stirred, it is spare to form evenly dispersed seed suspension liquid, polymer seeds solid content in seed suspension liquid
For 8g/L, and polystyrene seed and the weight ratio of ammonium hydroxide (mass percentage concentration containing ammonia is 25%) are 1:9；
(2) ethyl orthosilicate is added in ethyl alcohol, stirs evenly that form teos solution spare, wherein positive silicon
The ratio between volume of acetoacetic ester and ethyl alcohol is 1:8；
(3) it is standby that ammonium hydroxide (mass percentage concentration containing ammonia be 25%) is configured to initiator solution by a certain percentage with ethyl alcohol
With, wherein the ratio between volume of ammonium hydroxide and ethyl alcohol is 1:5；
(4) teos solution and initiator solution are added to constant speed addition in seed suspension liquid simultaneously,
The addition speed for controlling teos solution is 4mL/min, and the addition speed for controlling initiator solution is 2.5mL/min, is reached
Stop that seed suspension agent and initiator solution is added after to preset microspherulite diameter, after reacting 4 hours, stands, centrifuge
To polystyrene SiO 2 composite microsphere, microballoon is washed using absolute ethyl alcohol.
(5) will washing it is dry after polystyrene SiO 2 composite microsphere carry out calcination processing, calcining furnace 400 DEG C with
5 DEG C of speed per minute heat up, and heating maintains 700 DEG C to calcine 5 hours after 1 hour, obtains porous silica microballoon.
Its grain size is measured using Beckman Counter and particle diameter distribution obtains：Grain size is 65 μm, aperture 50nm, CV
(coefficient of variation) is 2.9%.
Embodiment 7
(1) it is constant under room temperature, polystyrene seed granularity (1.5 μm, CV=3%) is added to containing ammonium hydroxide
Ethyl alcohol in, be sufficiently stirred, it is spare to form evenly dispersed seed suspension liquid, polymer seeds solid content in seed suspension liquid
For 8g/L, and polystyrene seed and the weight ratio of ammonium hydroxide (mass percentage concentration containing ammonia is 25%) are 1:7；
(2) ethyl orthosilicate is added in ethyl alcohol, stirs evenly that form teos solution spare, wherein positive silicon
The ratio between volume of acetoacetic ester and ethyl alcohol is 1:3；
(3) it is standby that ammonium hydroxide (mass percentage concentration containing ammonia be 25%) is configured to initiator solution by a certain percentage with ethyl alcohol
With, wherein the ratio between volume of ammonium hydroxide and ethyl alcohol is 1:5；
(4) teos solution and initiator solution are added to constant speed addition in seed suspension liquid simultaneously,
The addition speed for controlling teos solution is 4mL/min, and the addition speed for controlling initiator solution is 2.5mL/min, is reached
Stop that seed suspension agent and initiator solution is added after to preset microspherulite diameter, after reacting 4 hours, stands, centrifuge
To polystyrene SiO 2 composite microsphere, microballoon is washed using absolute ethyl alcohol.
(5) will washing it is dry after polystyrene SiO 2 composite microsphere carry out calcination processing, calcining furnace 400 DEG C with
5 DEG C of speed per minute heat up, and heating maintains 700 DEG C to calcine 5 hours after 1 hour, obtains porous silica microballoon.
Its grain size is measured using Beckman Counter and particle diameter distribution obtains：Grain size is 10 μm, aperture 10nm, CV
(coefficient of variation) is 2.5%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of monodisperse silica microspheres, which is characterized in that include the following steps：
(1) polymer seeds are added in the organic solvent containing ammonium hydroxide, form evenly dispersed seed suspension liquid, the seed
Polymer seeds solid content is 4-8g/L in suspension；
(2) ethyl orthosilicate is added in organic solvent, stirs evenly to form teos solution；
(3) ammonium hydroxide and ethyl alcohol are configured to initiator solution by a certain percentage；
(4) teos solution is added to the initiator solution in the seed suspension liquid simultaneously, and respectively
The addition constant airspeed of the teos solution and the initiator solution is controlled, stands, centrifuges after the completion of reaction
Obtain SiO 2 composite microsphere.
2. a kind of preparation method of monodisperse silica microspheres according to claim 1, which is characterized in that the step
(1) polymer seeds described in are polystyrene seed, and the polymer seeds and the weight ratio of the ammonium hydroxide are 1:5-
1:10。
3. a kind of preparation method of monodisperse silica microspheres according to claim 1, which is characterized in that the step
(2) the ratio between ethyl orthosilicate described in and the volume of the organic solvent are 1:3-1:10.
4. a kind of preparation method of monodisperse silica microspheres according to claim 1, which is characterized in that the step
(3) in, the ratio between volume ammonium hydroxide：Ethyl alcohol is 1:2-1:5.
5. a kind of preparation method of monodisperse silica microspheres according to claim 1, which is characterized in that the step
(4) the addition speed of teos solution described in is 0.1-5mL/min, and the addition speed of the initiator solution is 0.5-
2.5mL/min。
6. a kind of preparation method of monodisperse silica microspheres according to claim 1 has described in the step (1)
Solvent is ethyl alcohol.
7. a kind of preparation method of monodisperse silica microspheres according to claim 1, which is characterized in that the step
(2) organic solvent described in is ethyl alcohol, ethylene glycol or tetrahydrofuran.
8. a kind of preparation method of monodisperse silica microspheres according to claim 1, which is characterized in that specifically include
Following steps：
(1) polystyrene seed is added in the ethyl alcohol containing ammonium hydroxide, forms evenly dispersed seed suspension liquid, the seed is outstanding
Polymer seeds solid content is 6-8g/L in supernatant liquid, and polystyrene seed and the weight ratio of ammonium hydroxide are 1:6-1:8；
(2) ethyl orthosilicate is added in tetrahydrofuran, stirs evenly to form teos solution, the ethyl orthosilicate
It is 1 with the ratio between the tetrahydrofuran volume:6-1:10；
(3) ammonium hydroxide and ethyl alcohol are configured to initiator solution by a certain percentage, the ratio between the volume of the ammonium hydroxide and ethyl alcohol is 1:3；
(4) teos solution and initiator solution are added to constant speed in seed suspension liquid simultaneously, the positive silicon
The addition speed of acetate solution is 2mL/min, and the addition speed of the initiator solution is quiet after the completion of 1.5mL/min reacts
It sets, is centrifugally separating to obtain SiO 2 composite microsphere.
9. a kind of preparation method of monodisperse silica microspheres according to any one of claim 1-8, the step
(4) further include following step after：
(5) SiO 2 composite microsphere described in step (4) is subjected to calcination processing at 500-800 DEG C, wherein calcination time
It is 3-6 hours, obtains porous silica microballoon.
10. a kind of preparation method of monodisperse silica microspheres according to claim 9, which is characterized in that described to forge
Burning processing procedure heating rate is 2-10 DEG C/min.
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| 中空多空SIO2颗粒的制备及自修复超疏水表面的构筑;张治东;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20160115;第18页 * |
| 种子聚合法制备大粒径单分散聚合物微球及其应用;王冬;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20141215;第35页 * |
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