CN104003409A - Method for preparing controllable monodisperse spherical large-particle-size nano-silicon dioxide - Google Patents
Method for preparing controllable monodisperse spherical large-particle-size nano-silicon dioxide Download PDFInfo
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- CN104003409A CN104003409A CN201410259362.2A CN201410259362A CN104003409A CN 104003409 A CN104003409 A CN 104003409A CN 201410259362 A CN201410259362 A CN 201410259362A CN 104003409 A CN104003409 A CN 104003409A
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Abstract
The invention relates to a method for preparing controllable monodisperse spherical large-particle-size nano-silicon dioxide. According to the method, on the basis of the Stober sol-gel method, tetraethoxysilane hydrolyzes to obtain orthosilicic acid, and dehydration synthesis is carried out through the method for replenishing tetraethoxysilane intermittently to obtain silicon dioxide. The method is simple in technological process, moderate in condition, high in production efficiency and suitable for industrial production, and the post-treatment mode is easy and convenient to perform. By replenishing the reagent intermittently, the large-particle-size nano-silicon dioxide particles can be synthesized in a controllable mode. The nano-silicon dioxide particles obtained through the preparation method have the advantages of being regular in spherical shape, excellent in monodispersity and the like.
Description
Technical field:
The present invention relates to the preparation method of the large grain diameter nano silicon-dioxide of a kind of controlled monodisperse spherical, utilize
the method that sol-gel method is combined with intermittent injecting reactant, the spherical SiO that controlledly synthesis monodispersity is good
2particle, belongs to the synthetic field of nano material.
Background technology:
In recent years, nano-silicon dioxide particle has research more widely in scientific research and industrial circle.Wherein, nano silicon can be used for the preparation of shear thickening liquid, for the research of soft bullet-resistant garment.Shear thickening fluid is to be generally dispersed in liquid and to be obtained by certain density solids.Shear thickening fluid is generally made up of two-phase dispersion system, and one is made up of nanoparticle mutually, such as silicon-dioxide, calcium carbonate, PMMA particle etc., and another is carrier fluid mutually, such as water, polyoxyethylene glycol etc., dispersed phase particles disperses wherein.Shear thickening fluid is a kind of non-Newtonian fluid, and shear thickening behavior is the behavior that certain density dispersion system shows, and when higher than critical shear rate, its viscosity sharply rises, and macroscopic view is the transformation of liquid dispersion system to solid-phase.
The particle diameter of nano-silicon dioxide particle and monodispersity have a great impact the performance of shear thickening system.Wherein, along with nano particle diameter reduces, shear thickening system critical shear rate increases.The monodispersity of nano-silicon dioxide particle declines, and causes the critical thickening starting point of system to move to high shear rate direction.This is disadvantageous for STF in the application aspect soft protective material.Therefore, the requirement of the nano-silicon dioxide particle of good, the large particle diameter of preparation monodispersity is very urgent.
For the synthesis technique of nano-silicon dioxide particle, mainly contain at present three kinds of methods.Pileni utilizes microemulsion method to prepare size can to reach the silicon dioxide granule of thousands of nanometers.This method with
synthetic method is compared, and be more suitable for the silicon dioxide granule at 30-60nm in compound particle size, and particle has good monodispersity.But this preparation process needs a large amount of tensio-active agent (in general large than the massfraction of silicon dioxide granule) formation to stablize micelle.Therefore, product pellet needs further to process, to eliminate the tensio-active agent of particle surface.In addition, maintain stable homogeneous micella composition in soft sensitivity in mutually also very difficult.
Balthis and Mendenhall (J.H.Balthis.P.Wendenhall.Prepration of sols from finely divided silicon, USP2614994.1952) reported a kind of method for hydrolysis that utilizes pre-treatment elemental silicon, the single small particle size nano silicon that disperses of preparation.Reaction is by ammonia-catalyzed, and temperature of reaction is controlled at 20-90 DEG C.Meanwhile, the clear superiority of this method, is before reaction, and reactant is through acid solution, deionized water, and ethanol, ether are processed successively, and the oxide containing silicon of particle surface can be removed, outside clean silicon face is exposed to.In patent, prepared the good nano-silicon dioxide particle of 8-15nm regularity, the particle diameter that this patent provides is less, can not meet the required size of particles requirement of preparation shear thickening liquid.
The present invention with
sol-gel method is basis, probes into affecting the synthetic processing condition of particle, has optimized catalyst concn, TEOS and has reacted the factors such as mol ratio with water.Control reaction conditions, under less dropping number of times, made dispersed good, large grain diameter nano silicon dioxide granule.Reaction system is simple, aftertreatment is easily gone, and is the method for the large grain diameter nano silicon-dioxide of controlledly synthesis.
Summary of the invention:
The object of this invention is to provide the preparation method of the large grain diameter nano silicon-dioxide of a kind of controlled monodisperse spherical, with
sol-gel method is basis, and tetraethoxy obtains orthosilicic acid through hydrolysis, by the method for intermittent injecting tetraethoxy, dehydrating condensation obtains silicon-dioxide, and the method technical process is simple, mild condition, post processing mode is easy, and production efficiency is high, is applicable to suitability for industrialized production.By intermittent injecting reactant, the large grain diameter nano silicon dioxide granule of controlledly synthesis.The nano-silicon dioxide particle product that this preparation method obtains has spherical regular, the feature such as monodispersity is good.
The present invention with
sol-gel method is basis, tetraethoxy (TEOS) obtains orthosilicic acid through hydrolysis, dehydrating condensation obtains silicon-dioxide, adopts weak base catalysis, and the method for intermittently adding step by step tetraethoxy makes good, the spherical large grain diameter nano silicon-dioxide of monodispersity.
The preparation method of the large grain diameter nano silicon-dioxide of controlled monodisperse spherical provided by the invention, concrete steps and condition are:
(1) ammoniacal liquor is scattered in dehydrated alcohol or ethanolic soln, the mol ratio of ethanol and ammoniacal liquor is 8～40:1, preferably 10～20:1, and dispersed with stirring is even; Tetraethoxy is added in mixing solutions, and control rate of addition is 10～60ml/min, preferably 20～40ml/min, tetraethoxy and H
2o mol ratio is 1:2～20, preferably 1:3～6;
(2), under normal temperature, control stirring velocity 200～750r/min, preferably 500-750r/min, reaction times 2～8h, preferably 4～6h, obtains silicon dioxide gel;
(3) in the silicon dioxide gel obtaining in step (2), drip tetraethoxy, adding and adding the mol ratio of tetraethoxy in the amount of tetraethoxy and step (1) is 1:10～4:1; Preferably 1:2～4:1.Preferably point carry out for 2～4 times adding of tetraethoxy, after being added dropwise to complete at every turn, stirring reaction 2～4h, then drip next time.
(4) reactant that step (3) obtains is through centrifugation, remove supernatant liquor, product is scattered in solvent again, through dispersion, centrifugation again repeatedly, until supernatant liquor is neutral, the preferred ultrasonic dispersion of dispersing mode, solvent is selected from dehydrated alcohol, acetone or deionized water, make target product finally by vacuum-drying, oven dry, bake out temperature is preferably 60-90 DEG C.
Reaction equation prepared by silicon-dioxide is:
Si(OC
2H
5)
4+2H
2O→SiO
2+4C
2H
5OH
Wherein, the hydrolysis of tetraethoxy: Si (OC
2h
5)
4+ 4H
2o → Si (OH)
4+ 4C
2h
5oH is main reaction, and this reaction is Si (OC
2h
5)
4nucleophilic substitution reaction, the Siliciumatom positively charged in TEOS, in reaction process, the Siliciumatom of the hydroxyl radical attacks positively charged of water, oxyethyl group is left away, and obtains orthosilicic acid.Base catalysis is conducive to the carrying out of nucleophilic substitution reaction, and in this reaction system, ammoniacal liquor is catalyzer, and along with the increase of catalyst concn, particle diameter increases, but size distribution broadens, and monodispersity declines.Therefore, for take into account particle diameter, particle spherical with the problem such as monodispersity, need to select suitable ammonia concn, this is also key problem in technology of the present invention.
In the dispersion process of step (1), add the process of tetraethoxy, not only need to control tetraethoxy add-on, also need to control and add speed, preferably the mol ratio of tetraethoxy and water is 1:3～1:6, rate of addition is 20～40ml/min preferably, and especially, in the time that ammonia concn is higher, the rate of addition of TEOS has larger impact to balling-up regularity and particle diameter.
In the reaction process of step (2), stirring velocity is preferably 500-750r/min.In reaction process, stirring velocity is constant, avoids the nanoparticle generating to reunite.Reaction times is preferably 4-6h.The particle diameter for the treatment of nano-silicon dioxide particle no longer changes, and reactant reacts completely, and particle forms stable spherical.
In step (3) in order to obtain large grain diameter nano silicon dioxide granule, adopt " intermittently dripping growth method ", in the nano-silicon dioxide particle colloidal sol having formed, add tetraethoxy, taking generate silicon-dioxide as core, by the further reaction of tetraethoxy, particle diameter is increased.Adding in the amount of tetraethoxy and step (1) adds the mol ratio of tetraethoxy to be preferably 1:2～4:1.In reaction process, interval sampling characterizes, to obtain the silicon dioxide granule of required particle diameter.
The present invention compared with prior art, has the following advantages:
Under existing reaction system, determine the processing parameter that affects particle diameter and regularity in sol-gel method.Adopt substep to add the method for reactant, realized the large grain diameter nano silicon dioxide granule of controlledly synthesis, and particle monodispersity is good.The method technical process is simple, mild condition, and post processing mode is easy, and production efficiency is high, is applicable to suitability for industrialized production.In addition, the large grain diameter nano silicon dioxide granule that patent supplying method synthesizes, in shear thickening liquid field, has potential using value.
The present invention characterizes the testing tool of using: German BRUKER TENSOR27 type Fourier infrared spectrograph, the S4800 of Hitachi scanning electronic microscope (sweep voltage 5KV), the Tecnai G of FEI Hong Kong company limited
220 transmission electron microscopes, Japanese Shimadzu XRD-6000, MCR301 rheometer.
The main experimental drug that the present invention is used: ammoniacal liquor, analytical pure, Beijing Chemical Plant; Tetraethoxy, analytical pure, Beijing Yili Fine Chemicals Co., Ltd.; Ethanol, analytical pure, Beijing Chemical Plant; Acetone, analytical pure, Beijing Chemical Plant.
Brief description of the drawings:
Fig. 1. the particle diameter that embodiment 1 makes is about 290nm SiO
2sEM picture
Fig. 2. the SiO that embodiment 1 makes
2infrared spectrum
Fig. 3. the particle diameter that embodiment 2 makes is about 340nm SiO
2sEM picture
Fig. 4. embodiment 2 makes SiO
2xRD spectra
Fig. 5. the particle diameter that embodiment 3 makes is about 410nm SiO
2sEM picture
Fig. 6. the particle diameter that embodiment 3 makes is about 410nm SiO
2tEM picture
Fig. 7. the SEM picture (1) of the MP4540M silicon-dioxide that Japanese Nissan chemical company produces
Fig. 8. the SEM picture (2) of the MP4540M silicon-dioxide that Japanese Nissan chemical company produces
Fig. 9. the particle diameter that embodiment 4 makes is about 500nm SiO
2sEM picture
Figure 10. the particle diameter that embodiment 5 makes is about 600nm SiO
2sEM picture
Figure 11. the STF viscosity of massfraction 53.5% is with the change curve of shearing rate
Figure 12. the STF viscosity of massfraction 53.5% is with the change curve of shear-stress
From the stereoscan photograph of Fig. 1, Fig. 3, Fig. 5, Fig. 9, Figure 10 silicon dioxide granule, by controlling the processing condition of embodiment 1-5, prepare spherical regular, the particle that monodispersity is good of the about 300-600nm of particle diameter.Infrared, XRD from Fig. 2, Fig. 4 and Fig. 6 to product pellet and TEM (transmission electron microscope) analysis, the particle of known preparation is noncrystal solid spherical silicon dioxide granule.From Fig. 5, Fig. 6, the 410nm particle that embodiment 3 makes and the MP4540M particle contrast of producing from Japanese Nissan chemical company, product pellet that method provided by the invention makes spherical regular, monodispersity is excellent.
Figure 11, Figure 12 are that the silicon dioxide granule that utilizes particle diameter in embodiment 5 to be about 600nm is prepared STF, massfraction is 53.5%, by its rheology testing, the critical thickening starting point of system is lower, compared with showing shear thickening behavior under low shear rate, illustrate that prepared product has using value.
Embodiment:
Below in conjunction with comparative example and embodiment, the present invention is described further.
Embodiment 1
(1) a certain amount of ammoniacal liquor is scattered in ethanolic soln, the mol ratio of ethanol and ammoniacal liquor is 16:1, and electric stirring is uniformly dispersed, and tetraethoxy is added in mixing solutions, and control rate of addition is 25ml/min, TEOS and H
2o mol ratio is 1:5.
(2) normal temperature, controls stirring velocity 650r/min, and reaction 5h, obtains silicon dioxide gel.
(3) in the silicon dioxide gel obtaining in step (2), substep adds TEOS, controlling 650r/min constant speed stirs, constant pressure funnel drips TEOS, control rate of addition is 25ml/min, with the mol ratio of the TEOS adding in step (1) be 1:2, once add, after dropwising, control 650r/min constant speed and stir, reaction 4h.
(4) reactant that step (3) obtains, through centrifugation, is removed supernatant liquor, and centrifugal thing is scattered in acetone again.Redissolve, lock out operation are neutral to supernatant liquor.
(5) product is placed in to vacuum drying oven, in 80 DEG C, dries 20h.
Sampling respectively after step (1) and step (3) are added TEOS, by SEM and laser particle size analysis test, the particle diameter that step (1) obtains is about 170nm, and after step (3) reaction finishes, obtaining particle diameter is 290nm.In addition, from infrared test result, the method has successfully been prepared nano-silicon dioxide particle, and post-treating method is feasible, and product purity is high.
Analyze 1103cm from product infrared spectrum
-1the absorption band of Qiang Erkuan is Si-O-Si antisymmetric stretching vibration peak, 800cm
-1, 470cm
-1the peak at place is Si-O key symmetrical stretching vibration peak, 3442cm
-1the broad peak at place is water of constitution-OH antisymmetric stretching vibration peak, 1633cm
-1near peak is the H-O-H flexural vibration peak of water, 950cm
-1the peak at place belongs to the flexural vibration absorption peak of Si-OH.
In spectrogram, without the assorted peak of other groups, illustrate that preparation and last handling process are feasible.
Embodiment 2
(1) a certain amount of ammoniacal liquor is scattered in ethanolic soln, the mol ratio of ethanol and ammoniacal liquor is 13:1, and electric stirring is uniformly dispersed, and tetraethoxy is added in mixing solutions, and control rate of addition is 20ml/min, TEOS and H
2o mol ratio is 1:4.
(2) normal temperature, controls stirring velocity 600r/min, and reaction 5h, obtains silicon dioxide gel.
(3) in the silicon dioxide gel obtaining in step (2), substep adds TEOS, control stirring velocity 600r/min, constant pressure funnel drips TEOS, control rate of addition is 20ml/min, with the mol ratio of the TEOS adding in step (1) be 1:1, add at twice, after dropwising at every turn, control stirring velocity 600r/min constant speed and stir, reaction 3h.
(4) reactant that step (3) obtains, through centrifugation, is removed supernatant liquor, and centrifugal thing is scattered in dehydrated alcohol again.Redissolve, lock out operation are neutral to supernatant liquor.
(5) product is placed in to vacuum drying oven, in 70 DEG C, dries 22h.
Sampling respectively after step (1) and step (3) are added TEOS, by SEM and laser particle size analysis test, the particle diameter that step (1) obtains is about 210nm, step is added TEOS twice in (3), finally obtains the silicon dioxide granule that particle diameter is 340nm.Illustrate through substep and add TEOS, can make silicon-dioxide particle diameter increase gradually, and reaction conditions gentleness, reaction process is controlled.
In addition, from the XRD figure spectrum of particle, be about 23 ° occur wide diffraction peak at 2 θ, the nanoparticle that reaction makes is non-crystalline material.
Embodiment 3
(1) a certain amount of ammoniacal liquor is scattered in ethanolic soln, the mol ratio of ethanol and ammoniacal liquor is 11:1, and electric stirring is uniformly dispersed, and tetraethoxy is added in mixing solutions, and control rate of addition is 40ml/min, TEOS and H
2o mol ratio is 1:6.
(2) normal temperature, controls stirring velocity 700r/min, and reaction 6h, obtains silicon dioxide gel.
(3) in the silicon dioxide gel obtaining in step (2), substep adds TEOS, control stirring velocity 700r/min, constant pressure funnel drips TEOS, control rate of addition is 40ml/min, with the mol ratio of the TEOS adding in step (1) be 2:1, point add for three times, after dropwising at every turn, control stirring velocity 700r/min constant speed and stir, reaction 2h.
(4) reactant that step (3) obtains, through centrifugation, is removed supernatant liquor, and centrifugal thing is scattered in dehydrated alcohol again.Redissolve, lock out operation are neutral to supernatant liquor.
(5) product is placed in to vacuum drying oven, in 90 DEG C, dries 16h.
After step (1) has been reacted with step (3), sampling characterizes by SEM and laser particle size analysis test, the particle diameter that step (1) obtains is about 260nm, after step (3) reacts completely, particle diameter is 410nm (as Fig. 8 shows), Fig. 9 and Figure 10 are the scanning electron microscope picture of the MP4540M (large particle is 450nm) of Japanese Nissan chemical company production, contrast known, the product pellet that embodiment 4 obtains is spherical regular, and monodispersity is good.
Embodiment 4
(1) a certain amount of ammoniacal liquor is scattered in ethanolic soln, the mol ratio of ethanol and ammoniacal liquor is 10:1, and electric stirring is uniformly dispersed, and tetraethoxy is added in mixing solutions, and control rate of addition is 30ml/min, TEOS and H
2o mol ratio is 1:1.
(2) normal temperature, controls stirring velocity 750r/min, and reaction 6h, obtains silicon dioxide gel.
(3) in the silicon dioxide gel obtaining in step (2), substep adds TEOS, control stirring velocity 750r/min, constant pressure funnel drips TEOS, with the mol ratio of the TEOS adding in step (1) be 1:3, divide and add for three times, after dropwising, control stirring velocity 750r/min constant speed and stir, reaction 2h.
(4) reactant that step (3) obtains, through centrifugation, is removed supernatant liquor, and centrifugal thing is scattered in deionized water again.Redissolve, lock out operation are neutral to supernatant liquor.
(5) product is placed in to vacuum drying oven, in 90 DEG C, dries 16h.
After step (3) has been reacted, sampling characterizes by SEM and laser particle size analysis test, and the particle diameter obtaining is about 500nm, can be observed product pellet spherical regular from the scanning electron microscope picture of product pellet, and monodispersity is good.
Embodiment 5
(1) a certain amount of ammoniacal liquor is scattered in ethanolic soln, the mol ratio of ethanol and ammoniacal liquor is 10:1, and electric stirring is uniformly dispersed, and tetraethoxy is added in mixing solutions, and control rate of addition is 30ml/min, TEOS and H
2o mol ratio is 1:1.
(2) normal temperature, controls stirring velocity 750r/min, and reaction 6h, obtains silicon dioxide gel.
(3) in the silicon dioxide gel obtaining in step (2), substep adds TEOS, control stirring velocity 750r/min, constant pressure funnel drips TEOS, control rate of addition is 30ml/min, with the mol ratio of the TEOS adding in step (1) be 1:4, point add for 4 times, after dropwising at every turn, control stirring velocity 750r/min constant speed and stir, reaction 2h.
(4) reactant that step (3) obtains, through centrifugation, is removed supernatant liquor, and centrifugal thing is scattered in deionized water again.Redissolve, lock out operation are neutral to supernatant liquor.
(5) product is placed in to vacuum drying oven, in 90 DEG C, dries 16h.
After step (3) has been reacted, sampling characterizes by SEM and laser particle size analysis test, and the particle diameter obtaining is about 600nm, can be observed product pellet spherical regular from the scanning electron microscope picture of product pellet, and monodispersity is good.
The particle diameter that embodiment 5 is made is about the silicon dioxide granule of 600nm for the preparation of shear thickening liquid, and 4.6g product pellet is scattered in 4gPEG400 (polyoxyethylene glycol), adds dehydrated alcohol 40ml to increase system dispersiveness.Room temperature magnetic agitation is disperseed 6h, obtains uniform dispersion system.System, in 80 DEG C of water-bath distillation processing, is removed to small-molecule substance ethanol, obtain the STF of massfraction 53.5%.System is cooled to after room temperature, vacuumizes, with the bubble in the system of removing.
The shear thickening liquid preparing utilizes MCR301 rheometer to carry out rheometer test, and test procedure is:
1,0.1-1000pa carries out stress scans 180s
2, creep 60s under the shearing rate of 1s-1
3,, in zero shearing, zero stress is replied 60s
4, from 0.1-1000pa stress scans
If Figure 11, Figure 12 viscosity that is shear thickening fluid is with the change curve of shearing rate and shear-stress, shear thickening system as can be seen from Figure 11 presents shear shinning characteristic, 0.2s at low shear rate
-1for critical thickening point, when shearing rate further increases, system viscosity has a larger variation, shows the performance of shear thickening.With domestic literature comparison, critical thickening starting point is lower,, under low shear rate, can show the performance of shear thickening.(Xu Yulei, Gong Xinglong, Jiang Wanquan, etc. the preparation of STF and performance characterization thereof [J]. functional materials, 2007,38 (10): 3904-3906.).
Claims (10)
1. the preparation method of the large grain diameter nano silicon-dioxide of controlled monodisperse spherical, taking sol-gel method as basis, obtain orthosilicic acid by teos hydrolysis, dehydrating condensation obtains silicon-dioxide, adopt weak base catalysis, intermittently substep is added the method for tetraethoxy, makes the large grain diameter nano silicon-dioxide of monodisperse spherical.
2. according to the preparation method of claim 1, it is characterized in that: concrete steps and condition are:
(1) ammoniacal liquor is scattered in dehydrated alcohol or ethanolic soln, the mol ratio of ethanol and ammoniacal liquor is 8～40:1, and dispersed with stirring is even; Tetraethoxy is added in mixing solutions, and control rate of addition is 10～60ml/min, tetraethoxy and H
2o mol ratio is 1:2～20;
(2), under normal temperature, stirring reaction 2～8h, obtains silicon dioxide gel;
(3) in the silicon dioxide gel obtaining in step (2), drip tetraethoxy, adding and adding the mol ratio of tetraethoxy in the amount of tetraethoxy and step (1) is 4:1～1:10;
(4) reactant that step (3) obtains, through separating, is removed supernatant liquor, and product obtains target product through washing, be dried, drying.
3. according to the preparation method of claim 1, it is characterized in that: in step (1), the mol ratio of ethanol and ammoniacal liquor is 10～20:1, tetraethoxy and H
2the mol ratio of O is 1:3～6, and control rate of addition is 20～40ml/min.
4. according to the preparation method of claim 1, it is characterized in that: in step (3), adding and adding the mol ratio of tetraethoxy in the amount of tetraethoxy and step (1) is 1:10～4:1.
5. according to the preparation method of claim 1 or 4, it is characterized in that: point carry out for 2～4 times adding of tetraethoxy in step (3), after being added dropwise to complete at every turn, stirring reaction 2～4h, then drip next time.
6. according to the preparation method of claim 3, it is characterized in that: in the reaction of step (2), controlling stirring velocity is 200～750r/min.
7. according to the preparation method of claim 1 or 6, it is characterized in that: the reaction times of step (2) is 4～6h.
8. according to the preparation method of claim 1, it is characterized in that: the product of removing after supernatant liquor in step (4) is scattered in solvent again, through dispersion, centrifugation again repeatedly, until supernatant liquor is neutral, solvent is selected from dehydrated alcohol, acetone or deionized water, makes target product finally by vacuum-drying, oven dry.
9. preparation method according to Claim 8, is characterized in that: in step (4), dispersing mode is ultrasonic dispersion.
10. preparation method according to Claim 8, is characterized in that: in step (4), bake out temperature is 60-90 DEG C.
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| CN106365172A (en) * | 2016-11-15 | 2017-02-01 | 中国海油石油总公司 | Preparation method of spherical silicon dioxide |
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