CN102557051B - Method for preparing hollow mesocellular silica nanometer particles based on polymer formwork - Google Patents
Method for preparing hollow mesocellular silica nanometer particles based on polymer formwork Download PDFInfo
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- CN102557051B CN102557051B CN2012100009045A CN201210000904A CN102557051B CN 102557051 B CN102557051 B CN 102557051B CN 2012100009045 A CN2012100009045 A CN 2012100009045A CN 201210000904 A CN201210000904 A CN 201210000904A CN 102557051 B CN102557051 B CN 102557051B
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Abstract
The invention belongs to the technical field of inorganic nanometer cellular materials, particularly relates to a method for preparing hollow mesocellular silica nanometer particles based on a polymer formwork. Firstly emulsion is used for preparing stable and uniform t-butyl methacrylate nanometer microballoon spheres in polymerization mode; secondly cetyl trimethyl ammonium bromide serves as a pore-forming agent, and a composite silica casing layer is wrapped on the surfaces of the microballoon spheres, and finally the polymer formwork and the pore-forming agent in an ethanol solution of ammonium nitrate are removed by one step to obtain the hollow mesocellular silica nanometer particles with complete structures and properties. The method avoids the traditional method of using high-temperature calcination to remove the formwork, is energy-saving and environment-friendly, and can obtain the hollow mesocellular silica nanometer particles with different hollow sizes and casing layer thicknesses by adjusting the proportion of the pore-forming agent and a silicon source. The hollow mesocellular silica nanometer particles are stable in structure and apt to adjust size, can stably dispersed in water, and have good application prospects in the biomedical field.
Description
Technical field
The invention belongs to inorganic nano porous material technical field, be specifically related to a kind of preparation method of hollow mesoporous silicon dioxide nano particle.
Background technology
Hollow Metaporous silicon dioxide material is a kind of shell duct ordered arrangement, pore size is generally 2 ~ 50nm, and the hollow inorganic nano material that distributes narrow, because it has good biocompatibility, medicine carrying efficiency is high, larger specific surface area and pore volume, thus chemistry and thermostability and the siliceous hydroxyl of rich surface are beneficial to the advantages such as further functionalization preferably, are widely used at medicine carrying and drug release field.But, traditional hollow mesoporous silicon oxide particle preparation method always relates to utilize high-temperature calcination to remove template and pore former, at high temperature, dehydrating condensation can occur in the silicon hydroxyl of particle surface, have a strong impact on redispersibility and the stability of particle, be unfavorable for research and the application of hollow mesoporous silicon dioxide nano particle.
The present invention utilizes a kind of polymkeric substance of pure dissolubility as template, the characteristics of utilizing pore former to remove by ion-exchange, in ethanolic soln, remove simultaneously template and pore former, avoided the process of high-temperature calcination, the hollow mesoporous silicon dioxide nano particle minor structure homogeneous obtained, hollow size and shell thickness are easily adjusted, and the energy stable dispersion, in the aqueous solution, is conducive to its applied research in biomedicine field.
This base polymer template mainly comprises esters of acrylic acid, and for example tert-butyl acrylate, can obtain different sizes, the narrow polymer nano-microspheres of size distribution very easily by letex polymerization.By this polymkeric substance, be that synthetic hollow mesoporous silicon dioxide nano particle of template still belongs to pioneering.
Summary of the invention
The object of the invention is to propose the preparation method of a kind of energy-conserving and environment-protective, Stability Analysis of Structures, functional hollow mesoporous silicon dioxide nano particle.
The preparation method of hollow mesoporous silicon dioxide nano particle that the present invention proposes, the solvent of use only relates to water and dehydrated alcohol, nontoxic, energy-conserving and environment-protective; The hollow mesoporous silicon dioxide nano particle minor structure obtained is stable, and hollow size and shell thickness are easily adjusted, can stable dispersion in water, farthest guaranteed the integrity of gained morphology of particles and character, and at biomedicine field, good application prospect is arranged.Its concrete steps that prepare are as follows:
Step 1, be added to the tert-butyl acrylate monomer in the aqueous solution of cetyl trimethylammonium bromide, and the weight concentration of the cetyl trimethylammonium bromide aqueous solution is 0.6-1.2wt%; Rapid stirring, at room temperature logical nitrogen 30-60 min, then be warming up to 65-70
oC, add the catalyzer potassium persulfate solution, initiated polymerization, and the weight concentration of potassium persulfate solution is 0.1-0.2wt%, reaction 6-8 h; The add-on of regulating monomer is the 7-20wt% of whole reflection system weight, obtains the polyacrylic acid tert-butyl ester Nano microsphere of different-grain diameter;
Step 2, by the sol-gel process at the surperficial coating mesoporous silicon-dioxide of polymer microballoon (polyacrylic acid tert-butyl ester Nano microsphere).Concrete steps are: using the 0.3-0.6g cetyl trimethylammonium bromide as pore former, be dissolved in the mixing solutions of water that 75--80 mL volume ratio is 2:1--3:1 and ethanol, add again 0.05-0.06 g polymer microballoon as template, ultrasonic 5-10 min mixes, under room temperature, stir 30-60min, add successively in ammoniacal liquor (the ammoniacal liquor weight concentration is 25%) and tetraethyl orthosilicate, the part by weight of ammoniacal liquor and tetraethyl orthosilicate is 0.6:1--0.8:1, w/w, 35--45
oUnder C, react 20--24h.By the centrifugal reaction product that obtains, use deionized water and dehydrated alcohol repetitive scrubbing 2-3 time.Then product is dispersed in the ammonium nitrate ethanolic soln that concentration is 8--12mg/mL to 75--80
oUnder C, reaction 30-60 min, remove polymer template agent and pore former simultaneously, obtains hollow mesoporous silicon dioxide nano particle of Stability Analysis of Structures, uniform dispersion.
The method of hollow mesoporous silicon dioxide nano particle of preparation mainly adopts the method for high-temperature calcination to remove hollow template and pore former at present, and comparatively speaking, the present invention has following characteristics:
(1) utilize the polymkeric substance of pure dissolubility to be template, can in ethanolic soln, remove simultaneously template and pore former, simplified the removing template process;
(2) prepared hollow mesoporous silicon dioxide nano particle has good dispersiveness and stability in solution;
(3) the hollow size of particle and shell thickness can regulate and control very easily, and the Stability Analysis of Structures obtained, big or small homogeneous;
(4) this class particle has very high carrying drug ratio, and application prospect is very widely arranged aspect biological medicine.
The accompanying drawing explanation
The transmission electron microscope photo of Fig. 1, hollow mesoporous silicon dioxide nano particle.
Embodiment
Embodiment 1: 12 mL tert-butyl acrylates is added in the 80 mL aqueous solution that are dissolved with 1 g cetyl trimethylammonium bromide, and rapid stirring, at room temperature logical nitrogen 30min, then be warming up to 70
oC, add catalyzer potassium persulfate solution (0.1%) initiated polymerization, reaction 6 h.Having obtained particle diameter is the polyacrylic acid tert-butyl ester microballoon of 70 nm.
Embodiment 2: 20 mL tert-butyl acrylates is added in the 80 mL aqueous solution that are dissolved with 0.5 g cetyl trimethylammonium bromide, and rapid stirring, at room temperature logical nitrogen 30min, then be warming up to 70
oC, add catalyzer potassium persulfate solution (0.1%) initiated polymerization, reaction 6 h.Having obtained particle diameter is the polyacrylic acid tert-butyl ester microballoon of 120 nm.
Embodiment 3: getting the 70 nm polymer microballoons that 0.6 g makes is template, is dispersed in the mixing solutions (3:1) of 80 mL water and ethanol, adds 0.3 g cetyl trimethylammonium bromide as pore former, 40
oUnder C, stir 30 min, then add 0.85 mL ammoniacal liquor (25%) and 1.16 mL tetraethyl orthosilicates, reaction 24 h.Product is centrifugal, and water and ethanol wash respectively 3 times.Then be dispersed in the ammonium nitrate ethanolic soln of 10mg/mL 80
oC reacts 30 min, removes template and pore former, and the centrifugal hollow size obtained as shown in Figure 1 is 70nm, and shell thickness is hollow mesoporous silicon dioxide nano particle of 40 nm.
Embodiment 4: getting the 200 nm polymer microballoons that 0.6 g makes is template, is dispersed in the mixing solutions (3:1) of 80 mL water and ethanol, adds 0.3 g cetyl trimethylammonium bromide as pore former, 40
oUnder C, stir 30 min, then add 0.85 mL ammoniacal liquor (25%) and 0.24 mL tetraethyl orthosilicate, reaction 24 h.Product is centrifugal, and water and ethanol wash respectively 3 times.Then be dispersed in the ammonium nitrate ethanolic soln of 10mg/mL 80
oC reacts 60 min, removes template and pore former, centrifugally obtains hollow mesoporous silicon dioxide nano particle that hollow size is 180 nm.
Embodiment 5: the polymer microballoon of getting 70 nm that 0.6 g makes is template.Be dispersed in the mixing solutions (3:1) of 80 mL water and ethanol, add 0.64 g cetyl trimethylammonium bromide as pore former, 40
oUnder C, stir 30 min, then add 0.85 mL ammoniacal liquor (25%) and 2.49 mL tetraethyl orthosilicates, reaction 24 h.Product is centrifugal, and water and ethanol wash respectively 3 times.Then be dispersed in the ammonium nitrate ethanolic soln of 10mg/mL 80
oC reacts 60 min, removes template and pore former, and centrifugal to obtain hollow size be 70 nm, and shell thickness is mesoporous silicon dioxide nano particle of 65 nm.
Embodiment 6: the Zorubicin aqueous solution of preparation 1mg/mL.Get a certain amount of Zorubicin solution and mix with the sub-carrier of hollow mesoporous silicon dioxide nano particle, the mass ratio of medicine and carrier is 0.3, stirs 24h under room temperature, and centrifugation is washed 3 times repeatedly with deionized water, obtains the nanoparticle of medicine carrying.The supernatant liquor of collecting, for the uv-absorbing test, show that carrying drug ratio is 19%, and encapsulation rate is 83%.
Claims (1)
1. the method for hollow mesoporous silicon dioxide nano particle of the preparation based on polymer template is characterized in that concrete steps are as follows:
Step 1, be added to the tert-butyl acrylate monomer in the aqueous solution of cetyl trimethylammonium bromide, and the weight concentration of the cetyl trimethylammonium bromide aqueous solution is 0.6-1.2wt%; Rapid stirring, at room temperature logical nitrogen 30-60 min, then be warming up to 65-70
oC, add the catalyzer potassium persulfate solution, initiated polymerization, and the weight concentration of potassium persulfate solution is 0.1-0.2wt%, reaction 6-8 h; The add-on of regulating monomer is the 7-20wt% of whole reaction system weight, obtains the polyacrylic acid tert-butyl ester Nano microsphere of different-grain diameter;
Step 2, by the sol-gel process at the coating mesoporous silicon-dioxide in polyacrylic acid tert-butyl ester Nano microsphere surface, concrete steps are: using the 0.3-0.6g cetyl trimethylammonium bromide as pore former, be dissolved in the mixing solutions of water that 75--80 mL volume ratio is 2:1--3:1 and ethanol, add again 0.05-0.06 g polyacrylic acid tert-butyl ester Nano microsphere as template, ultrasonic 5-10 min mixes, under room temperature, stir 30-60min, adding successively weight concentration is in 25% ammoniacal liquor and tetraethyl orthosilicate, the part by weight of ammoniacal liquor and tetraethyl orthosilicate is 0.6:1--0.8:1, w/w, 35--45
ounder C, react 20--24h, by the centrifugal reaction product that obtains, use deionized water and dehydrated alcohol repetitive scrubbing 2-3 time, then product is dispersed in the ammonium nitrate ethanolic soln that concentration is 8--12mg/mL to 75--80
ounder C, reaction 30-60 min, remove template and pore former simultaneously, obtains hollow mesoporous silicon dioxide nano particle of Stability Analysis of Structures, uniform dispersion.
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| CN105923636B (en) * | 2016-04-13 | 2018-03-27 | 哈尔滨工业大学 | The preparation method of the hollow mesoporous silicon dioxide nano microballoon of single dispersing |
| CN106167265B (en) * | 2016-07-05 | 2018-09-21 | 南京工业大学 | Preparation method of honeycomb silicon dioxide microspheres |
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| CN102050453A (en) * | 2009-11-06 | 2011-05-11 | 中国科学院上海硅酸盐研究所 | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material |
| CN102153094A (en) * | 2011-03-21 | 2011-08-17 | 厦门大学 | Method for preparing ordered mesoporous hollow silica spheres |
| CN102275936A (en) * | 2011-06-09 | 2011-12-14 | 华东师范大学 | Preparation method of mesoporous spherical Sio2 nanoparticles |
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| CN101259401B (en) * | 2004-11-11 | 2010-06-23 | 中国科学院化学研究所 | Method for preparing hollow ball and hollow ball with complex structure by template method |
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| CN101708853A (en) * | 2009-07-08 | 2010-05-19 | 济南大学 | Hollow silicon dioxide microsphere with different surface configurations and preparation method thereof |
| CN102050453A (en) * | 2009-11-06 | 2011-05-11 | 中国科学院上海硅酸盐研究所 | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material |
| CN102153094A (en) * | 2011-03-21 | 2011-08-17 | 厦门大学 | Method for preparing ordered mesoporous hollow silica spheres |
| CN102275936A (en) * | 2011-06-09 | 2011-12-14 | 华东师范大学 | Preparation method of mesoporous spherical Sio2 nanoparticles |
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