CN109399648A - Micron size porous silica microballoon and preparation method thereof - Google Patents
Micron size porous silica microballoon and preparation method thereof Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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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- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a kind of preparation methods of micron size porous silica microballoon, it is using a kind of novel porous polysilsesquioxane microballoon as template, dinectly bruning removes organic principle, and the monodisperse porous silicon dioxide microsphere material of partial size and pore size controllably can be obtained.The micron size porous silica microballoon that this method is prepared is also disclosed, the partial size of silicon dioxide microsphere is at 3-10 μm, and pore volume is in 0.3-0.9cm3/ g, specific surface area is in 100-400m2/ g, aperture is in 3-100nm.Compared with traditional handicraft, the preparation method is simple, economy, without gradation sizing, porous silica microballoon spherical shape rounding obtained, particle diameter distribution is uniform, has meso-hole structure, it may be directly applied to Stationary Phase of HPLC, can also be applied to the fields such as catalytic carrier, coating, cosmetic additive agent.
Description
Technical field
The invention belongs to the preparation technical fields of the monodisperse mesoporous silica microballoon of efficient liquid phase, and in particular to a kind of
Micron size porous silica microballoon and preparation method thereof, more particularly, to the fixed partial size of high performance liquid chromatography point
Cloth is the preparation method of 3-10 μm of monodisperse porous silicon dioxide microsphere.
Background technique
Monodispersed porous silica microballoon because of its high mechanical strength, large specific surface area, have meso-hole structure and surface
It is abundant can functionalization silicone hydroxyl the features such as, have in biomedicine, cosmetics, coating, chemistry and chromatographic field extensive
Application prospect.Monodisperse porous silicon dioxide microsphere of the partial size in 3-10 μ m is taken on emphatically in efficient liquid phase stationary phase
The role wanted can effectively reduce flow resistance and resistance to mass tranfer in chromatographic process.
The preparation method of monodisperse silica has and much has classical sol-gal process, synthesized by molecular template, polymer in-mold
Plate method.Sol method is generally used to synthesis nano sphericity mesoporous silicon dioxide, because partial size is too small, causes it not to be able to satisfy chromatography and fills out
The demand of material.Synthesized by molecular template is to be with ethyl orthosilicate as template using surfactant or with block copolymer mixture
Silicon source is hydrolyzed by catalyst, is deposited in the template of surfactant micellar formation, and calcining removes surfactant, can
To obtain the material of high-specific surface area, orderly pore structure, it is widely used in medicament slow release, chromatographic field.But pass through molecule
The material aperture of template preparation is generally less than 4nm, cannot be directly used to chromatograph stationary-phase stuffing, application field receives limit
System.Polymer template method is also another effective way for preparing silicon dioxide microsphere, using polyethylene-divinylbenzene (PS-
) etc. DVB polymer microballoons are template, with ethyl orthosilicate (TEOS) for presoma, pass through polymerisation induced or Electrostatic Absorption will
Silica solution deposits in the hole of polymer, then high-temperature calcination removes polymer template, and the silica of macropore can be prepared
Microballoon, because template removing leaves biggish hole, resulting silicon dioxide microsphere specific surface area is low, mechanical strength is inadequate, general to use
In the analysis of high molecular weight protein etc..Therefore it is suitable for the preparation and technique essence of the monodisperse mesoporous silica microballoon of efficient liquid phase
Letter is also badly in need of furtheing investigate.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, and it is micro- to provide a kind of micron size porous silica
Ball and preparation method thereof.
The present invention is to solve the technical issues of proposing in background technique, the technical solution adopted is as follows: micron size
The preparation method of porous silica microballoon, includes the following steps:
1) the monosubstituted trialkoxy silane of 20g is added in 100mL deionized water, the hydrochloric acid of 0-400 μ L pH 1 is added
Solution is stirred at room temperature reaction 1-4h, obtains polysilsesquioxane hydrolyzate；
2) 10-50 μ L concentrated ammonia liquor is added in polysilsesquioxane hydrolyzate, stirs evenly, stands reaction 2-12h, filtering
Mother liquor is removed, microballoon is collected with 95% ethanol washing and obtains polysilsesquioxane gel micro-ball；
3) mass volume ratio 0.1 is pressed, 1g polysilsesquioxane gel micro-ball is dispersed in the ethyl alcohol of 10mL 80%, is mixed
It is even；
4) sodium hydroxide solution that concentration is 0.01-0.6M is added in the mixed solution that step (3) obtains, mixing is equal
Even, 70 DEG C of water-bath concussion reaction 10h are filtered to remove solvent；
5) 95% ethyl alcohol of microballoon, water alternately wash, until filtrate is neutrality, 50 DEG C are dried overnight, and can be obtained porous
Polysilsesquioxane template microsphere；
6) template microsphere is heated under the rate of 10 DEG C/min, is warming up to 600 DEG C, calcined 6h, obtain porous dioxy
SiClx microballoon.
Second technical solution of the invention is micron size porous silica microballoon, using above-mentioned preparation method
It is made, the partial size of silicon dioxide microsphere is at 3-10 μm, and pore volume is in 0.3-0.9cm3/ g, specific surface area is in 100-400m2/ g, hole
Diameter is in 3-100nm.
Beneficial effect
1, it is template present invention employs novel monodisperse porous polysilsesquioxane microballoon, is removed by high-temperature calcination
Silicon dioxide microsphere can be obtained in organic principle, and preparation process is simple, and obtained microballoon has pattern rounding, monodisperse, partial size
The features such as narrowly distributing, partial size and adjustable pore structure；It is not screened to may be directly applied to chromatographic stationary phases.
2, cost of material is low, condition controllability is strong, partial size and pore structure are controllable.
Detailed description of the invention
Fig. 1 is that the scanning electron microscope of the silicon dioxide microsphere prepared by template of poly methyl silsesquioxane microballoon is shone
Piece.
Fig. 2 is the N of the silicon dioxide microsphere prepared by template of poly methyl silsesquioxane microballoon2Adsorption-desorption isothermal
Curve and graph of pore diameter distribution.
Fig. 3 is the scanning electricity of the silicon dioxide microsphere of the different-grain diameter prepared by template of poly methyl silsesquioxane microballoon
Sub- microscope photo: A-10.0 μm；B-5.0μm；C-3.4μm.
It in prepared silicon dioxide microsphere is chromatographic stationary phases that Fig. 4, which is column criterion liquid (phenol, parachloronitrobenzene, naphthalene),
Separation: 1- phenol, 2- parachloronitrobenzene, 3- naphthalene.
Fig. 5 is the pressure current curve for preparing silicon dioxide microsphere chromatograph packing material.
Fig. 6 is benzene homologue (toluene, ethylbenzene, propyl benzene, butylbenzene, penta benzene) in the C of preparation18Bonded silica microballoon is color
Compose the separation of stationary phase: 1- toluene, 2- ethylbenzene, 3- propyl benzene, 4- butylbenzene, penta benzene of 5-.
Specific embodiment
Combined with specific embodiments below, the present invention is further elaborated.The embodiment of the present invention is to make this field
Technical staff more fully understand the present invention, not to the present invention make any limitation.The method is unless otherwise instructed
Conventional method, the raw material can obtain unless otherwise instructed from public commercial source.
Embodiment 1
Silicon dioxide microsphere is prepared using poly methyl silsesquioxane microballoon as template
(1) 20g methyltrimethoxysilane is added in 100mL deionized water, the hydrochloric acid solution of 0 μ L pH 1 is added,
Reaction 1h is stirred at room temperature, obtains polysilsesquioxane hydrolyzate；
(2) 10 μ L concentrated ammonia liquors are added in polysilsesquioxane hydrolyzate, stir evenly, stands reaction 4h, is filtered to remove
Mother liquor collects microballoon with 95% ethanol washing and obtains polysilsesquioxane gel micro-ball；
(3) mass volume ratio 0.1 is pressed, 1g polysilsesquioxane gel micro-ball is dispersed in the ethyl alcohol of 10mL 80%, is mixed
It is even；
(4) sodium hydroxide is added in the mixed solution that step (3) obtains, being allowed to concentration is 0.05M, is uniformly mixed, 70
DEG C water-bath concussion reaction 10h is filtered to remove solvent, and 95% ethyl alcohol of microballoon, water alternately wash, until filtrate is neutrality, 50 DEG C
It is dried overnight, porous polysilsesquioxane template microsphere can be obtained.
(5) by template microsphere under the conditions of 10 DEG C/min of the rate of heat addition, 600 DEG C are warming up to, high-temperature calcination 6h.After calcining,
Resultant product is porous silicon dioxide microsphere.
The characterize data of silica obtained microballoon: Fig. 1 is morphology characterization；Pore structure data are as follows: 7.0 μm of average grain diameter, compare hole
Hold 0.8cm3/ g, specific surface area 300m2/ g, average pore size 9.7nm.
Embodiment 2
The silicon dioxide microsphere of different pore size is prepared using poly methyl silsesquioxane microballoon as template
(1) 20g methyltrimethoxysilane is added in 100mL deionized water, the hydrochloric acid solution of 0 μ L pH 1 is added,
Reaction 1h is stirred at room temperature, obtains polysilsesquioxane hydrolyzate；
(2) 10 μ L concentrated ammonia liquors are added in polysilsesquioxane hydrolyzate, stir evenly, stands reaction 4h, is filtered to remove
Mother liquor collects microballoon with 95% ethanol washing and obtains polysilsesquioxane gel micro-ball；
(3) mass volume ratio 0.1 is pressed, 1g polysilsesquioxane gel micro-ball is dispersed in the ethyl alcohol of 10mL 80%, is mixed
It is even；
(4) sodium hydroxide is added in the mixed solution that step (3) obtains, being allowed to concentration is respectively 0.01,0.025M, is mixed
It closes uniformly, 70 DEG C of water-bath concussion reaction 10h, is filtered to remove solvent, 95% ethyl alcohol of microballoon, water alternately wash, until filtrate is
Neutrality, 50 DEG C are dried overnight, and the porous polysilsesquioxane template microsphere of Different Pore Structures can be obtained.
(5) template microsphere is heated under the rate of 10 DEG C/min, is warming up to 600 DEG C, high-temperature calcination 6h.It obtains porous
Silicon dioxide microsphere.
The characterize data of microballoon: Fig. 2 is isothermal curve and graph of pore diameter distribution；What table 1 was listed is the dioxy of Different Pore Structures
The pore structure parameter and particle diameter distribution of SiClx microballoon.
The pore structure parameter and particle diameter distribution of the silicon dioxide microsphere of 1. different pore size of table
Embodiment 3
The silicon dioxide microsphere of different-grain diameter diameter is prepared using poly methyl silsesquioxane microballoon as template
(1) 20g methyltrimethoxysilane is added in 100mL deionized water, the hydrochloric acid solution of 0 μ L pH 1 is added,
Reaction 1h is stirred at room temperature, obtains polysilsesquioxane hydrolyzate；
(2) it is separately added into 5,20,50 μ L concentrated ammonia liquors in polysilsesquioxane hydrolyzate, stirs evenly, stands respectively anti-
4,3,2h are answered, mother liquor is filtered to remove, microballoon is collected with 95% ethanol washing and obtains the polysilsesquioxane gel of different-grain diameter
Microballoon；
(3) mass volume ratio 0.1 is pressed, 1g polysilsesquioxane gel micro-ball is dispersed in the ethyl alcohol of 10mL 80%, is mixed
It is even；
(4) sodium hydroxide is added in the mixed solution that step (3) obtains, being allowed to concentration is respectively 0.05,0.1,0.6M,
It is uniformly mixed, 70 DEG C of water-bath concussion reaction 10h, is filtered to remove solvent, 95% ethyl alcohol of microballoon, water alternately wash, until filtrate
For neutrality, 50 DEG C are dried overnight, and porous polysilsesquioxane template microsphere can be obtained.
(5) template microsphere is heated under the rate of 10 DEG C/min, is warming up to 600 DEG C, high-temperature calcination 6h.It obtains porous
Silicon dioxide microsphere.
The characterize data of microballoon: Fig. 3 is morphology characterization；What table 2 was listed is the silica microballoon of different-grain diameter
Pore structure parameter and particle diameter distribution.
The pore structure parameter and particle diameter distribution of the silicon dioxide microsphere of 2. different-grain diameter of table
Embodiment 4
Silicon dioxide microsphere is prepared using polyvinyl silsesquioxane microballoon as template
(1) 20g vinyltrimethoxysilane is added in 100mL deionized water, the hydrochloric acid of 400 μ L pH 1 is added
Solution is stirred at room temperature reaction 4h, obtains polysilsesquioxane hydrolyzate；
(2) 10 μ L concentrated ammonia liquors are added in polysilsesquioxane hydrolyzate, stir evenly, stands reaction 2h, is filtered to remove
Mother liquor collects microballoon with 95% ethanol washing and obtains polysilsesquioxane gel micro-ball；
(3) mass volume ratio 0.1 is pressed, 1g polysilsesquioxane gel micro-ball is dispersed in the ethyl alcohol of 10mL 80%, is mixed
It is even；
(4) sodium hydroxide is added in the mixed solution that step (3) obtains, being allowed to concentration is 0.1M, is uniformly mixed, 70 DEG C
Water-bath concussion reaction 10h is filtered to remove solvent, and 95% ethyl alcohol of microballoon, water alternately wash, until filtrate is neutrality, 50 DEG C dry
It is dry overnight, porous polysilsesquioxane template microsphere can be obtained.
(5) template microsphere is heated under the rate of 10 DEG C/min, is warming up to 600 DEG C, high-temperature calcination 6h.It obtains porous
Silicon dioxide microsphere.
The characterize data of microballoon: it is two prepared by template that table 3 was listed, which is using polyvinyl silsesquioxane microballoon,
The pore structure parameter and particle diameter distribution of silicon oxide microsphere.
Table 3. prepares the pore structure parameter and partial size of silicon dioxide microsphere using polyvinyl silsesquioxane microballoon as template
Distribution
Embodiment 5
Silicon dioxide microsphere is prepared using poly- mercapto propylsilsesquioxane microballoon as template
(1) 20g r-chloropropyl trimethoxyl silane is added in 100mL deionized water, the hydrochloric acid of 400 μ L pH 1 is added
Solution is stirred at room temperature reaction 4h, obtains polysilsesquioxane hydrolyzate；
(2) 10 μ L concentrated ammonia liquors are added in polysilsesquioxane hydrolyzate, stir evenly, stands reaction 12h, is filtered to remove
Mother liquor collects microballoon with 95% ethanol washing and obtains polysilsesquioxane gel micro-ball；
(3) mass volume ratio 0.1 is pressed, 1g polysilsesquioxane gel micro-ball is dispersed in the ethyl alcohol of 10mL 80%, is mixed
It is even；
(4) sodium hydroxide is added in the mixed solution that step (3) obtains, being allowed to concentration is 0.05M, is uniformly mixed, 70
DEG C water-bath concussion reaction 10h is filtered to remove solvent, and 95% ethyl alcohol of microballoon, water alternately wash, until filtrate is neutrality, 50 DEG C
It is dried overnight, porous polysilsesquioxane template microsphere can be obtained.
(5) template microsphere is heated under the rate of 10 DEG C/min, is warming up to 600 DEG C, high-temperature calcination 6h.It obtains porous
Silicon dioxide microsphere.
The characterize data of microballoon: what table 4 was listed is the dioxy using poly- mercapto propylsilsesquioxane microballoon for template preparation
The pore structure parameter and particle diameter distribution of SiClx microballoon.
The pore structure parameter and grain for the silicon dioxide microsphere that table 4. is prepared using poly- mercapto propylsilsesquioxane microballoon as template
Diameter distribution
Embodiment 6
The chromatographic applications of monodisperse silica microspheres
(1) in there-necked flask, it is (real that the silicon dioxide microsphere that 3.5g average grain diameter is 5 μm the derivatization process of microballoon: is added
Apply example 3 preparation) with 70mL mass fraction be 10% hydrochloric acid, 250rpm mechanical stirring be uniformly mixed, in 105 DEG C of oil baths, heating
Flow back 8.0h.It is washed to neutrality, 90 DEG C of vacuum drying after ethanol washing after reaction.In another there-necked flask, 3g acid is added
Silica gel microball and 80mL dry toluene after changing drying, 250rpm mechanical stirring are uniformly mixed, and 0.5mL triethylamine, nitrogen is added
Under protection, 110 DEG C, 2mL octadecyl trichlorosilane alkane is added after being stirred 30min in 250rpm, continues back flow reaction 8h.Reaction
After successively with toluene, ethyl alcohol, water, after ethanol washing, 90 DEG C of vacuum drying.
(2) chromatographic applications: taking appropriate 18 bonded silica gel of carbon, and high-pressure homogenization is packed into stainless steel chromatographic column.With column criterion
Liquid evaluates the chromatographic performance of prepared chromatograph packing material, and chromatogram is as shown in Figure 4.The result shows that chromatographic column is to several small points
Son can be good at separating, and chromatographic peak is symmetrical, and prepared microballoon can be used for the separation of chromatography.
On this basis, the pressure current curve of chromatographic column is tested, as shown in figure 5, pressure and flow velocity as the result is shown
Linear relationship is good, illustrates that the mechanical strength of microballoon is fine, meets the needs of chromatograph packing material.With the chromatographic column of filling and to benzene
Homologue is separated, as shown in fig. 6, chromatographic column separates very well several substituted benzenes, methylene based selective is
0.186 is suitable with commodity column, illustrates C18Silica chromatography microballoon after bonding meets the needs of chromatograph packing material.
It should be understood that embodiment and example discussed herein simply to illustrate that, to those skilled in the art
For, it can be improved or converted, and all these modifications and variations all should belong to the protection of appended claims of the present invention
Range.
Claims (2)
1. the preparation method of micron size porous silica microballoon, which comprises the steps of:
1) the monosubstituted trialkoxy silane of 20g is added in 100mL deionized water, the hydrochloric acid that 0-400 μ L pH 1 is added is molten
Liquid is stirred at room temperature reaction 1-4h, obtains polysilsesquioxane hydrolyzate；
2) 10-50 μ L concentrated ammonia liquor is added in polysilsesquioxane hydrolyzate, stirs evenly, stands reaction 2-12h, is filtered to remove
Mother liquor collects microballoon with 95% ethanol washing and obtains polysilsesquioxane gel micro-ball；
3) mass volume ratio 0.1 is pressed, 1g polysilsesquioxane gel micro-ball is dispersed in the ethyl alcohol of 10mL 80%, is mixed；
4) sodium hydroxide solution that concentration is 0.01-0.6M is added in the mixed solution that step (3) obtains, is uniformly mixed, 70
DEG C water-bath concussion reaction 10h, is filtered to remove solvent；
5) 95% ethyl alcohol of microballoon, water alternately wash, until filtrate is neutrality, 50 DEG C are dried overnight, and can be obtained porous poly- times
Half siloxanes template microsphere；
6) template microsphere is heated under the rate of 10 DEG C/min, is warming up to 600 DEG C, calcined 6h, obtain porous silica
Microballoon.
2. the micron size porous silica microballoon that preparation method according to claim 1 is prepared, feature
It is, the partial size of silicon dioxide microsphere is at 3-10 μm, and pore volume is in 0.3-0.9cm3/ g, specific surface area is in 100-400m2/ g, hole
Diameter is in 3-100nm.
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| CN108110091A (en) * | 2018-01-15 | 2018-06-01 | 山西奥元威德科技有限公司 | Application of the silica slightly soluble liquid in photovoltaic plating is brilliant |
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| CN111848206A (en) * | 2020-07-20 | 2020-10-30 | 贵州正业龙腾新材料开发有限公司 | Preparation method of monodisperse micron-sized hollow ceramic microspheres |
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