CN101804986B - Method for preparing hollow silicon dioxide microsphere with controllable wall thickness by taking polystyrene microsphere as template - Google Patents
Method for preparing hollow silicon dioxide microsphere with controllable wall thickness by taking polystyrene microsphere as template Download PDFInfo
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- CN101804986B CN101804986B CN2009102274024A CN200910227402A CN101804986B CN 101804986 B CN101804986 B CN 101804986B CN 2009102274024 A CN2009102274024 A CN 2009102274024A CN 200910227402 A CN200910227402 A CN 200910227402A CN 101804986 B CN101804986 B CN 101804986B
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Abstract
The invention discloses a method for preparing hollow silicon dioxide microsphere with controllable wall thickness by taking polystyrene microsphere as the template, which includes the steps of, according to weight/volume proportion, putting 0.05-0.5g of polystyrene microsphere and 1-8ml of tetraethoxysilane in a supercritical reactor with constant temperature of 25-60 DEG without contacting each other, introducing carbon dioxide to the supercritical reactor until the pressure reaches 9-25Mpa, reacting for 1-10h, relieving the pressure to the normal pressure, opening the reactor to get out of the processed polystyrene microsphere to obtain compound microsphere, dispersing the compound microsphere in the mixture solution of 0.3-4ml of ammonia and 10ml of ethanol, at the same time adding 0-0.66ml of tetraethoxysilane to the mixture solution, hydrolyzing for 2-24h under 20-40 DEG C, separating the solid and the liquid of the system after the hydrolysis process, and sintering the compound microsphere which is separated out. In this way, the hollow silicon dioxide microsphere can be obtained. The method finishes the modification of the polymer microshere and the implantation of the inorganic presoma in one step, and is simple in process, simple and convenient to operate, energy-saving and environment-friendly, and the hollow silicon dioxide microsphere prepared through the method has controllable wall thickness.
Description
Technical field
The invention belongs to the preparing technical field of inorganic hollow microballoon, being specifically related to a kind of is the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere.
Background technology
Because hollow silica microsphere is in controllable release, artificial cell, light filler, aspects such as catalysis and confinement reactor have a wide range of applications, simultaneously himself excellent biological compatibility is arranged again, characteristics such as lower density and higher heating power and mechanical stability, therefore the research about its preparation and character has caused vast scientific and technological work person's great interest.The ordinary method of preparation hollow silica microsphere mainly contains sedimentation layer by layer, polymer microballoon sulfonation method etc. at present.Although these methods can be prepared size and the controlled hollow silica microsphere of wall thickness, they also exist self inherent defective in some aspects.Sedimentation is when the preparation hollow microsphere layer by layer, although it can realize the accuracy controlling to the microballoon wall thickness, but because it will be through processes such as repeatedly absorption and centrifuge washings, not only efficient is lower, simultaneously also will waste a large amount of water and power resource, thereby limit the application in practice of this method.Owing to the restriction of polyelectrolyte self, the wall thickness of the hollow microsphere of this method preparation is generally thinner simultaneously.Although the polymer microballoon sulfonation method can be controlled the sulfonation degree of microballoon by regulating the sulfonation time, thereby realizes the control to final hollow silica microsphere wall thickness.But long sulfonation time and these sulfonation microballoons are handled to necessary centrifuge washing process when neutral not only can cause environmental pollution, and can cause a large amount of wastes of water resources and power resource, reduce production efficiency.
Supercritical co is nontoxic, and the chemical stability height cheaply is easy to get, environmental friendliness and have lower critical temperature and pressure (Tc=31 ℃, Pc=73.8bar).Supercritical co all has very high solubleness in most of organic solvents, this makes it have good organic micromolecular characteristic of carrying.Supercritical co all has certain dissolving power in different polymkeric substance, this can make polymkeric substance plastify under lower temperature.Polymkeric substance is in case plastify, then supercritical co carry such as organic molecules such as dyestuff, medicine and metal organic precursor bodies just than being easier to be penetrated into polymkeric substance inside.After the system release, these small molecules just are trapped in the polymeric matrix of vitreous state.Utilize the above-mentioned part character of supercritical co, people have prepared macroporous silica material and hollow silica microsphere.For example, be template with the polyalcohol colloid crystal, utilize the good character of carrying tetraethoxy of supercritical co, people such as Renuncio prepared orderly silicon-dioxide macroporous membrane (
A.; Enciso, E.; Carbajo, M.C.; Torralvo, M.J.; Pando, C.; Renuncio, J.A.R.Chem.Mater.2005,17,6137-6145.).Utilize the polymer microballoon of hollow to be template, having synthesized finishing the people such as auxiliary poplar down of supercritical co has Eu
2O
3.Fe
2O
3And Co
3O
4Compound hollow microsphere (the Wang J.Q. of nanoparticle; Zhang, C.L.; Liu, Z.M.:Ding, K.L.; Yang, Z.Z.Macromol.Rapid Commun.2005,27,787-792).At the interface of supercritical co and water, people such as king have synthesized silicon dioxide microsphere (Wang, the J.W. of the bigger hollow of distribution of sizes; Xia, Y.; Wang, W.X.; Poliakoff, M.; Mokaya, R.J.Mater.Chem.2006,16,1751-1756.).But up till now, do not enter the bibliographical information that polymer microballoon is realized the preparation and the modification of complex microsphere as yet, also do not see to have and utilize supercritical co to carry inorganic precursor to enter the bibliographical information that polymer microballoon prepares the controlled inorganic hollow microballoon of wall thickness about utilizing supercritical co to carry the inorganics presoma.
Summary of the invention
For overcoming the deficiencies in the prior art part, it is the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere that purpose of the present invention aims to provide a kind of.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A kind of is the method that template prepares the controlled hollow silica microsphere of wall thickness in the polystyrene microsphere: with the mass/volume ratio, the tetraethoxy of the polystyrene microsphere of 0.05～0.5g and 1～8ml do not contacted mutually place 25～60 ℃ of homothermic supercritical reaction containers, feeding carbonic acid gas to pressure simultaneously in this supercritical reaction container is 9～25Mpa, behind reaction 1～10h, unload and be depressed into normal pressure, open reaction vessel and take out the polystyrene microsphere acquisition complex microsphere of handling, and it is dispersed in the mixing solutions of being made up of 0.3～4ml ammoniacal liquor and 10ml ethanol, add the tetraethoxy that 0～0.66ml is arranged simultaneously in this mixing solutions, hydrolysis 2～24h under 20～40 ℃ of temperature, with the system solid-liquid separation after the hydrolysis, promptly get hollow silica microsphere after the complex microsphere calcination of separating then.
The preferred crosslinked polystyrene microsphere of described polystyrene microsphere.Crosslinked polystyrene microsphere can prepare in a large number by existing emulsifier-free emulsion polymerization or emulsion polymerization, but concrete reference 1, Yan Li, Jiafu Chen, Qun Xu, Linghao He, and Zhimin Chen, J.Phys.Chem.C 2009,113, and 10085～10089; 2, application number is " 200910064897.3 ", and denomination of invention is the Chinese patent of " a kind of method for preparing the controlled monodisperse carbon microsphere of form ".
The degree of crosslinking of crosslinked polystyrene microsphere is 3～30%.
The preparation used preferred ethylene glycol dimethyl double methacrylate of linking agent (EGDMA) or Vinylstyrene (DVB) during crosslinked polystyrene microsphere.
For polystyrene microsphere and tetraethoxy are not contacted mutually, preferably polystyrene microsphere is placed supercritical reaction container top, tetraethoxy is placed the supercritical reaction container bottom.
During calcination, be warming up to 400～800 ℃ of calcination 3～6h with the speed of 5～15 ℃/min.
During hydrolysis, first ultra-sonic dispersion 5～15min, and then under the stir speed (S.S.) of 200～800rpm, finish hydrolytic process.
Polystyrene microsphere wraps up with permeable material, makes supercritical co can enter this parcel system and the tetraethoxy of separating out in the system after the release can not directly contact with polystyrene microsphere.Permeable material among the present invention can be cotton, hospital gauze, filter cloth, filter paper etc.
The speed that feeds carbonic acid gas is 150～300ml/h.
Solid-liquid separation is centrifugation, and centrifugal rotational speed is 6000～9500rpm, centrifugation time 10～30min.
Among the present invention, common practise as those skilled in the art, in the supercritical reaction container, feed carbonic acid gas and to reaction pressure, need excluding air, the slow release mode of also taking those skilled in the art to use always during release, the release time is controlled within 5～60min.
The present invention is as supplementary means with supercritical co, with crosslinked polystyrene microsphere is template, utilizes supercritical co to come a step to realize the modification of polymer template microballoon and the implantation of inorganic precursor to good swelling property and its character of carrying inorganic precursor of polymer microballoon.
The present invention has the following advantages with respect to prior art:
Template microsphere required for the present invention can prepare in a large number by emulsifier-free emulsion polymerization or emulsion polymerization; The modification and being implanted in the step of inorganic precursor of polymer microballoon are finished, and technology is simple, and is easy and simple to handle; Supercritical co is a green solvent, energy-conserving and environment-protective; The hollow silica microsphere size that makes is more even, and wall thickness can be regulated and control by changing a plurality of experiment conditions within the specific limits; This hollow microsphere can be widely used in fields such as medicament slow release, catalysis and light filler.
Description of drawings
Fig. 1 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.1 preparations;
Fig. 2 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.2 preparations;
Fig. 3 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.3 preparations;
Fig. 4 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.4 preparations;
Fig. 5 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.5 preparations;
Fig. 6 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.6 preparations;
Fig. 7 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.7 preparations;
Fig. 8 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.8 preparations;
Fig. 9 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.9 preparations;
Figure 10 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.10 preparations;
Figure 11 is the transmission electron microscope picture of the hollow silica microsphere of the embodiment of the invention 2.11 preparations.
Embodiment
The invention will be further described below in conjunction with embodiment, and listed embodiment is being to implement under the prerequisite with the technical solution of the present invention all, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Prepare crosslinked polystyrene microsphere with EGDMA as linking agent, concrete experimentation is as follows: 1 three-necked bottle that is equipped with the 250ml of mechanical stirrer and reflux condensate device is placed in the thermostat water bath.In system, add 90ml deionized water, 0.24gNaHCO then
3, 1.2ml methacrylic acid and 10ml vinylbenzene.To keep churned mechanically speed under protection of nitrogen gas be 250rpm and the temperature of system risen to 70 ℃.Behind the constant temperature 30min, the aqueous solution that 10ml is dissolved with the 0.08g Potassium Persulphate is added in the reaction system as initiator.After polyreaction was carried out 1h, the EGDMA of 0.3ml was added into as linking agent.Just obtained crosslinked polystyrene microsphere in 24 hours 70 ℃ of following polymerizations then, degree of crosslinking is 3%.
The degree of crosslinking of above-mentioned polystyrene microsphere can be regulated by the consumption that changes EGDMA, and when the amount ranges of EGDMA was regulated between 0.3～0.6ml, the degree of crosslinking of polystyrene microsphere generally can be controlled between 3～6%.
Through centrifugal, drying treatment, it is standby fully to grind the back with mortar then with the crosslinked polystyrene microsphere of above-mentioned preparation.
Embodiment 2
Specifically be divided into following 5 individual system in the present embodiment, the wall thickness of research hollow silica microsphere is with the variation tendency of the addition (system 5) of tetraethoxy in the consumption (system 2) of the consumption (system 1) of tetraethoxy, crosslinked polystyrene microsphere, reaction times (system 3), system pressure (system 4), the hydrolytic process, and is specific as follows:
Embodiment 2.1 is with 2ml tetraethoxy (TEOS) the supercritical reaction still that to join 40 ℃ of homothermic volumes be 50ml bottom.Take by weighing the crosslinked polystyrene microsphere of 0.2g embodiment 1 preparation simultaneously, with be placed on behind the filter cloth parcel with the matching used stainless steel cage of supercritical reaction still in, then the stainless steel cage is placed supercritical reaction still top (the stainless steel cage is apart from reactor bottom 6cm).Speed with 200ml/h is injected CO in the supercritical reaction still
2, behind the excluding air 1min, continue to feed carbonic acid gas and react 4h to 10Mpa.Slowly unload and be depressed into (the release time is 30min) behind the normal pressure, open reactor and take out the polystyrene microsphere acquisition complex microsphere of handling.With above-mentioned complex microsphere under 30 ℃, first ultra-sonic dispersion 10min in the mixing solutions of 10ml ethanol and 1ml ammoniacal liquor, and then hydrolysis 8 hours under the magnetic agitation of 500rpm.With said hydrolyzed system later by whizzer centrifugal 10min under 9500rpm, the centrifugal complex microsphere that comes out was placed in the inherent retort furnace of porcelain crucible calcination 4 hours, calcination temperature and temperature rise rate are respectively 600 ℃ and 5 ℃/minute, promptly obtain the silicon dioxide microsphere of hollow after the calcination.
On the basis of embodiment 2.1,5 individual system are undertaken by following process respectively:
System 1: fixedly the consumption of crosslinked polystyrene microsphere is that 0.2g, system pressure are that 10Mpa, reaction times are 4h, the consumption of regulating tetraethoxy is observed the variation tendency of the wall thickness of hollow silica microsphere with the consumption of tetraethoxy between 1～8ml.
Embodiment 2.2 is adjusted to 1ml with the consumption of tetraethoxy, and other is all with embodiment 2.1.
Embodiment 2.3 is adjusted to 8ml with the consumption of tetraethoxy, and other is all with embodiment 2.1.
Fig. 1～3 are respectively the transmission electron microscope pictures (TEM) of embodiment 2.1, embodiment 2.2, embodiment 2.3 gained hollow silica microsphere: from this series of drawing as can be seen, along with the TEOS consumption becomes 2ml by 1ml, become 8ml again, the wall thickness of hollow silica microsphere correspondingly becomes 20nm from 12nm, become 48nm again, the wall thickness that hollow silica microsphere in above-mentioned amount ranges is described increases and thickening with the consumption of TEOS.
System 2: fixedly the consumption of tetraethoxy is that 2ml, system pressure are that 10Mpa, reaction times are 4h, the consumption of regulating crosslinked polystyrene microsphere is observed the variation tendency of the wall thickness of hollow silica microsphere with the consumption of crosslinked polystyrene microsphere between 0.05～0.5g.
Embodiment 2.4 is adjusted to 0.05g with the consumption of crosslinked polystyrene microsphere, and other is all with embodiment 2.1.
Embodiment 2.5 is adjusted to 0.5g with the consumption of crosslinked polystyrene microsphere, and other is all with embodiment 2.1.
Fig. 1,4,5 is respectively the transmission electron microscope picture (TEM) of embodiment 2.1, embodiment 2.4, embodiment 2.5 gained hollow carbonic acid gas microballoons: from this series of drawing as can be seen, along with the crosslinked polystyrene microsphere consumption becomes 0.2g by 0.05g, become 0.5g again, the wall thickness of hollow silica microsphere correspondingly becomes 20nm from 30nm, become 10nm again, illustrate by increasing the consumption of crosslinked polystyrene microsphere microballoon, can reduce the wall thickness of the hollow silica microsphere that generated.
System 3: fixedly the consumption of crosslinked polystyrene microsphere is that the consumption of 0.2g, tetraethoxy is that 2ml, system pressure are 10Mpa, and adjusting reaction time is observed the variation tendency of the wall thickness of hollow silica microsphere with the reaction times between 1～10h.
Embodiment 2.6 will be adjusted to 1h in the reaction times, and other is all with embodiment 2.1.
Embodiment 2.7 will be adjusted to 10h in the reaction times, and other is all with embodiment 2.1.
Fig. 1,6,7 is respectively the transmission electron microscope picture (TEM) of embodiment 2.1, embodiment 2.6, embodiment 2.7 gained hollow carbonic acid gas microballoons: from this series of drawing as can be seen, along with the reaction times becomes 4h by 1h, become 10h again, the wall thickness of hollow silica microsphere correspondingly becomes 20nm from 14nm, become 57nm again, explanation is along with the increase in reaction times, and the wall thickness of hollow silica microsphere presents the trend of increase.
System 4: fixedly the consumption of crosslinked polystyrene microsphere is that the consumption of 0.2g, tetraethoxy is that 2ml, reaction times are 1～10h, and regulation system pressure is observed the variation tendency of the wall thickness of hollow silica microsphere with system pressure between 9～25Mpa.
Embodiment 2.8 is adjusted to 9Mpa with system pressure, and other is all with embodiment 2.1.
Embodiment 2.9 is adjusted to 25Mpa with system pressure, and other is all with embodiment 2.1.
Fig. 1,8,9 is respectively the transmission electron microscope picture (TEM) of embodiment 2.1, embodiment 2.8, embodiment 2.9 gained hollow carbonic acid gas microballoons: from this series of drawing as can be seen, along with system pressure becomes 10Mpa by 9Mpa, become 25Mpa again, the wall thickness of hollow silica microsphere correspondingly becomes 20nm from 15nm, become 29nm again, explanation is along with the increase of system pressure, and the wall thickness of hollow silica microsphere also increases to a certain extent.
System 5: fixedly the consumption of crosslinked polystyrene microsphere is that the consumption of 0.2g, tetraethoxy is that 2ml, system pressure are 10Mpa, reaction times 10h, the addition of regulating tetraethoxy in the hydrolytic process is observed the variation tendency of the wall thickness of hollow silica microsphere with tetraethoxy addition in the hydrolytic process between 0～0.66ml.
Embodiment 2.10 adds tetraethoxy 0.33ml in the mixing solutions of ethanol and ammoniacal liquor, other is all with embodiment 2.1.
Embodiment 2.11 adds tetraethoxy 0.66ml in the mixing solutions of ethanol and ammoniacal liquor, other is all with embodiment 2.1.
Fig. 1,10,11 is respectively the transmission electron microscope picture (TEM) of embodiment 2.1, embodiment 2.10, embodiment 2.11 gained hollow carbonic acid gas microballoons: from this series of drawing as can be seen, along with tetraethoxy becomes 0.33ml by 0ml, become 0.66ml again, the wall thickness of hollow silica microsphere correspondingly becomes 70nm from 20nm, become 300nm again, explanation is along with the increase of the TEOS amount that adds in the last handling process, and the wall thickness of microballoon thickens.
Embodiment 3
Basic identical with embodiment 2.1, difference is: the thermostat temperature of supercritical reaction still is 25 ℃, it is 150ml/h that carbonic acid gas feeds speed, during hydrolysis earlier with complex microsphere under 20 ℃, ultra-sonic dispersion 5min in the mixing solutions of 10ml ethanol and 0.3ml ammoniacal liquor earlier, and then under the magnetic agitation of 200rpm hydrolysis 24h, centrifugation rate is 6000rpm, and centrifugation time 30min, calcination temperature are 400 ℃, temperature rise rate is 10 ℃/min, and calcination time is 6h.
Embodiment 4
Basic identical with embodiment 2.1, difference is: the thermostat temperature of supercritical reaction still is 60 ℃, it is 300ml/h that carbonic acid gas feeds speed, during hydrolysis earlier with complex microsphere under 40 ℃, ultra-sonic dispersion 15min in the mixing solutions of 10ml ethanol and 4ml ammoniacal liquor earlier, and then under the magnetic agitation of 800rpm hydrolysis 2h, centrifugation rate is 8000rpm, and centrifugation time 20min, calcination temperature are 800 ℃, temperature rise rate is 15 ℃/min, and calcination time is 3h.
Claims (9)
1. one kind is the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere, it is characterized in that: in the mass/volume ratio, the tetraethoxy of the polystyrene microsphere of 0.05～0.5g and 1～8ml do not contacted mutually place 40～60 ℃ of homothermic supercritical reaction containers, feeding carbonic acid gas to pressure simultaneously in this supercritical reaction container is 9～25Mpa, behind reaction 1～10h, unload and be depressed into normal pressure, open reaction vessel and take out the polystyrene microsphere acquisition complex microsphere of handling, and it is dispersed in the mixing solutions of being made up of 0.3～4ml ammoniacal liquor and 10ml ethanol, add the tetraethoxy that 0～0.66ml is arranged simultaneously in this mixing solutions, hydrolysis 2～24h under 20～40 ℃ of temperature, with the system solid-liquid separation after the hydrolysis, promptly get hollow silica microsphere after the complex microsphere calcination of separating then; Wherein, described polystyrene microsphere is a crosslinked polystyrene microsphere.
2. as claimed in claim 1 is the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere, it is characterized in that: the degree of crosslinking of crosslinked polystyrene microsphere is 3～30%.
3. as claimed in claim 2 is the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere, it is characterized in that: used linking agent is ethylene glycol dimethyl double methacrylate or Vinylstyrene during the preparation crosslinked polystyrene microsphere.
As claim 1～3 any one described be the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere, it is characterized in that: polystyrene microsphere is placed supercritical reaction container top, tetraethoxy is placed the supercritical reaction container bottom.
5. as claimed in claim 4 is the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere, it is characterized in that: during calcination, be warming up to 400～800 ℃ of calcination 3～6h with the speed of 5～15 ℃/min.
6. as claimed in claim 5 is the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere, it is characterized in that: during hydrolysis, and first ultra-sonic dispersion 5～15min, and then under the stir speed (S.S.) of 200～800rpm, finish hydrolytic process.
7. as claimed in claim 6 is the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere, and it is characterized in that: polystyrene microsphere wraps up with permeable material.
8. as claimed in claim 7 is the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere, it is characterized in that: the speed that feeds carbonic acid gas is 150～300ml/h.
9. as claimed in claim 8 is the method that template prepares the controlled hollow silica microsphere of wall thickness with the polystyrene microsphere, it is characterized in that: solid-liquid separation is centrifugation, and centrifugal rotational speed is 6000～9500rpm, centrifugation time 10～30min.
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| CN102502668B (en) * | 2011-10-25 | 2013-06-19 | 武汉大学 | Method for preparing hollow silicon dioxide microspheres |
| CN102530969B (en) * | 2012-02-10 | 2014-01-01 | 中国科学院上海硅酸盐研究所 | Method for preparing functional modified hollow mesoporous or core/shell mesoporous silicon dioxide nanometer granules |
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| CN109663573B (en) * | 2019-01-08 | 2022-02-11 | 苏州大学 | Imidazole zeolite framework nano composite material, preparation method and application thereof |
| CN109830670B (en) * | 2019-03-04 | 2021-11-12 | 郑州大学 | Hollow sandwich type SiO for lithium ion battery cathode material2/C/MoS2Hybrid microspheres |
| CN111573747B (en) * | 2020-05-06 | 2021-08-03 | 电子科技大学 | Preparation method of hollow microsphere material for lithium-sulfur battery positive electrode |
| CN111564614B (en) * | 2020-05-11 | 2022-07-01 | 厦门高容纳米新材料科技有限公司 | Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery |
| CN114790003B (en) * | 2022-03-29 | 2024-02-27 | 中触媒新材料股份有限公司 | Preparation method of simple and controllable hollow mesoporous silica microspheres |
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