CN102249245B - Preparation method of single-hole silicon dioxide hollow microsphere - Google Patents
Preparation method of single-hole silicon dioxide hollow microsphere Download PDFInfo
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- CN102249245B CN102249245B CN 201110107495 CN201110107495A CN102249245B CN 102249245 B CN102249245 B CN 102249245B CN 201110107495 CN201110107495 CN 201110107495 CN 201110107495 A CN201110107495 A CN 201110107495A CN 102249245 B CN102249245 B CN 102249245B
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Abstract
The invention discloses a preparation method of a single-hole silicon dioxide hollow microsphere, which comprises the steps of dissolving hydrophobic organic polymer in tetrahydrofuran to prepare the solution of tetrahydrofuran with the concentration thereof 0.2 g/L to 10. 0 g/L; mixing the solution with silicon dioxide precursor compounds, wherein the mass ratio of hydrophobic organic polymer to silicon dioxide precursor compounds is 1%-10%; injecting the mixed solution into water, wherein the volume ratio of the solution to water is 5%-50%; adding ammonia water to be taken as a catalyst for reacting for 6-24 hours to obtain a polymer-silicon dioxide composite microsphere; and separating, washing and drying the composite microsphere, and removing the polymer to finally obtain the needed single-hole silicon dioxide hollow microsphere. The hollow microsphere can be used for embedding and transporting macromolecules and nano-particles, thus having wide application prospect in biomedical fields such as targeted medicines, biomacromolecule carriers and the like.
Description
Technical field
The present invention relates to a kind of inorganic hollow microballoon and preparation method thereof, specifically is a kind of preparation method of single hole silicon-dioxide hollow microsphere.
Background technology
Hollow microsphere is meant that one type of size arrives micron dimension in nanometer, has the spherical shell type material of internal cavities.Silicon-dioxide is a kind of widely used inorganic shell layer material, has excellent biological compatibility, acid resistance, and easily through advantages such as Silanization reaction introducing various active groups.The silicon-dioxide hollow microsphere can be used as a kind of carrier, and the embedding and controlled that is used for medicine or bioactive molecules transports and discharges, and is with a wide range of applications in fields such as bio-science and medical diagnosiss.
In order to improve the mass transport efficient of material turnover hollow microsphere, need on shell wall, make up pore structure usually.At present, shell wall has micropore (less than 2nm), mesoporous (2～20nm), the hollow microsphere of macropore (greater than 20nm) structure has all had bibliographical information.Micropore and mesoporous hollow microsphere are applicable to micromolecular support and discharge, and for macromole, and like the supporting and discharge of albumen, polymkeric substance and nano particle, then the macropore hollow microsphere is more suitable for.According to hole number what, the macropore hollow microsphere can be divided into two types: large through-hole hollow microsphere and single hole hollow microsphere.The large through-hole hollow microsphere is meant to have a plurality of macropores on the shell wall, and microballoon has one type of microballoon of similar cage structure.This cage structure helps the turnover of macromolecular substance, but when shell wall was thin, because the existence of a plurality of macropores, shell wall was broken easily, and the microballoon physical strength is little.Big single hole hollow microsphere is meant one type of hollow microsphere that a macropore is only arranged on shell wall.This constitutional features has guaranteed that macromole turnover hollow microsphere has very high mass transport efficient, and in addition, under identical wall thickness condition, this texture ratio large through-hole hollow microsphere has better mechanical strength.Can predict, the silicon-dioxide hollow microsphere that this type has the single hole shell wall can be used as a kind of solid support material, is used for supporting and controlled release of biomacromolecule, will in biomedical sector, be able to use.
So far, the preparation of single hole silicon-dioxide hollow microsphere only has two pieces of bibliographical informations.(Small 2009,5,324-328) adopt emulsion method to prepare the ultra paramagnetic Fe of embedding in the shell wall for people such as Hyun Chung
3O
4The single hole silicon-dioxide hollow microsphere of nanoparticle and fluorescence quantum.With hydrophobic Fe
3O
4Nanoparticle and fluorescence quantum are scattered in the chloroform; Then with cetyl trimethylammonium bromide (CTAB) aqueous solution; 60 ℃ were heated 10 minutes; Add silica precursor tetraethoxy (TEOS) and catalyst n aOH again, can obtain single hole silicon-dioxide hollow microsphere after reaction for some time.People such as Hyun Chung think that following process has been passed through in the formation of this structure: under the stabilization of CTAB, chloroform and aqueous solution have formed the W/O emulsion.Under hydrophilic catalyst action, TEOS forms silica shell at emulsion water-oil interface hydrolytie polycondensation.Along with the carrying out of reaction, TEOS constantly in silica shell infiltration make shell constantly thicken, and chloroform also constantly evaporation leave and at the inner cavity that forms of emulsion.In initial reaction stage, the silica shell that TEOS hydrolysis and polycondensation form has very low cross-linking density, is difficult to tolerate ambient pressure, therefore, along with the evaporation of organic solvent, breaks and the single hole that forms in the thinnest part bending of silica shell.Emulsion method prepares the single hole hollow microsphere, often is easy to generate the solid particle of a large amount of non-hollows, and from the TEM photo that document provides, can find, the shared microballoon ratio of the cavity part of this microballoon is very little.If as the supported carrier functional materials, do not utilize the acquisition high loadings with this microballoon.(Langmuir 2007,23,1107-1113) through water-ethanol ratio and TEOS add-on in control water-ethanol-ammoniacal liquor-TEOS-CTAB system, obtained the single hole hollow silica microsphere for people such as Limin Qi.But the microballoon size that this method obtains is evenly (5～25 μ m) very greatly and inadequately.
Research contents
The objective of the invention is to the deficiency to prior art, a kind of preparation method of single hole silicon-dioxide hollow microsphere is provided, silicon-dioxide hollow microsphere provided by the present invention has unique eccentric cavity structure.
The object of the invention is realized through following technical scheme:
A kind of preparation method of single hole silicon-dioxide hollow microsphere comprises the steps: at first hydrophobic organic polymer to be dissolved in the THF, is made into the tetrahydrofuran solution that concentration is the hydrophobic organic polymer of 0.2g/L～10.0g/L; This solution is mixed with the silicon-dioxide precursor compound, the mass ratio of wherein said hydrophobic organic polymer and silicon-dioxide precursor compound is 1%～10% again, and above-mentioned mixing solutions is injected water; The volume ratio of this solution and water is 5%～50%; Add ammoniacal liquor again and make catalyzer, reacted 6～24 hours, obtain the polymer-silica complex microsphere; Above-mentioned complex microsphere is separated; Washing, drying is removed polymkeric substance and can be obtained required single hole silicon-dioxide hollow microsphere.
Also be added with acetonitrile, acetone, methyl alcohol or ethanol in the tetrahydrofuran solution of said hydrophobic organic polymer.
Said hydrophobic organic polymer is PS, methacrylic ester styrol copolymer, dialkyl maleate styrol copolymer or MBS.
The mass percent of said ammoniacal liquor is 25%.
Said silicon-dioxide precursor compound is tetramethoxy-silicane or tetraethoxysilane.
Compared with prior art, the present invention has following advantage and beneficial effect:
(1) but have the cavity and the big single hole of load function material.The cavity of hollow microsphere can load macromole, and biological example molecule or polymer also can be used for the load function nanoparticle, and big single hole helps macromole or nanoparticle turnover microballoon cavity.Handle in conjunction with follow-up sealing of hole, can realize material target controlledly transport and discharge.
(2) hollow microsphere of the present invention is easy to introduce reactive group through Silanization reaction; Be convenient to further application; In addition compared with prior art; The single hole size of single hole silicon-dioxide hollow microsphere size provided by the present invention, cavity size and shell is homogeneous and controllable in very large range, and the preparation method that the present invention adopted is simple, efficient, cost is low.
(3) pass through in the tetrahydrofuran solution of the present invention to add acetonitrile, acetone, methyl alcohol or ethanol, can effectively control the microsphere particle size of silicon-dioxide, and improve the particulate dimensional homogeneity.
(4) stability is good.Silicon-dioxide has good chemical stability.For reduced size, for example, in solution, also has good dispersion stabilization less than the silicon-dioxide hollow microsphere of 200nm.
Description of drawings
Fig. 1 is the stereoscan photograph of the prepared single hole silicon-dioxide hollow microsphere of embodiment 1.
Fig. 2 is the transmission electron microscope photo of the prepared single hole silicon-dioxide hollow microsphere of embodiment 1.
Embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiment of the present invention is not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.
Embodiment 1:
Get vinylbenzene-Sipacril 2739OF that 4mL concentration is 0.625g/L/tetrahydrofuran solution, this solution mixes with 4mL ethanol and 0.1mL tetraethoxysilane, then this mixing solutions is injected 24mL water fast; Add mass percent again and be 25% ammoniacal liquor 0.5mL, mix standing and reacting 24h; Obtain complex microsphere, with this complex microsphere spinning, and with after the washing with alcohol 3 times; 80 ℃ of oven dry; Put into retort furnace then,, can obtain single hole silicon-dioxide hollow microsphere in 500 ℃ of calcinings 4 hours.The stereoscan photograph of this microballoon is as shown in Figure 1, and transmission electron microscope photo is as shown in Figure 2.The inner unique eccentric cavity structure of visible silicon-dioxide hollow microsphere from electromicroscopic photograph; And the microballoon size range is 100nm～300nm; Median size is 180nm, and its internal cavities is of a size of 60nm～150nm, and the single hole on the silicon-dioxide wall is of a size of 20nm～70nm.
Embodiment 2:
Get the organic solution that 4mL concentration is MBS/THF of 1.5g/L, this organic solution is mixed with the 0.1mL tetraethoxysilane, then this mixing solutions is injected 80mL water fast; Add mass percent again and be 25% ammoniacal liquor 2.0mL, mix standing and reacting 24h; Obtain complex microsphere, with this complex microsphere spinning, and with washing with alcohol 3 times; 80 ℃ of oven dry; Put into retort furnace then,, can obtain single hole silicon-dioxide hollow microsphere in 500 ℃ of calcinings 4 hours.This microballoon size range is 2 μ m～30 μ m, and median size is 25.0 μ m, and its internal cavities is of a size of 1 μ m～10 μ m, and the single hole size range on the silicon-dioxide wall is 0.5 μ m～5 μ m.
Embodiment 3:
Get the organic solution that 4mL concentration is PS/THF of 2.0g/L, this organic solution is mixed with 4mL acetonitrile and 0.1mL tetraethoxysilane, then this mixing solutions is injected 24mL water fast; Add mass percent again and be 25% ammoniacal liquor 0.5mL, mix standing and reacting 12h; Obtain complex microsphere, with this complex microsphere spinning, and with washing with alcohol 3 times; 80 ℃ of oven dry; Put into retort furnace then,, obtain single hole silicon-dioxide hollow microsphere at last in 500 ℃ of calcinings 4 hours.This microballoon size range is 100nm～250nm, and median size is 150nm, and its internal cavities is of a size of 50nm～150nm, and the single hole size range on the silicon-dioxide wall is 20nm～85nm.
Embodiment 4:
Get the organic solution of vinylbenzene-Sipacril 2739OF that 4mL concentration is 0.2g/L/THF, this organic solution is mixed with 4mL acetone and 0.05mL tetraethoxysilane, then this mixing solutions is injected 18mL water fast; Add mass percent again and be 25% ammoniacal liquor 0.5mL, mix standing and reacting 6h; Obtain complex microsphere, with this complex microsphere spinning, and with washing with alcohol 3 times; 80 ℃ of oven dry; Put into retort furnace then,, obtain single hole silicon-dioxide hollow microsphere at last in 500 ℃ of calcinings 4 hours.This microballoon size range is 150nm～280nm, and median size is 226nm, and its internal cavities is of a size of 60nm～140nm, and the single hole size range on the silicon-dioxide wall is 50～120nm.
Embodiment 5:
Getting 4mL concentration is the organic solution of dialkyl maleate styrol copolymer/THF of 0.5g/L; This organic solution is mixed with 4mL methyl alcohol and 0.2mL tetramethoxy-silicane; Then this mixing solutions is injected 30mL water fast; Add mass percent again and be 25% ammoniacal liquor 0.2mL, mix.Standing and reacting 18h obtains complex microsphere, with this complex microsphere spinning, and with washing with alcohol 3 times, 80 ℃ of oven dry, puts into retort furnace then, in 500 ℃ of calcinings 4 hours, obtains single hole silicon-dioxide hollow microsphere at last.This microballoon size range is 40nm～80nm, and median size is 50nm, and its internal cavities is of a size of 20nm～50nm, and the single hole size range on the silicon-dioxide wall is 20～30nm.
Embodiment 6:
Get the organic solution of vinylbenzene-Sipacril 2739OF that 4mL concentration is 5.0g/L/THF; This organic solution is mixed with 4mL ethanol and 0.2mL tetramethoxy-silicane; Then this mixing solutions is injected 8mL water fast, add 25% ammoniacal liquor 0.5mL again, mix.Standing and reacting 24h obtains complex microsphere, with this complex microsphere spinning, and with washing with alcohol 3 times, 80 ℃ of oven dry, puts into retort furnace then, in 500 ℃ of calcinings 4 hours, obtains single hole silicon-dioxide hollow microsphere at last.This microballoon size range is 0.5 μ m～5 μ m, and median size is 2 μ m, and its internal cavities is of a size of 0.3 μ m～3 μ m, and the single hole size range on the silicon-dioxide wall is 100nm～500nm.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. the preparation method of a single hole silicon-dioxide hollow microsphere is characterized in that, comprises the steps: at first hydrophobic organic polymer to be dissolved in the THF; Be made into the tetrahydrofuran solution that concentration is the hydrophobic organic polymer of 0.2g/L～10.0g/L, this solution mixed with the silicon-dioxide precursor compound again, the mass ratio of wherein said hydrophobic organic polymer and silicon-dioxide precursor compound is 1%～10%; Above-mentioned mixing solutions is injected water, and the volume ratio of this solution and water is 5%～50%, adds ammoniacal liquor again and makees catalyzer; Reacted 6～24 hours; Obtain the polymer-silica complex microsphere, above-mentioned complex microsphere is separated, washing; Drying is removed polymkeric substance and can be obtained required single hole silicon-dioxide hollow microsphere.
2. preparation method according to claim 1 is characterized in that, also is added with acetonitrile, acetone, methyl alcohol or ethanol in the tetrahydrofuran solution of said hydrophobic organic polymer.
3. preparation method according to claim 2; It is characterized in that said hydrophobic organic polymer is PS, methacrylic ester styrol copolymer, dialkyl maleate styrol copolymer or MBS.
4. preparation method according to claim 3 is characterized in that, the mass percent of said ammoniacal liquor is 25%.
5. preparation method according to claim 4 is characterized in that, said silicon-dioxide precursor compound is tetramethoxy-silicane or tetraethoxysilane.
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| CN102923721B (en) * | 2012-11-20 | 2014-06-11 | 黑龙江大学 | Preparation method of monodisperse microspheres with hollow silica core/mesoporous silica shell structures |
| CN103559973B (en) * | 2013-10-30 | 2016-07-27 | 华南理工大学 | A kind of Fe3O4SiO2Magnetic single hole hollow microsphere and preparation method thereof |
| CN103551093B (en) * | 2013-11-15 | 2015-12-09 | 中国工程物理研究院化工材料研究所 | Microcapsules of the coated liquid of a kind of silica core-shell and preparation method thereof |
| CN105535999B (en) * | 2016-01-11 | 2018-10-16 | 中国科学院化学研究所 | A kind of intelligent magnetic single hole hollow nano-sphere and the preparation method and application thereof |
| CN106074448B (en) * | 2016-08-11 | 2019-10-15 | 中山大学 | A kind of application of the bias microballoon in drug ultrasonically controlled-release |
| CN116924418A (en) * | 2017-12-26 | 2023-10-24 | Ａｇｃ株式会社 | Method for producing hollow silica particles |
| WO2020138106A1 (en) * | 2018-12-25 | 2020-07-02 | Ａｇｃ株式会社 | Spherical hollow silica particle group, encapsulation agent, liquid dispersion, and aqueous dispersion |
| CN112744851B (en) * | 2019-10-31 | 2022-11-15 | 中国石油化工股份有限公司 | Raspberry type oxide microsphere and preparation method and application thereof |
| CN112742401B (en) * | 2019-10-31 | 2022-07-15 | 中国石油化工股份有限公司 | FT synthesis catalyst, preparation method and application thereof |
| JP2022554291A (en) * | 2019-10-31 | 2022-12-28 | 中国石油化工股▲ふん▼有限公司 | Support and FT synthesis catalyst, its preparation method, and its application |
| CN114849604B (en) * | 2022-04-12 | 2023-08-18 | 中怡(深圳)医疗科技集团有限公司 | Preparation method of single-hole microsphere |
| CN115367765B (en) * | 2022-09-01 | 2023-07-25 | 安徽农业大学 | Small-size single-hole hollow silica sphere and preparation method and application thereof |
| CN117975921A (en) * | 2024-04-02 | 2024-05-03 | 瑞声光电科技(常州)有限公司 | Sound absorption microsphere, preparation method and loudspeaker |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101683983A (en) * | 2008-09-27 | 2010-03-31 | 中国科学院大连化学物理研究所 | Method for preparing hollow mesoporous lamella spherical silica material |
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| CN101683983A (en) * | 2008-09-27 | 2010-03-31 | 中国科学院大连化学物理研究所 | Method for preparing hollow mesoporous lamella spherical silica material |
Non-Patent Citations (1)
| Title |
|---|
| Huijuan Zhang et al..Facile synthesis of monodisperse microspheres and gigantic hollow shells of mesoporous silica in mixed water-ethanol solvents.《Langmuir》.2007,第23卷(第3期),第1107-1113页，实验结果和讨论部分，图1. * |
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