CN104211073A - Preparation method of monodisperse nano spherical silicon dioxide and nano silicon dioxide - Google Patents
Preparation method of monodisperse nano spherical silicon dioxide and nano silicon dioxide Download PDFInfo
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- CN104211073A CN104211073A CN201410483218.7A CN201410483218A CN104211073A CN 104211073 A CN104211073 A CN 104211073A CN 201410483218 A CN201410483218 A CN 201410483218A CN 104211073 A CN104211073 A CN 104211073A
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Abstract
The invention relates to a preparation method of monodisperse nano spherical silicon dioxide and a nano silicon dioxide. The method comprises the following steps: 1) dissolving lysine and octane in pure water, and stirring at 60 DEG C at the rate of 800 r/min for 10-30 minutes to obtain a solution A; 2) adding ethyl orthosilicate into the solution A, and stirring at 50-70 DEG C at the rate of 400 r/min for 15-25 hours; 3) heating to 100 DEG C, and stirring at the rate of 400 r/min for 15-25 hours to obtain a solution B; 4) adding aminopropyltriethoxy silane into the solution B, and heating for 1-5 hours until the solution B becomes milk white from the clear state and is accompanied with a colloid precipitate; and 5) centrifuging the precipitate at the rate of 3000 r/min for 3-10 minutes, adding pure water, carrying out ultrasonic cleaning until the precipitate is completely dispersed in water, recentrifuging, and drying to obtain the nano spherical silicon dioxide with different sizes. The method has the advantages of low cost, simple process, high yield, environmental protection and energy saving.
Description
Technical field
The invention belongs to Material Field, relate to a kind of preparation method and goods of silicon-dioxide, the preparation method particularly relating to a kind of dispersed nano preparing spherical SiO 2 and the nanometer spherical silicon-dioxide formed based on the method.
Background technology
Nano silicon is unbodied white powder, is a kind of nontoxic, tasteless, free of contamination non-metallic material.Its molecule becomes three-dimensional chain-like structure, and surface exists the hydroxyl of undersaturated outstanding key and different bond styles.Nano silicon is less than 100 nanometers due to size, thus has high-ratio surface effect, small-size effect, quantum size effect and macro quanta tunnel effect; And therefore produce the properties such as unusual mechanics, electricity, magnetics, optics, calorifics and chemistry.This type of nano material can be widely used in the fields such as polymer composite, electronic package material, plastics, coating, pigment, rubber, pottery, makeup, biological medicine, catalyzer.The performance of nano material and the particle size of material and pattern closely related, the performance such as many optics, electricity, magnetics of material only the size of material and pattern comparatively evenly time can macroscopically show.Therefore control size and the pattern of material granule, particularly to have particle little in preparation, and the single dispersing material of size uniform and pattern rule is the study hotspot in present material science.In recent years, along with deepening continuously of research, increasing result of study display, nano silicon ball has impayable good characteristic, particularly for biological medicine carrier and the field such as energy conversion, conduction.
At present, Many researchers has adopted multiple method to prepare nano-level sphere silicon-dioxide on a laboratory scale, but due to nano-silicon dioxide particle surface action can be strong, reaction process is complicated, and particle is easily reunited each other, still there is following problem:
1) be difficult to obtain diameter lower than 100 nanometers and the uniform monodisperse nano silicon dioxide spheroidal particle of pattern;
2) complex manufacturing, productive rate is low, and cost is high;
3) building-up process condition is harsh, and laboratory method cannot be amplified and be carried out large-scale industrial production.
Summary of the invention
In order to solve the above-mentioned technical problem existed in background technology, the invention provides a kind of with low cost, preparation process is simple, productive rate is high and the preparation method of the dispersed nano preparing spherical SiO 2 of environmental protection and energy saving and nano silicon.
Technical solution of the present invention is: the preparation method that the invention provides a kind of dispersed nano preparing spherical SiO 2, and its special character is: said method comprising the steps of:
1) octane of the Methionin of 1 ~ 0.01 mol/L and 1 ~ 0.01 mol/L is dissolved in pure water, under the condition of 60 DEG C and 800r/min, stirs 10-30 minute, form solution A;
2) tetraethoxy of 4.35 ~ 0.0435 mol/L is added to step 1) in the solution A that obtains, keep 50 DEG C-70 DEG C, and under the condition of 400r/min return stirring 15-25 hour;
3) temperature of reaction is promoted to 100 DEG C in the mode of 10 DEG C/min, return stirring 15-25 hour under the condition of 400r/min, forms solution B;
4) aminopropyl triethoxysilane of 0.9 ~ 0.01 mol/L is added step 3) in the solution B that obtains, heating 1-5 hour, solution B becomes oyster white from clarification, and with gelatinous precipitate;
5) by step 4) throw out that obtains carries out centrifugation 3-10 minute under the condition of 3000r/min, then pure water ultrasonic cleaning is added, until precipitation is scattered in water completely, and then under the condition of 3000r/min centrifugation 3-10 minute, the nanometer spherical silicon-dioxide of different size can be obtained after drying.
Above-mentioned steps 1) in be that the octane of the Methionin of 1 ~ 0.01 mol/L and 1 ~ 0.01 mol/L is dissolved in pure water, stir 20 minutes under the condition of 60 DEG C and 800r/min, form solution A.
Above-mentioned steps 2) be that the tetraethoxy of 4.35 ~ 0.0435 mol/L is added to step 1) in the solution A that obtains, keep 60 DEG C, and reflux stirs 20 hours under the condition of 400r/min.
Above-mentioned steps 3) be that temperature of reaction is promoted to 100 DEG C, return stirring 20 hours under the condition of 400r/min, forms solution B.
A kind of dispersed nano preparing spherical SiO 2 prepared based on the preparation method of dispersed nano preparing spherical SiO 2 as above.
The present invention with reported that at present compared with business-like preparation method, tool has the following advantages:
First, product yield is high (the method productive rate higher than 80%, and method similar with it (1.Yokoi, T., et al., Chemistry of Materials, 2009.21 (15): p.3719-3729.2.Yang, S.-M., et al., Nanomachining by Colloidal Lithography.Small, 2006.2 (4): p.458-475.) be only 10-20%);
The second, product is dispersed nano ball, pattern and size uniform, and particle is controlled in 10-100 nanometer, and diameter controlled (as 20,50,70,100 nanometers);
3rd, manufacturing condition is simple, and equipment requirements is low, can industrialization scale operation; Cost is low, and market competition advantage is obvious, and the market requirement is large, and commercialization is worth high;
4th, product performance stable (can preserve some months in the liquid phase and the dispersed spherical in shape that remains unchanged), have good specific surface effect, small-size effect, quantum size effect and macro quanta tunnel effect simultaneously.
Finally, reaction medium is pure water (the ratio <5% of the organic solvent such as octane), less pollution, temperature of reaction low (60-100 DEG C), energy-conserving and environment-protective.
Due to nano silicon ball not only good product performance prepared by the method, preparation method is simple, productive rate is high, and the cost of this preparation method is compared with congenic method, there is huge advantage, no matter this will be also for being scientific research or business development from now on, have the meaning of perspective, guidance quality and wide practicality.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the nano silicon spheroidal particle obtaining different size specification according to preparation method provided by the present invention;
Fig. 2 is the schematic flow sheet preparing nano silicon ball provided by the present invention.
Specific embodiments
Core of the present invention there is provided a kind of preparation method of monodisperse silica nanometer ball, the method is in the silica spheres preparation of below 100 nanometers, break away from traditional experiment room and prepare the following silica spheres of 100 nanometer, need accurately to control reaction conditions, productive rate is low, cannot the restriction such as scale operation, there is great breakthrough meaning.The inventive method is prepared and is kept the pattern of product even, and size is controlled, stability of characteristics, and specific surface area is large, has good surface effects, small-size effect, quantum size effect and macro quanta tunnel effect etc. simultaneously.
See Fig. 2, the invention provides the preparation method of the nano silicon spheroidal particle of a kind of simple, environmental protection and expense relative moderate, the method comprises the following steps:
1) octane of the Methionin of 1 ~ 0.01 mol/L and 1 ~ 0.01 mol/L is dissolved in pure water, at 60 DEG C, stirs (800r/min) 10-30 minute, preferably 20 minutes.
2) add in above-mentioned solution by the tetraethoxy of 4.35 ~ 0.0435 mol/L, keep 50 DEG C-70 DEG C, preferably 60 DEG C, reflux stirs (400r/min) 15-25 hour, preferably 20 hours.
3) temperature of reaction is promoted to 100 DEG C, return stirring (400r/min) 15-25 hour, preferably 20 hours.
4) aminopropyl triethoxysilane of 0.9 ~ 0.01 mol/L is added reaction soln, heat 1 hour, solution becomes oyster white from clarification, and with gelatinous precipitate.
5) throw out is carried out centrifugation (3000r/min) about 3 minutes, then pure water ultrasonic cleaning is added, until precipitation is scattered in water completely, and then centrifugation (3000r/min) about 3 minutes, the nanometer spherical silicon-dioxide (see Fig. 1) of different size (being directly 10-100nm) can be obtained after drying.
When Schwellenwert is got in all pharmaceutical chemicals meterings, the diameter of nanometer spherical silicon-dioxide is 10 ~ 15nm.Along with the increase that the pharmaceutical chemicals participating in reaction measures, the diameter of nanometer spherical silicon-dioxide also increases thereupon.
Below, will be described in detail to method provided by the present invention in conjunction with specific embodiments:
The synthesis step embodiment of nano silicon ball material
First the octane of the Methionin of 0.146 gram and 7.3 grams is dissolved in the pure water of 139 grams, at 60 DEG C, stirs (800r/min) 20 minutes.Again the tetraethoxy of 10.41 grams is added in above-mentioned solution, at 60 DEG C, return stirring (400r/min) 20 hours.Then temperature of reaction is promoted to 100 DEG C, return stirring (400r/min) 20 hours.Finally the aminopropyl triethoxysilane (concentration 99.99%) of 2 milliliters is added reaction soln, heat 1 hour, solution becomes oyster white from clarification, and with gelatinous precipitate.Throw out is carried out centrifugation (3000r/min) about 3 minutes, then pure water ultrasonic cleaning is added, until precipitation is scattered in water completely, and then centrifugation (3000r/min) about 3 minutes, the nanometer spherical silicon-dioxide that diameter is 25nm can be obtained after drying.
The preparation-obtained nanometer spherical earth silicon material of the present invention, has been applied to following several field at present:
1) biological medicine.Be less than the preparing spherical SiO 2 of 100 nanometers, be widely used in pharmaceutical carrier, because silicon-dioxide is harmless to human non-toxic, be not absorbed by the body, and in microcirculation in human body system, there is good flowing through property, be excellent drug carrier material, the research of current numerous anticancer aspect such as antitumor is all based on nano silicon spherical support materials.
2) energy conversion.Because nanometer spherical silicon-dioxide has good specific surface effect, small-size effect, quantum size effect and macro quanta tunnel effect, be also widely used in energy and material.Such as, solar energy optical-thermal converting system assembly etc.
3) nano-polishing agent.The main advantage of nanometer spherical silicon-dioxide shape rumbling compound is: precision controlling is high, size impact is little, and polishing is even, strengthens the corrosion resistance of polished surface, roughness reduces, and smooth finish, hard durable, notch sensitivity reduce, frictional coefficient declines, wearing and tearing reduce.Be mainly used in the sanding and polishing etc. of precision instrument parts at present.
Claims (5)
1. a preparation method for dispersed nano preparing spherical SiO 2, is characterized in that: said method comprising the steps of:
1) octane of the Methionin of 1 ~ 0.01 mol/L and 1 ~ 0.01 mol/L is dissolved in pure water, under the condition of 60 DEG C and 800r/min, stirs 10-30 minute, form solution A;
2) tetraethoxy of 4.35 ~ 0.0435 mol/L is added to step 1) in the solution A that obtains, keep 50 DEG C-70 DEG C, and under the condition of 400r/min return stirring 15-25 hour;
3) temperature of reaction is promoted to 100 DEG C in the mode of 10 DEG C/min, return stirring 15-25 hour under the condition of 400r/min, forms solution B;
4) aminopropyl triethoxysilane of 0.9 ~ 0.01 mol/L is added step 3) in the solution B that obtains, heating 1-5 hour, solution B becomes oyster white from clarification, and with gelatinous precipitate;
5) by step 4) throw out that obtains carries out centrifugation 3-10 minute under the condition of 3000r/min, then pure water ultrasonic cleaning is added, until precipitation is scattered in water completely, and then under the condition of 3000r/min centrifugation 3-10 minute, the nanometer spherical silicon-dioxide of different size can be obtained after drying.
2. the preparation method of dispersed nano preparing spherical SiO 2 according to claim 1, it is characterized in that: described step 1) in be that the octane of the Methionin of 1 ~ 0.01 mol/L and 1 ~ 0.01 mol/L is dissolved in pure water, stir 20 minutes under the condition of 60 DEG C and 800r/min, form solution A.
3. the preparation method of dispersed nano preparing spherical SiO 2 according to claim 2, it is characterized in that: described step 2) be that the tetraethoxy of 4.35 ~ 0.0435 mol/L is added to step 1) in the solution A that obtains, keep 60 DEG C, and reflux stirs 20 hours under the condition of 400r/min.
4. the preparation method of dispersed nano preparing spherical SiO 2 according to claim 3, is characterized in that: described step 3) be that temperature of reaction is promoted to 100 DEG C, return stirring 20 hours under the condition of 400r/min, forms solution B.
5. the dispersed nano preparing spherical SiO 2 prepared based on the preparation method of the dispersed nano preparing spherical SiO 2 as described in claim as arbitrary in claim 1-4.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340674A (en) * | 2022-08-17 | 2022-11-15 | 广东工业大学 | Silicone resin for rapid 3D printing and preparation method and application thereof |
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| CN1757598A (en) * | 2005-10-26 | 2006-04-12 | 太原理工大学 | Method for preparing super fine hydrophobic silicon dioxide |
| CN102430349A (en) * | 2011-12-22 | 2012-05-02 | 中国海洋大学 | Reverse osmosis composite membrane and preparation method thereof |
| CN103395794A (en) * | 2013-07-29 | 2013-11-20 | 扬州大学 | Preparation method of monodispersed silicon dioxide grains with uniform grain sizes |
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Patent Citations (3)
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| CN1757598A (en) * | 2005-10-26 | 2006-04-12 | 太原理工大学 | Method for preparing super fine hydrophobic silicon dioxide |
| CN102430349A (en) * | 2011-12-22 | 2012-05-02 | 中国海洋大学 | Reverse osmosis composite membrane and preparation method thereof |
| CN103395794A (en) * | 2013-07-29 | 2013-11-20 | 扬州大学 | Preparation method of monodispersed silicon dioxide grains with uniform grain sizes |
Non-Patent Citations (3)
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| NASER GHAREHBASH: "Modification of the surface of silica nanoparticles; studying its structure and thermal properties in order to strengthen it in preparing Nano composites", 《JOURNAL OF AMERICAN SCIENCE》, vol. 9, no. 4, 31 December 2013 (2013-12-31), pages 602 - 606 * |
| SEUNG-MAN YANG: "Nanomachining by Colloidal Lithography", 《COLLOIDAL LITHOGRAPHY》, vol. 2, no. 4, 31 December 2006 (2006-12-31), pages 458 - 475, XP055130082, DOI: doi:10.1002/smll.200500390 * |
| TOSHIYUKI YOKOI: ""Periodic Arrangement of Silica Nanospheres Assisted by Amino Acids", 《JOURNAL OF AMERICAN CHEMICAL SOCIETY》, vol. 128, no. 42, 3 October 2006 (2006-10-03), pages 13664 - 13665, XP002736861, DOI: doi:10.1021/JA065071Y * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340674A (en) * | 2022-08-17 | 2022-11-15 | 广东工业大学 | Silicone resin for rapid 3D printing and preparation method and application thereof |
| CN115340674B (en) * | 2022-08-17 | 2023-09-29 | 广东工业大学 | Silicon resin for rapid 3D printing and preparation method and application thereof |
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