CN102718225A - Preparation method of ordered mesoporous silica microspheres with hollow structures - Google Patents
Preparation method of ordered mesoporous silica microspheres with hollow structures Download PDFInfo
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- CN102718225A CN102718225A CN201210248779XA CN201210248779A CN102718225A CN 102718225 A CN102718225 A CN 102718225A CN 201210248779X A CN201210248779X A CN 201210248779XA CN 201210248779 A CN201210248779 A CN 201210248779A CN 102718225 A CN102718225 A CN 102718225A
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- mesoporous silica
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004005 microsphere Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000003093 cationic surfactant Substances 0.000 claims abstract 5
- 239000011259 mixed solution Substances 0.000 claims abstract 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical group [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 3
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 29
- 238000005406 washing Methods 0.000 abstract description 16
- 239000007787 solid Substances 0.000 abstract description 12
- 238000001035 drying Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000005530 etching Methods 0.000 abstract description 5
- 239000000839 emulsion Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000012377 drug delivery Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000003384 imaging method Methods 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 24
- 238000002156 mixing Methods 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 12
- 241000282326 Felis catus Species 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WENLKAKVZDPNQX-UHFFFAOYSA-N methanetetrol silicic acid Chemical compound C(O)(O)(O)O.[Si](O)(O)(O)O WENLKAKVZDPNQX-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of ordered mesoporous silica microspheres with hollow structures, which comprises the steps of dissolving a cationic surfactant in a mixed solution of ethanol and water, sequentially adding ammonia water and a silicon source into the mixed solution under the conditions of heating and stirring, and reacting for a period of time to obtain solid silica microspheres; washing the obtained silicon dioxide, transferring the silicon dioxide to water for etching, and reacting for a period of time to obtain hollow silicon dioxide microspheres; and finally, collecting the hollow silica, drying and roasting to obtain the ordered mesoporous silica microsphere product with the hollow structure. The preparation method does not need to prepare a sacrificial hard template or an emulsion template in advance, and has the characteristics of simple process, mild reaction conditions, low cost and environmental friendliness; the prepared hollow mesoporous silica microspheres have great application potential in the biomedical fields of ultrasonic imaging, drug delivery and the like.
Description
Technical field
The present invention relates to a kind of preparation method of ordered mesoporous silica dioxide microballoon of hollow structure, belong to the preparation field of inorganic materials.
Background technology
It with the tensio-active agent research focus that the mesoporous material in synthetic high-ratio surface of template and homogeneous aperture has become Materials science.These mesoporous materials have been widely used in physics, chemistry and biomedical sector.Can synthesize multiple mesoporous material through the control reaction conditions with higher structure and special appearance, as: film, fiber, ball, hollow ball etc.Wherein, the mesoporous silicon dioxide micro-sphere that has a hollow structure has caused people's extensive concern because of its particular structural and function.At first, researcher uses O/w emulsion, supercritical CO
2And microcapsule have successfully prepared mesoporous silicon oxide (S. Schacht, Q. Huo, I. G. Voigt-Martin, G. D. Stucky, F. Schuth, Science, 1996,273,768 with hollow structure as hollow template; J. Wang, Y. Xia, W. Wang, M. Poliakoff, R. Mokaya, J. Mater. Chem., 2006,16,1751; P. T. Tanev, T. J. Pinnavaia, Science 1996,271, and 1267).Yet because these soft template have low stability and relatively poor homogeneity in reaction soln, thereby the mesoporous silicon oxide of the hollow structure for preparing has irregular pattern and wide distribution of sizes usually.In addition, adopt the soft template technology to be difficult to realize the regulation and control of cavity size and shell thickness.In order to overcome the deficiency of soft template technology of preparing, people have developed and have utilized polymkeric substance or colloidal inorganic particle to make to sacrifice hard template strategy (Z. Chen, Z.-M. Cui, the F. Niu of template; L. Jiang, W.-G. Song, Chem. Commun.; 2010,46,6524; Y. Zhao, L.-N. Lin, Y. Lu, S.-F. Chen, L. Dong, S.-H. Yu, Adv. Mater. 2010,22,5255; X. Fang, C. Chen, Z. Liu, P. Liu, N. Zheng, Nanoscale, 2011,3,1632).Yet the preparation of sacrificial hard template and removal often relate to the reaction process of a plurality of complicacies, and the preparation process is consuming time, and cost is also higher relatively, is inappropriate for the expansion production of industriallization and commercialization.In addition, because surfactant micelle trend lies low in the surface of sacrificing template reducing surface energy, thereby the mesopore orbit of the hollow ball for preparing is parallel to microsphere surface usually, and this is unfavorable for the transmission of guest molecule in hollow ball shell both sides.
Summary of the invention
Goal of the invention: in order to overcome the deficiency that exists in the prior art, the present invention provides a kind of method of ordered mesoporous silica dioxide microballoon of simple preparation hollow structure.
Technical scheme: for realizing above-mentioned purpose; The preparation method of the ordered mesoporous silica dioxide microballoon of hollow structure of the present invention comprises: at first cats product is dissolved in the mixing solutions of second alcohol and water, adding ammoniacal liquor and silicon source make the solid silicon dioxide microsphere with mesoscopic structure in the mixing solutions of the second alcohol and water that contains cats product; And then prepare hollow silica ball through the technological process of simple water etching; Method through roasting is removed the ordered mesoporous silica dioxide microballoon that cats product promptly obtains having the hollow structure in radial duct at last.
The concrete synthesis step of the ordered mesoporous silica dioxide microballoon of hollow structure of the present invention is following:
(1) cats product is dissolved in the mixing solutions of second alcohol and water; Under 10～50 ℃, agitation condition, ammoniacal liquor and silicon source are joined in the mixing solutions of cation tensio-active agent; Reaction 3～24 h; Generate white precipitation of silica, the mol ratio of cats product, silicon source, ammoniacal liquor, second alcohol and water is 1:10～40: 30～120: 1000～5000:6000～25300;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions in the water, at 20～90 ℃ of condition held 1～150 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 500～600 ℃ of roasting 5 ~ 7 h, finally obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
As preferably, described cats product is a kind of in Trimethyllaurylammonium bromide, TTAB, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide or the palmityl trimethyl ammonium chloride.
Described silicon source is a kind of in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate or positive silicic acid four butyl esters.
The concentration of described silica dispersions is 0.1～5 mg/mL
Described agitation condition is 200～800 rev/mins.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that the employing method for preparing obtains is 200～800 nm; Shell thickness is 25～200 nm; Mesopore orbit is six side's ordered arrangement, and the aperture is 2.5～4.0 nm; The specific surface area of the ordered mesoporous silica dioxide microballoon of described hollow structure is 900～1600 m
2/ g.
Beneficial effect: compared with prior art, the preparation method of the ordered mesoporous silica dioxide microballoon of hollow structure of the present invention has the following advantages:
1, the present invention is a template with cats product commonly used, that cost is low, can prepare the ordered mesoporous silica dioxide microballoon of hollow structure through simple technological process;
2, the present invention adopts pure water to synthesize solid silicon-dioxide, and then has characteristics low for equipment requirements, with low cost, eco-friendly through the process that water etching prepares the ordered mesoporous silica dioxide microballoon of hollow structure; The productive rate that adopts the hollow ball that this method prepares is up to 98%, is of value to industriallization and enlarges and produce;
3, can regulate and control the cavity size and the shell thickness of tiny balloon effectively through the temperature and time of regulation and control etching.
Adopt the ordered mesoporous silica dioxide microballoon of the hollow structure that preparation method of the present invention makes, have the following advantages:
1, the ordered mesoporous silica dioxide microballoon of this hollow structure has the spherical morphology and the size of homogeneous; The hollow ball surface has abundant silicon hydroxyl, has good polar solvent dispersing property and biocompatibility; This hollow ball has huge application potential at biomedical sectors such as ultrasonic contrast, medicine transmission;
2, the ordered mesoporous silica dioxide microballoon of this hollow structure has the aperture of high specific surface area, pore volume and homogeneous; Mesopore orbit is six side's ordered arrangement (spacer: P6mm), be radial, help the transmission of medicine equimolecular in the mesoporous lamella both sides;
3, hollow ball shakes in 60 Hz ultrasonic cleaners did not have breakage in 10 minutes, explained that hollow ball has favorable mechanical stability; Morphology change does not take place through 600 ℃ high-temperature roasting in hollow ball, explains that hollow ball has good thermostability.
Description of drawings
The electron micrograph of the silicon-dioxide solid sphere that Fig. 1 the present invention makes under the processing condition of embodiment 1;
The electron micrograph of the ordered mesoporous silica dioxide tiny balloon with hollow structure that Fig. 2 the present invention makes under the processing condition of embodiment 1: in Fig. 2, a is the low power stereoscan photograph of hollow ball; B is for grinding the high power stereoscan photograph of broken hollow ball; C is the transmission electron microscope photo of hollow ball; D is the transmission electron microscope photo of the mesoporous lamella of hollow ball;
The X-ray diffractogram of the ordered mesoporous silica dioxide microballoon of the hollow structure that Fig. 3 the present invention makes under the processing condition of embodiment 1;
Nitrogen adsorption-the desorption isotherm and the pore distribution curve of the ordered mesoporous silica dioxide microballoon of the hollow structure that Fig. 4 the present invention makes under the processing condition of embodiment 1;
The transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that Fig. 5 the present invention makes under the processing condition of embodiment 4;
The transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that Fig. 6 the present invention makes under the processing condition of embodiment 5;
The transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that Fig. 7 the present invention makes under the processing condition of embodiment 6.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done explanation further.
The preparation method of the ordered mesoporous silica dioxide microballoon of hollow structure of the present invention; At first cats product is dissolved in the mixing solutions of second alcohol and water; In mixing solutions, add ammoniacal liquor and silicon source under the condition of heating and stirring successively, obtain solid silicon dioxide microsphere after reaction for some time; The silicon-dioxide that washing obtains, and be transferred to etching in the water, obtain the hollow silicon dioxide microballoon after reaction for some time; At last, collect hollow silicon dioxide, dry, roasting obtains the ordered mesoporous silica dioxide microspheres product of hollow structure.This preparation method uses cheap cats product to be template, can prepare the ordered mesoporous silica dioxide microballoon of hollow structure through simple technological process.That the preparation process has is low for equipment requirements, technological process is simple, eco-friendly characteristics.The productive rate of the order mesoporous microballoon of the hollow structure for preparing is of value to industriallization and enlarges production up to 98%.The mesopore orbit of the mesoporous silicon dioxide micro-sphere of the hollow structure that obtains in order, be radial, help the transmission of molecule and ion in the shell both sides.
Embodiment of the present invention is following:
Embodiment 1:
(1) 0.08 g cetyl trimethylammonium bromide is dissolved in the mixing solutions of 30 ml ethanol and 50 ml water, at 30 ℃, under the 500 rpm agitation conditions with 1 ml strong aqua (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and the positive tetraethyl orthosilicate of 1 ml join in the mixing solutions, react 12 h, obtain white solid silicon dioxide microsphere (Fig. 1);
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (2 mg/ml) in the water, under 50 ℃ of conditions, stir 20 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6 h, obtain the ordered mesoporous silica dioxide microballoon (referring to Fig. 2) of hollow structure.
The silicon-dioxide that obtains through step (1) is the solid sphere with spherical morphology.The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 550 nm, has hollow structure, and shell thickness is about 100 nm; It is radial that mesopore orbit is, and has six side's ordered structures (Fig. 3); The aperture with homogeneous (as shown in Figure 4) of mesoporous silicon dioxide micro-sphere, aperture size is 2.6 nm; Specific surface area is 987 m
2/ g.
Embodiment 2:
(1) 0.08 g Trimethyllaurylammonium bromide is dissolved in the mixing solutions of 15 ml ethanol and 100 ml water, at 10 ℃, under the 200 rpm agitation conditions with 0.5 ml strong aqua (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and the positive tetraethyl orthosilicate of 0.5 ml join in the mixing solutions, react 24 h, obtain white solid silicon dioxide microsphere;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (0.1 mg/ml) in the water, under 20 ℃ of conditions, stir 1 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 500 ℃ of roasting 6 h, obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 210 nm, has hollow structure, and shell thickness is about 40 nm; It is radial that mesopore orbit is, and has six side's ordered structures; The aperture with homogeneous of mesoporous silicon oxide, aperture size are 3.0 nm; Specific surface area is 1124 m
2/ g.
Embodiment 3:
(1) 0.08 g cetyl trimethylammonium bromide is dissolved in the mixing solutions of 60 ml ethanol and 25 ml water, at 50 ℃, under the 500 rpm agitation conditions with 1.9 ml strong aquas (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and the positive tetraethyl orthosilicate of 1.9 ml join in the mixing solutions, react 3 h, obtain white solid silicon dioxide microsphere;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (5 mg/ml) in the water, under 90 ℃ of conditions, stir 120 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 600 ℃ of roasting 7 h, obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 780 nm, has hollow structure, and shell thickness is about 60 nm; It is radial that mesopore orbit is, and has six side's ordered structures; The aperture with homogeneous of mesoporous silicon oxide, aperture size are 2.5 nm; Specific surface area is 913 m
2/ g.
Embodiment 4:
(1) 0.08 g octadecyl trimethylammonium bromide is dissolved in the mixing solutions of 30 ml ethanol and 50 ml water, at 30 ℃, under the 800 rpm agitation conditions with 1 ml strong aqua (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and the positive quanmethyl silicate of 1 ml join in the mixing solutions, react 12 h, obtain white solid silicon dioxide microsphere;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (2 mg/ml) in the water, under 25 ℃ of conditions, stir 18 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 550 ℃ of roasting 5 h, obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 650 nm, has hollow structure, and shell thickness is about 200 nm; It is radial that mesopore orbit is, and has hexagonal structure; The aperture with homogeneous of mesoporous silicon oxide, aperture size are 3.9 nm; Specific surface area is 987 m
2/ g.Fig. 5 is the transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that makes under the processing condition of present embodiment.
Embodiment 5:
(1) 0.08 g TTAB is dissolved in the mixing solutions of 25 ml ethanol and 60 ml water, at 30 ℃, under the 500 rpm agitation conditions with 1 ml strong aqua (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and positive silicic acid four butyl esters of 1 ml join in the mixing solutions, react 12 h, obtain white solid silicon dioxide microsphere;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (2 mg/ml) in the water, under 25 ℃ of conditions, stir 144 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6 h, obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 450 nm, has hollow structure, and shell thickness is about 40 nm; It is radial that mesopore orbit is, and has hexagonal structure; The aperture with homogeneous of mesoporous silicon oxide, aperture size are 3.1 nm; Specific surface area is 1548 m
2/ g.Fig. 6 is the transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that makes under the processing condition of present embodiment.
Embodiment 6:
(1) 0.08 g palmityl trimethyl ammonium chloride is dissolved in the mixing solutions of 28 ml ethanol and 55 ml water, at 30 ℃, under the 500 rpm agitation conditions with 1 ml strong aqua (the contained ammonia NH of this strong aqua
3Mass percentage concentration be 25 ~ 28%) and the positive silicic acid orthocarbonate of 1 ml join in the mixing solutions, react 12 h, obtain white solid silicon dioxide microsphere;
(2) with the centrifugal washing of step (1) gained silicon-dioxide, be transferred to and make silica dispersions (2 mg/ml) in the water, under 70 ℃ of conditions, stir 6 h;
(3) reaction product of step (2) gained is centrifugal, washing, drying; In 550 ℃ of roasting 6 h, obtain the ordered mesoporous silica dioxide microballoon of hollow structure.
The particle diameter of the ordered mesoporous silica dioxide microballoon of the hollow structure that obtains is 500 nm, has hollow structure, and shell thickness is about 25 nm; It is radial that mesopore orbit is, and has six side's ordered structures; The aperture with homogeneous of mesoporous silicon oxide, aperture size are 3.4 nm; Specific surface area is 1223 m
2/ g.Fig. 7 is the transmission electron microscope photo of the ordered mesoporous silica dioxide microballoon of the hollow structure that makes under the processing condition of present embodiment.
The above only is a preferred implementation of the present invention; Be noted that for those skilled in the art; Under the prerequisite that does not break away from the principle of the invention, can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (6)
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| CN116120834A (en) * | 2022-12-29 | 2023-05-16 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of closed porous flexible antireflection layer |
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