CN109607552A - A method of preparing three-dimensional ball chain structure silica - Google Patents
A method of preparing three-dimensional ball chain structure silica Download PDFInfo
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- CN109607552A CN109607552A CN201910034648.3A CN201910034648A CN109607552A CN 109607552 A CN109607552 A CN 109607552A CN 201910034648 A CN201910034648 A CN 201910034648A CN 109607552 A CN109607552 A CN 109607552A
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- ball chain
- dimensional ball
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 11
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000006227 byproduct Substances 0.000 claims abstract 2
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 239000002210 silicon-based material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- -1 γ-methacryloxypropyl Chemical group 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The present invention is a kind of method for preparing three-dimensional ball chain structure silica.This method comprises the following steps: dehydrated alcohol and distilled water are mixed, add Surfactant CTAB, ethyl orthosilicate (TEOS) and ammonium hydroxide are sequentially added after dissolution under stirring condition, it is finally added dropwise to γ-methacryloxypropyl trimethoxy silane (KH570), obtains white suspension；White suspension is reacted into 1-6h at 25-50 DEG C, then by product separation, washing, drying, then 5~8h is roasted at 450-700 DEG C and obtains final product, i.e. three-dimensional ball chain silica.The earth silicon material that the present invention synthesizes, the material with three dimensional skeletal structure effectively can improve or solve the problems of the prior art, and sphere size is controllable in a certain range.
Description
Technical field
The present invention relates to a kind of methods for preparing three-dimensional ball chain silica, belong to field of material technology.
Background technique
Silica is as a kind of tasteless, nontoxic, free of contamination nonmetallic materials, except in ceramics, electronics, metallurgy and machine
Outside being widely used in the various fields such as tool, because it has the characteristics that excellent chemical stability, thermal stability and bio-compatibility,
It also plays an important role in chemical fields such as catalysis, medicine, coating, so obtained extensive research.Earth silicon material
Dimension, size, pattern (especially micro-/ nano scale) there is large effect to its performance, with its application field
It expands and the raising of performance requirement, the earth silicon material with unique morphology structure receives close attention.
So far, reported silicon dioxide structure includes spherical, rodlike, fibrous, flower-shaped, mushroom, chain etc.；But with
When this low dimensional material is catalyst or catalyst carrier, scantling is smaller to be will cause separation and recovery difficult (especially liquid is solid
Reaction), size is larger, the problems such as inner diffusing rate being caused slow again；In addition above structure material is easy to reunite, as rubber
The filler majority of material is poor with polymer compatibility, needs to carry out surface and is modified, is otherwise extremely difficult to ideal composite material
Performance.
Summary of the invention
It is an object of the present invention to for deficiency present in current techniques, provide a kind of to prepare three-dimensional ball chain structure dioxy
The method of SiClx.This method is on the basis of the synthetic system formed with ethyl orthosilicate and water-alcohol mixture, by the way that silane is added
Coupling agent KH570, by parameters such as modulation water alcohol ratio, dosage of surfactant, mixing speeds, having synthesized has 3 D stereo ball
The silica of chain structure, and realize controllable within the scope of material sphere size some scale.The titanium dioxide that the present invention synthesizes
Silicon materials, the material with three dimensional skeletal structure effectively can improve or solve the problems of the prior art, and sphere is big
It is small controllable in a certain range.
The technical solution of the present invention is as follows:
A method of three-dimensional ball chain structure silica is prepared, is included the following steps:
(1) dehydrated alcohol and distilled water are mixed, adds Surfactant CTAB, successively added under stirring condition after dissolution
Enter ethyl orthosilicate (TEOS) and ammonium hydroxide, be finally added dropwise to γ-methacryloxypropyl trimethoxy silane (KH570),
Obtain white suspension；
Wherein, volume ratio dehydrated alcohol: distilled water: ethyl orthosilicate: ammonium hydroxide: γ-methacryloxypropyl front three
Oxysilane=50-150:50-150:1-4:2-5:0.5-2.5；Every 50~150 milliliters of dehydrated alcohols add Surfactant CTAB
0.20-2.00g；
(2) white suspension obtained to step (1) reacts 1-6h at 25-50 DEG C under agitation, then will
Then product separation, washing, drying roast 5~8h at 450-700 DEG C and obtain final product, i.e. three-dimensional ball chain titanium dioxide
Silicon.
Speed of agitator in the step (1) and step (2) is 200-1000rpm.
Step (2) heating rate roasted at 450-700 DEG C is 1-5 DEG C/min.
Advantages of the present invention and beneficial effect achieved are:
1. process used in the present invention is simple, reaction condition is mild, controllability is strong；Ball chain shape silica is through height
After temperature roasting, it is still able to maintain good pattern, there is good thermal stability；Prepared silica surface exists big simultaneously
Silicone hydroxyl (the 5 IR Characterization result 3400cm of attached drawing of amount-1And 960cm-1Infrared peak at wave number is the characteristic absorption of silicone hydroxyl
Peak), for the later period, the material is provided conveniently in different field using modified, has very high potential using value.
2. ball chain shape earth silicon material prepared by the present invention has three-dimensional structure, (SEM being detailed in attached drawing 1-3 shines
Piece), using prepared material as catalyst or catalyst carrier, the interstructural extra space of ball chain is the expansion of reactant, product
It dissipates and convenience is provided, be conducive to the influence for eliminating interior diffusion；In addition the oversize of 3 D stereo is more advantageous to the separation of catalyst；
Material sphere scale is adjustable in a certain range, provides convenient and possible, example for its structural requirement for meeting different field application
Porous material such as inorganic template agent synthesis different pore size.
3. ball chain shape earth silicon material prepared by the present invention can be used directly without calcination process, at this time chain in material
Body portion contains a large amount of organic chain, can effectively improve its compatibility between polymer, improves its knot between polymer
With joint efforts, to assign composite material special function.
Detailed description of the invention
Attached drawing 1 is the scanning electron microscope (SEM) photograph of 1 gained three-dimensional ball chain silica sample of embodiment；Wherein, Fig. 1 a is gained
Scanning electron microscope (SEM) photograph before sample roasting；Fig. 1 b is the scanning electron microscope (SEM) photograph after the roasting of gained sample；
Attached drawing 2 is the scanning electron microscope (SEM) photograph of 2 gained three-dimensional ball chain silica sample of embodiment；
Attached drawing 3 is the scanning electron microscope (SEM) photograph of 3 gained three-dimensional ball chain silica sample of embodiment；
Attached drawing 4 is the XRD characterization result of 1 gained three-dimensional ball chain silica sample of embodiment；
Attached drawing 5 is the IR Characterization result of 1 gained three-dimensional ball chain silica sample of embodiment roasting front and back.
Specific embodiment
Below by examples illustrate the present invention, described embodiment is only further solved with to of the invention in detail
It releases and illustrates, but protection scope of the present invention is not limited to following embodiments, the skilled artisan is according to the present invention
The nonessential modifications and adaptations that content is made, still fall within protection scope of the present invention.
Embodiment 1:
75mL dehydrated alcohol is uniformly mixed with 125mL distilled water, 0.400g Surfactant CTAB is then added,
1.75mL ethyl orthosilicate is successively added dropwise under 400rpm stirring again, then used time 5min is added dropwise 2.5mL ammonium hydroxide with 3min, stirs
Solution switchs to milky after mixing 10min, and 0.75mL KH570 finally is added with 3min, continues after reaction 3h is stirred at room temperature, by sample
Product separation, washing, are dried overnight, are then warming up to 600 DEG C with the speed of 1 DEG C/min and roast 6h, can be prepared by three-dimensional ball chain
Shape structural silica dioxide.
Obtained product roasting front and back silica sphere is not any change, and illustrates there is good stability；It is obtained
The three-dimensional ball chain structure sample roasting front and back pattern of sample is as shown in Fig. 1 stereoscan photograph, sphere diameter~700nm；It is attached
Sample obtained by XRD characterization result shown in Fig. 4 is pure silicon dioxide material；Attached drawing 5 show the red of sample roasting front and back
Outer spectrogram, wherein 1086cm-1And 805cm-1Absorption peak at wave number illustrates to form a large amount of Si-O-Si skeleton structures in material；
1721cm-1There is new absorption peak in place, is the stretching vibration absworption peak of the C=O group in silane coupling agent KH570,
2927cm-1And 2854cm-1Locate appearance-CH3Antisymmetry and symmetrical stretching vibration absorption peak, illustrate in sample containing largely having
Machine functional group.
Embodiment 2:
65mL dehydrated alcohol is uniformly mixed with 125mL distilled water, 0.400g Surfactant CTAB is then added,
It is successively added dropwise to 1.75mL ethyl orthosilicate again under 400rpm stirring, used time 5min, then 3min is added dropwise to 2.5mL ammonium hydroxide, stirs
Solution switchs to milky after mixing half an hour, and 0.75mL KH570 finally is added with 3min, continues after reaction 3h is stirred at room temperature, by sample
Product separation, washing, are dried overnight, are warming up at 600 DEG C with the speed of 1 DEG C/min and roast 6h, can be prepared by three-dimensional ball chain knot
Structure silica.Roasting front and back silica sphere is unchanged, roasts the stereoscan photograph of sample as shown in Fig. 2, sphere is straight
Diameter~300nm.
Embodiment 3:
75mL dehydrated alcohol is uniformly mixed with 125mL distilled water, 0.400g Surfactant CTAB is then added,
1.75mL ethyl orthosilicate is sequentially added under 400rpm stirring, used time 5min, then 3min is added dropwise to 2.5mL ammonium hydroxide, stirring
Solution switchs to milky after 10min, and 1.75mL KH570 finally is added with 7min, continues after reaction 3h is stirred at room temperature, by sample
Separation, washing, are dried overnight, are warming up at 600 DEG C with the speed of 1 DEG C/min and roast 6h, can be prepared by three-dimensional ball chain structure
Silica.Roasting front and back silica sphere is unchanged, roasts the stereoscan photograph of sample as shown in figure 3, sphere diameter
~600nm.
Embodiment 4:
75mL dehydrated alcohol is uniformly mixed with 125mL distilled water, 1.200g Surfactant CTAB is then added,
3.5mL ethyl orthosilicate is sequentially added under 400rpm stirring, used time 10min, then 3min is added dropwise to 2.5mL ammonium hydroxide, stirring
Solution switchs to milky after half an hour, and 1.5mL KH570 finally is added with 6min, continues after reaction 5h is stirred at room temperature, by sample
Separation, washing, are dried overnight, are warming up at 500 DEG C with the speed of 5 DEG C/min and roast 6h, can be prepared by three-dimensional ball chain structure
Silica, roasting front and back silica sphere is unchanged, sphere diameter~300nm.
Embodiment 5:
75mL dehydrated alcohol is uniformly mixed with 125mL distilled water, 0.800g Surfactant CTAB is then added,
3.5mL ethyl orthosilicate is sequentially added under 800rpm stirring, used time 10min, then 3min is added dropwise to 2.5mL ammonium hydroxide, mixes half
Solution switchs to milky after hour, is eventually adding 1.5mL KH570, continues after reaction 5h is stirred at room temperature, by sample separation, washes
It washs, is dried overnight, be warming up at 500 DEG C with 5 DEG C/min degree speed and roast 6h, can be prepared by three-dimensional ball chain structure titanium dioxide
Silicon, roasting front and back silica sphere is unchanged, sphere diameter~200nm.
Embodiment 6:
75mL dehydrated alcohol is uniformly mixed with 125mL distilled water, 0.400g Surfactant CTAB is then added,
1.75mL ethyl orthosilicate is sequentially added under 400rpm stirring, used time 5min, then 6min is added dropwise to 5mL ammonium hydroxide, mixes 10min
Solution switchs to milky afterwards, is eventually adding 0.75mL KH570, continues after reaction 1h is stirred at room temperature, sample separation, washing are done
It is dry overnight, it is warming up at 500 DEG C with the speed of 1 DEG C/min and roasts 6h, can be prepared by three-dimensional ball chain structure silica, roasted
Front and back silica sphere is unchanged, sphere diameter~700nm.
In conclusion the sphere diameter for the ball chain shape structural silica dioxide that this method is reported can stir speed by modulation
The parameters such as degree, the alcohol water ratio in system and dosage of surfactant are controllable within the scope of 200-700nm.Improve mixing speed
Be conducive to dispersion of the ethyl orthosilicate in synthetic system, so the cream that the higher ethyl orthosilicate of mixing speed is formed in system
Liquid drop is also smaller, and last sphere obtained is also just smaller；The more surfactant the easier in ethyl orthosilicate droplet surface
Protective layer is formed, effectively prevents the polymerization of these droplet collisions from growing up, to be formed after guaranteeing hydrolysis compared with spherula particle；Alcohol water
Surface tension than increasing system reduces, and is formed by that emulsion droplet is bigger, the sphere diameter for hydrolyzing preparation is also bigger.
Unaccomplished matter of the present invention is well-known technique.
Claims (3)
1. a kind of method for preparing three-dimensional ball chain structure silica, it is characterized in that this method comprises the following steps:
(1) dehydrated alcohol and distilled water are mixed, adds Surfactant CTAB, is sequentially added just under stirring condition after dissolution
Silester (TEOS) and ammonium hydroxide are eventually adding γ-methacryloxypropyl trimethoxy silane (KH570), obtain white
Color suspension；
Wherein, volume ratio dehydrated alcohol: distilled water: ethyl orthosilicate: ammonium hydroxide: γ-methacryloxypropyl trimethoxy
Silane=50-150:50-150:1-4:2-5:0.5-2.5；Every 50 ~ 150 milliliters of dehydrated alcohols add Surfactant CTAB 0.20-
2.00 g；
(2) white suspension obtained to step (1) reacts 1-6 h at 25-50 DEG C under agitation, then by product
Separation, washing, drying then heat to 450-700 DEG C, and 5 ~ 8 h of roasting obtain final product, i.e. three-dimensional ball chain titanium dioxide
Silicon.
2. the method for preparing three-dimensional ball chain structure silica as described in claim 1, it is characterized in that the step (1)
It is 200-1000 rpm with the speed of agitator in step (2).
3. the method for preparing three-dimensional ball chain structure silica as described in claim 1, it is characterized in that the step (2)
The heating rate roasted at 450-700 DEG C is 1-5 DEG C/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910034648.3A CN109607552B (en) | 2019-01-15 | 2019-01-15 | Method for preparing silicon dioxide with three-dimensional ball chain structure |
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| CN201910034648.3A CN109607552B (en) | 2019-01-15 | 2019-01-15 | Method for preparing silicon dioxide with three-dimensional ball chain structure |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209389A (en) * | 2020-09-11 | 2021-01-12 | 江苏大学 | Preparation method of superfine nano silicon dioxide spheres |
| CN114373949A (en) * | 2020-10-15 | 2022-04-19 | 丰田自动车株式会社 | Porous carbon, catalyst carrier, and method for producing porous carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112209389A (en) * | 2020-09-11 | 2021-01-12 | 江苏大学 | Preparation method of superfine nano silicon dioxide spheres |
| CN114373949A (en) * | 2020-10-15 | 2022-04-19 | 丰田自动车株式会社 | Porous carbon, catalyst carrier, and method for producing porous carbon |
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