CN102701226B - Preparation method of mono-dispersed silicon dioxide nanometer microspheres - Google Patents
Preparation method of mono-dispersed silicon dioxide nanometer microspheres Download PDFInfo
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Abstract
The invention relates to a preparation method of mono-dispersed silicon dioxide nanometer microspheres. The method comprises the following steps of: using sodium dodecyl benzene sulfonate (SDBS) as a template agent and a silicate compound as a silicon source, and controlling the diameter of the microspheres by regulating the adding amount of a dispersant to synthesize the silicon dioxide nanometer microspheres by one step so as to obtain the mono-dispersed silicon dioxide nanometer microspheres at relatively low temperature. The prepared silicon dioxide nanometer microspheres prepared by the method provided by the invention have a typical spherical structure, the diameter distribution is concentrated on 130-150nm more or less, problems such as an overlarge size distribution range and a poor dispersion degree of a past silicon dioxide synthesis process are resolved. The method provided by the invention is simple in process, easy to control, low in cost and suitable for large-scale industrial production.
Description
Technical field
The present invention relates to field of nanometer material technology, specifically, relate to a kind of preparation method of monodisperse silica Nano microsphere.
Background technology
Nano silicon is one of ultra tiny New Inorganic Materials of extremely important high-tech, because its particle diameter is very little, specific area is large, superficial attractive forces is strong, surface energy is large, and the aspects such as chemical purity is high, dispersive property good, thermal resistance, resistance have special performance, with its superior stability, reinforcing, thickening property and thixotropy, show unique characteristics in numerous subject and field, have the effect do not replaced.Nano silicon is commonly called as " ultra-fine white carbon black ", be widely used in every profession and trade as additive, catalyst carrier, petrochemical industry, decolorizer, delustering agent, rubber reinforcing filler, plastics filler, ink thickeners, the soft buffing compound of metal, insulation and thermal insulation filler, the various fields such as high-grade daily-use cosmetics filler and sprayed on material, medicine, environmental protection.
Nano silicon (SiO
2) because being easy to realize controlled synthesis, there are good optical transparence, chemical inertness, bio-compatibility etc., in the preparation of modern new material, nano composite material, take on key player.Nano silicon strengthens field as reinforcer at organosilicon and is used widely.Monodisperse superfine silicon dioxide microsphere fills swollen application widely in catalysis, pottery, chromatogram.Spherical nano-silicon dioxide, owing to having the superior function such as high dielectric, high heat-resisting, high moisture-proof, high filler loading capacity, low bulk, low-pressure, low impurity, low friction systems, can be applied to the numerous areas such as electronics, electrical equipment and chemical industry.
Prepare the existing a lot of report of nano silicon, in recent years, along with the development of nanometer technology, the design of functionalized nano composite and controlled synthesis become the study hotspot of Material Field.The nano material that preparation size is controlled, single dispersing degree is good is not only a kind of challenge technically, is also that the research of relation between the microstructure of nano material and macro property provides object simultaneously.The one proposed from Stober etc. is since in alcohol medium, ammonia hydrolysising positive acid ester (TEOS) synthesizes the method for monodisperse silica, and single dispersing is silica one of monodisperse system becoming most study.
At present, the research that silicon dioxide nanosphere is applied in shear thickening fluid, sequential 2 D nano-particles self assemble array, three-D photon crystal etc. achieves remarkable result.Due to necessarily require at these field nanometer grade silica microballoons high circularity, single dispersing, particle size controlled, can within the specific limits continuously and narrow ditribution, this proposes strict requirement to preparing nanometer grade silica microballoon.
CN 1608985A relates to a kind of method preparing single dispersing high specific surface area silica micropore microballoon.The method adopts alkylamine to make template and catalyst, promote that compound of silicate class is in the system take alcohols as solvent and water being decentralized photo, by the self assembling process of two stage hydrolytie polycondensation and template, the microporous silica microballoon particle diameter prepared is 600 ~ 1500m in 500 ~ 1500nm, BET method N2 adsorption specific area
2/ g, porosity is 40 ~ 60%, and pore volume is 0.43 ~ 0.60cm
3/ g, aperture is 1.1 ~ 1.9nm.
CN 102070148A discloses a kind of preparation method of monodisperse micron level spherical mesopore silicon oxide MCM-41 material and application relates to porous material preparation and separation of biopolymer field.Material preparation process is: in aqueous phase, add template CTAB and alkali source, obtain settled solution, add amorphous silicon oxide ball under room temperature, then introduce Morphological control agent aminoalkoxysilane (3-TSL 8330; Or 3-(2-amino-ethyl) propyl trimethoxy silicane), crystallization obtains former powder, and after filtration drying, at 550 DEG C, calcining 4 hours or acid ethanol solution extracting and washing obtain product of the present invention.Its specific area is 500 ~ 900m
2/ g, pore volume are 0.7 ~ 1.0cm
3/ g.
The Nano microsphere Size Distribution that the existing multiple method preparing silica nanosphere obtains not evenly or is easily reunited, and method therefor more complicated, require higher to operating condition, be not suitable for extension and produce.Numerous researcher seeks new method to make a breakthrough always for many years.
Summary of the invention
The object of the present invention is to provide a kind of size and morphology controllable, and the preparation method of the monodisperse silica Nano microsphere of narrow size distribution, the particle size range of gained silicon dioxide nanosphere is at 130 ~ 150nm.
Above-mentioned purpose is achieved by the following technical solution: do template with neopelex (SDBS), compound of silicate class does silicon source, one-step synthesis silicon dioxide microsphere, thus obtain monodispersed silicon dioxide nanosphere under relatively low temperature conditions.
In order to achieve the above object, the present invention is achieved through the following technical solutions:
A preparation method for monodisperse silica Nano microsphere, comprises the following steps:
(1) in SDBS solution, add dispersant, fully mix; Described SDBS solution concentration is 0.0015 ~ 0.0030g/ml;
(2), under alkali condition, in the solution that step (1) obtains, compound of silicate class is added, abundant hybrid reaction;
(3) monodisperse silica Nano microsphere is namely obtained by after the product cleaning of step (2), drying.
SDBS generates alkyl sulfonic acid by linear alkylbenzene (LAB) (LAB) sulfur trioxide or oleum sulfonation, then neutralization is made.The preferred 0.0021g/ml of SDBS solution concentration of the present invention.
Step of the present invention (1), (2) make solution fully mix preferably by ultrasonic or magnetic agitation mode.Other modes that solution system can be made to mix that those skilled in the art can be known all can be used for implementing the present invention, and such as standing a period of time or common agitating mode etc. can make solution system of the present invention mix.
Step of the present invention (1) stirs at least 20min at 50 ~ 80 DEG C of lower magnetic forces solution is fully mixed; Whipping temp can select 50.1 DEG C, 57 DEG C, 60.05 DEG C, 68 DEG C, 74.98 DEG C, 79.9 DEG C etc., preferably 60 ~ 75 DEG C, preferably 70 DEG C further; Mixing time can select 20.2min, 27min, 30.1min, 42min, 48min, 68min, 79.7min, 100min etc., preferably 30 ~ 80min, further preferred 45min.
Dispersant is the auxiliary agent that can improve and improve solid or liquid material dispersive property.During solid dye grinding, add dispersant, contribute to particle and pulverize and stop broken particle aggregation and keep dispersion stable.Water-fast oil-based liquid, under high shear force stirs, dispersibles into very little liquid pearl, after stopping stirring, and very fast layering under the effect of interfacial tension, and stir after adding dispersant, then can form stable emulsion.Its Main Function is the interfacial tension reducing liquid-between liquid and solid-liquid.Thus dispersant is also surfactant.Kind has anionic, cationic, nonionic, amphoteric and polymer electrolyte.The effect of dispersant uses wetting dispersing agent to reduce time required for dispersion process and energy, the stable pigment dispersion disperseed, modified pigment particle surface properties, the motility of adjustment pigment particles, is embodied in the following aspects: shorten jitter time, improve gloss, improve tinting strength, tinting power and covering power, improve color developing and toning property, prevent floating, prevent flocculation, prevent sedimentation.Dispersant of the present invention is selected from the mixture with a kind of in water soluble surfactant active or at least two kinds, preferred lauryl mercaptan, n-amyl alcohol, PVP further, other dispersants that SDBS powder can be enable better to be scattered in solution all can be used for the present invention.Lauryl mercaptan is colourless, water white or weak yellow liquid, slightly smell.Main application is the polymerization regulator of synthetic rubber, synthetic fibers, synthetic resin; Also for the production of PVC stabilizer, medicine, pesticide, bactericide, detergent etc.Preferred 96:0.01 ~ 0.05 of volume ratio of SDBS solution of the present invention and dispersant, such as 96:0.011,96:0.019,96:0.025,96:0.032,96:0.047,96:0.0498 equal proportion, further preferred 96:0.03.In SDBS solution, add dispersant can make SDBS powder disperse better, avoids reuniting, and is conducive to forming good dispersion, the silicon dioxide nanosphere that particle is homogeneous.
Step of the present invention (2) by adding alkaline solution to reach alkali condition in step (1) solution, and object is that the hydrolysis of compound of silicate class is carried out smoothly under alkaline environment; The NaOH solution that alkali condition of the present invention preferably adds 0.3 ~ 1.5ml 2mol/L realizes, and preferably adds the NaOH solution of 0.7ml2mol/L further.The present invention also can manufacture alkaline environment by adding other alkaline solutions, such as calcium hydroxide/NaOH/barium hydroxide etc., the aqueous solution of strong base-weak acid salt, such as sodium carbonate and sodium acid carbonate, and ammoniacal liquor also can be used for implementing the present invention.The concentration of alkaline solution and addition can be determined according to the experience of technical staff, and solution system can be made to realize alkaline environment.
Compound of silicate class of the present invention is selected from the mixture of a kind of in methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate or at least two kinds, such as ethyl orthosilicate and/or positive silicic acid propyl ester, methyl silicate, the combination of any compound of silicate class such as butyl silicate/ethyl orthosilicate all can be used as silicon source of the present invention, and other silicon sources that those skilled in the art can select according to common practise or personal experience all can be used for the present invention.The volume ratio of described SDBS solution and compound of silicate class is 96:0.8 ~ 2.3, such as 96:0.81,96:1,96:1.22,96:1.49,96:1.98,96:2.1,96:2.29 etc., preferred 96:1.2 ~ 2, further preferred 96:1.5.
Step of the present invention (2) stirs at least 1.2h at 50 ~ 85 DEG C of condition lower magnetic forces to make the abundant hybrid reaction of solution; Whipping temp can select 50.1 DEG C, 57 DEG C, 60.12 DEG C, 68 DEG C, 78 DEG C, 79.99 DEG C, 84.95 DEG C etc., preferably 60 ~ 80 DEG C, preferably 65 DEG C further; Mixing time can select 1.22h, 1.5h, 1.81h, 2.05h, 3.8h, 4.6h, 4.97h, 6h, 8.3h, 10h etc., preferably 1.8 ~ 5h, further preferred 2h.
Step of the present invention (3) by after the products in water of step (2) or ethanol purge under 50 ~ 120 DEG C of conditions dry 3 ~ 10h; Baking temperature can select 50.04 DEG C, 56 DEG C, 60.2 DEG C, 75 DEG C, 83 DEG C, 97 DEG C, 99.78 DEG C, 107.6 DEG C, 114 DEG C, 119.89 DEG C etc., preferably 60 ~ 100 DEG C, preferably 80 DEG C further; Drying time can select 3.01h, 5.2h, 6h, 7.3h, 7.99h, 8.9h, 9.89h etc., preferably 5 ~ 8h, further preferred 6h.
Compared with prior art scheme, the present invention has following beneficial effect:
The nano SiO 2 particle that the present invention obtains is homogeneous spherical, and very well dispersed, Size Distribution is very narrow.Not only energy consumption is low for the present invention's one-step synthesis used, and product purity is high, can also be controlled by the addition of dispersant to particle size.The method that the present invention prepares monodisperse silica nanosphere is simple, is easy to apply, and solvent for use is inexpensive, be easy to get, safety.
Accompanying drawing explanation
Accompanying drawing 1 is the scanned picture of the monodisperse silica Nano microsphere structure microscopic appearance figure of embodiment 1;
Accompanying drawing 2 is the transmission pattern picture of the monodisperse silica Nano microsphere structure of embodiment 3.
The present invention is described in more detail below.But following example is only simple and easy example of the present invention, does not represent or limits the scope of the present invention, and interest field of the present invention is as the criterion with claims.
Detailed description of the invention
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1:
0.2g neopelex (SDBS) is dissolved in 96ml distilled water, adds NaOH (NaOH) solution and the 0.01ml lauryl mercaptan (C of 0.7ml 2mol/L
12-SH) at the temperature of 80 DEG C, magnetic agitation 30 minutes, 1.5ml ethyl orthosilicate (TEOS) is added fast after stirring completes, continue to stir 2h at the temperature of 80 DEG C, the product distilled water stirred is cleaned collected by suction, by product dry 8h at the temperature of 60 DEG C, obtain monodisperse silica Nano microsphere structure.Carry out electron-microscope scanning to observe its microscopic appearance to the present embodiment product, result as shown in Figure 1, can find out that the size uniformity of all products, decentralization are high.
Embodiment 2:
0.144g neopelex (SDBS) is dissolved in 96ml distilled water, add NaOH (NaOH) solution of 0.3ml 2mol/L and 0.03ml n-amyl alcohol at the temperature of 50 DEG C, magnetic agitation 80 minutes, 0.8ml ethyl orthosilicate (TEOS) is added fast after stirring completes, continue to stir 5h at the temperature of 60 DEG C, the product distilled water stirred is cleaned collected by suction, by product dry 5h at the temperature of 100 DEG C, obtain monodisperse silica Nano microsphere structure.
Embodiment 3:
0.2g neopelex (SDBS) is dissolved in 96ml distilled water, adds NaOH (NaOH) solution and the 0.01ml lauryl mercaptan (C of 0.7ml 2mol/L
12-SH), at the temperature of 70 DEG C, magnetic agitation 30 minutes, has stirred and has added 1.5ml ethyl orthosilicate (TEOS) fast afterwards, continued to stir 2h at the temperature of 70 DEG C; By the product washing collected by suction stirred, by product dry 8h at the temperature of 60 DEG C, obtain monodisperse silica Nano microsphere structure.Carry out transmission electron microscope analysis to observe its transmission pattern to the present embodiment product, as shown in Figure 2, can find out that product is solid construction, granularity is at about 130 ~ 150nm for result.
Embodiment 4:
0.289g neopelex (SDBS) is dissolved in 96ml distilled water, adds NaOH (NaOH) solution and the 0.05ml lauryl mercaptan (C of 1.5ml 2mol/L
12-SH), at the temperature of 60 DEG C, magnetic agitation 45 minutes, 2.3ml ethyl orthosilicate (TEOS) is added fast after stirring completes, continue to stir 1.2h at the temperature of 65 DEG C, by the product ethanol purge collected by suction stirred, by product dry 10h at the temperature of 50 DEG C, obtain monodisperse silica Nano microsphere structure.
Embodiment 5:
0.230g neopelex (SDBS) is dissolved in 96ml distilled water, add sodium carbonate liquor and the 0.02ml n-amyl alcohol of 2.5ml 1mol/L, at the temperature of 75 DEG C, magnetic agitation 20 minutes, add 2ml ethyl orthosilicate and methyl silicate fast after stirring completes, continue to stir 1.2h at the temperature of 85 DEG C, by the product ethanol purge collected by suction stirred, by product dry 3h at the temperature of 120 DEG C, obtain monodisperse silica Nano microsphere structure.
Embodiment 6:
0.185g neopelex (SDBS) is dissolved in 96ml distilled water, add ammonia spirit and the 0.03ml PVP of 0.7ml 2mol/L, at the temperature of 80 DEG C, magnetic agitation 100 minutes, add the positive silicic acid propyl ester of 1.2ml after stirring completes fast, continue to stir 2h at the temperature of 50 DEG C, the product distilled water stirred is cleaned collected by suction, by product dry 6h at the temperature of 80 DEG C, obtain monodisperse silica Nano microsphere structure.
As can be seen from accompanying drawing, the nano SiO 2 particle obtained by preparation method of the present invention is homogeneous spherical, and particle size is controlled.Dispersed very well, can narrow size distribution continuously within the specific limits.The particle size range of gained silicon dioxide nanosphere is at 130 ~ 150nm.
Applicant states, the present invention illustrates preparation method of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned preparation process, does not namely mean that the present invention must rely on above-mentioned preparation process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (25)
1. a preparation method for monodisperse silica Nano microsphere, is characterized in that, comprises the following steps:
(1) in SDBS solution, add dispersant, stir at least 20min at 50 ~ 80 DEG C of lower magnetic forces and solution is fully mixed; Described SDBS solution concentration is 0.0015 ~ 0.0030g/mL; The volume ratio of described SDBS solution and dispersant is 96:0.01 ~ 0.05;
(2) under alkali condition, in the solution that step (1) obtains, add compound of silicate class, stir at least 1.2h at 50 ~ 85 DEG C of condition lower magnetic forces and make the abundant hybrid reaction of solution;
(3) monodisperse silica Nano microsphere is namely obtained by after the product cleaning of step (2), drying.
2. the method for claim 1, is characterized in that, step (1), (2) make solution fully mix by magnetic agitation mode.
3. method as claimed in claim 1 or 2, it is characterized in that, described SDBS solution concentration is 0.0021g/mL.
4. method as claimed in claim 1 or 2, it is characterized in that, step (1) whipping temp is 60 ~ 75 DEG C.
5. method as claimed in claim 4, it is characterized in that, step (1) whipping temp is 70 DEG C.
6. method as claimed in claim 1 or 2, it is characterized in that, step (1) mixing time is 30 ~ 80min.
7. method as claimed in claim 6, it is characterized in that, step (1) mixing time is 45min.
8. method as claimed in claim 1 or 2, is characterized in that, described dispersant is selected from the mixture with a kind of in water soluble surfactant active or at least two kinds.
9. method as claimed in claim 8, it is characterized in that, described dispersant is lauryl mercaptan, n-amyl alcohol or PVP.
10. method as claimed in claim 1 or 2, it is characterized in that, the volume ratio of described SDBS solution and dispersant is 96:0.03.
11. methods as claimed in claim 1 or 2, is characterized in that, step (2) by adding alkaline solution to reach alkali condition in step (1) solution.
12. methods as claimed in claim 11, it is characterized in that, step (2) adds the NaOH solution of 0.3 ~ 1.5mL 2mol/L.
13. methods as claimed in claim 12, it is characterized in that, step (2) adds the NaOH solution of 0.7mL 2mol/L.
14. methods as claimed in claim 1 or 2, is characterized in that, described compound of silicate class is selected from the mixture of a kind of in methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate or at least two kinds; The volume ratio of described SDBS solution and compound of silicate class is 96:0.8 ~ 2.3.
15. methods as claimed in claim 14, is characterized in that, the volume ratio of described SDBS solution and compound of silicate class is 96:1.2 ~ 2.
16. methods as claimed in claim 15, is characterized in that, the volume ratio of described SDBS solution and compound of silicate class is 96:1.5.
17. methods as claimed in claim 1 or 2, it is characterized in that, step (2) whipping temp is 60 ~ 80 DEG C.
18. methods as claimed in claim 17, it is characterized in that, step (2) whipping temp is 65 DEG C.
19. methods as claimed in claim 1 or 2, it is characterized in that, step (2) mixing time is 1.8 ~ 5h.
20. methods as claimed in claim 19, it is characterized in that, step (2) mixing time is 2h.
21. methods as claimed in claim 1 or 2, is characterized in that, step (3) by after the products in water of step (2) or ethanol purge under 50 ~ 120 DEG C of conditions dry 3 ~ 10h.
22. methods as claimed in claim 21, it is characterized in that, step (3) baking temperature is 60 ~ 100 DEG C.
23. methods as claimed in claim 22, it is characterized in that, step (3) baking temperature is 80 DEG C.
24. methods as claimed in claim 21, it is characterized in that, step (3) drying time is 5 ~ 8h.
25. methods as claimed in claim 24, it is characterized in that, step (3) drying time is 6h.
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| CN107140650B (en) * | 2017-04-07 | 2021-04-20 | 河南大学 | Silicon dioxide nano surfactant and preparation method thereof |
| CN108892144B (en) * | 2018-06-22 | 2021-09-28 | 南京亘闪生物科技有限公司 | Preparation method of functionalized porous particle size monodisperse silicon dioxide spherical material |
| CN109574023A (en) * | 2018-12-26 | 2019-04-05 | 江苏德鑫新材料科技有限公司 | The technique that one-step method prepares preparing spherical SiO 2 |
| CN110780361B (en) * | 2019-11-29 | 2021-08-17 | 大连理工大学 | Double-layer photonic crystal optical switch thin film device and preparation method thereof |
| CN112226221B (en) * | 2020-10-19 | 2022-03-01 | 河南大学 | Nano silicon dioxide oil displacement agent and preparation method and application thereof |
| CN113023736B (en) * | 2021-04-01 | 2021-11-19 | 广州市飞雪材料科技有限公司 | Preparation method of silicon dioxide for high-oil-absorption low-viscosity toothpaste |
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| CN101857233A (en) * | 2010-06-03 | 2010-10-13 | 中国药科大学 | Method for synthesizing mesoporous silicon dioxide microsphere through regulating and controlling of anionic surface active agent |
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