CN110203936A - One kind having surface topology nano silica microsphere and preparation method thereof - Google Patents
One kind having surface topology nano silica microsphere and preparation method thereof Download PDFInfo
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- CN110203936A CN110203936A CN201910508292.2A CN201910508292A CN110203936A CN 110203936 A CN110203936 A CN 110203936A CN 201910508292 A CN201910508292 A CN 201910508292A CN 110203936 A CN110203936 A CN 110203936A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/141—Preparation of hydrosols or aqueous dispersions
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- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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Abstract
The invention discloses a kind of preparation methods with surface topology nano silica microsphere, comprising the following steps: under agitation, first mixes silicon source according to a certain percentage with deionized water；Then, small molecule surface reactive material (R-X) is added, obtains the mixed liquor of clear；Then, basic catalyst is added, reaction generates silicon dioxide gel (a)；Then, ammonia spirit is added, reaction generates silicon dioxide gel (b)；Finally, being obtained described with surface topology nano silica microsphere after being separated by solid-liquid separation, being washed to silicon dioxide gel (b).The features such as preparation method of the present invention is simple, mild condition, granular size are controllable and reaction is of large quantities, is a kind of environmental-friendly synthetic method, is with a wide range of applications.
Description
Technical field
The present invention relates to a kind of preparation methods with surface topology nano silica microsphere, and in particular to a kind of
Green has surface topology nano silica microsphere and preparation method thereof in batches, belongs to chemistry and inorganic material class skill
Art field.
Background technique
It is classicalMethod prepares monodisperse silica microspheres, uses alcohol as solvent, and water is urged as reactant, ammonium hydroxide
Agent.Alcohol, water and catalyst are first generally mixed to get alcohol-water-ammonia aqueous solution, then, under stirring conditions, by silicon
Source/alcoholic solution is added dropwise in alcohol-water-ammonia aqueous solution, and silicon source hydrolyzes to obtain (Si (OH)4), Si (OH)4Polycondensation-growth, obtains table
The smooth solid silicon dioxide microsphere in face.Coating, ceramics, cosmetics, colloidal crystal, in terms of be all widely used.
But it is limited with the smooth solid silicon dioxide microsphere specific surface area in surface and internal cavities, in the side such as absorption, catalysis, biomedicine
Difficulty is put in the application in face to good use.
With surface topology nano material in the targeting conveying of drug, pharmaceutical carrier, genophore, contrast agent, cancer
The fields of biomedicine such as disease treatment have extensive potential application.And organic material carrier itself intrinsic heat, chemical stability
The defect of difference causes the drug of cladding to be easy to generate the explosive release of drug because of the decomposition of organic carrier in human body,
And organic carrier haves the shortcomings that drug covering amount is relatively low.Inorganic nano pharmaceutical carrier with cellular structure has high
Drug load, easily modified inside and outside duct, good thermally and chemically stability, in the early diagnosis and targeting of major disease
Distinctive advantage is had shown that in drug conveying.Especially silica (SiO2) base mesoporous material have good biofacies
Capacitive and degradability (Journal of Inorganic Materials, 2013,28,1-11.).Surface topology nano silica microsphere with
Certain surface design feature and physical mechanical strength and biggish specific surface area cause extensive research interest
(Adv.Mater.2013, DOI:10.1002/adam.201302189).
The synthetic work of surface topology nano silica nanosphere has had made some progress.But current surface
A variety of surfactants (CN 103663478), synthesis technology are used in the synthesis of topological structure nano silica nanosphere
Complexity, and be difficult to batch and prepare.
Summary of the invention
To overcome the problems of the above-mentioned prior art, the present invention provides a kind of tools for not needing addition surfactant
There is the preparation method of surface topology nano silica microsphere.First by silicon source and water and small molecule surface reactive material medium
It mixes according to a certain percentage, obtains the mixed liquor of clear；On this basis, basic catalyst is added, starting reaction generates
Silicon dioxide gel (a), ammonia spirit is added into colloidal sol, and reaction generates silicon dioxide gel (b)；To obtained silica
Colloidal sol (b) is separated by solid-liquid separation, is washed, and is obtained described with surface topology nano silica microsphere.Present invention preparation
Target product have high-specific surface area (84.91~426.02m2/ g), have in absorption, catalysis, biomedical aspect wide
Application prospect have surface topology nano silica microsphere.
In order to achieve the goal above, the technical scheme adopted by the invention is as follows:
A kind of preparation method with surface topology nano silica microsphere, comprising the following steps:
(1) silicon source/H2The preparation of O emulsion: silicon source is mixed with deionized water, obtains silicon source/H2O emulsion；
(2) silicon source/R-X/H2The preparation of O mixed liquor: under agitation, by small molecule surface reactive material and step
(1) silicon source/H obtained2O emulsion is mixed, and silicon source/R-X/H of clear is obtained2O mixed liquor；
(3) preparation of silicon dioxide gel: silicon source/R-X/H that basic catalyst addition step (2) is obtained2O mixed liquor
Middle reaction certain time generates silicon dioxide gel (a)；
(4) with the preparation of topological structure silicon dioxide gel: under certain temperature, stirring condition, by ammonia spirit plus
Enter the silicon dioxide gel (a) that step (3) obtains, reacts certain time, obtain silicon dioxide gel (b)；
(5) silicon dioxide gel (b) obtained to step (4) is separated by solid-liquid separation, is washed, and obtains described opening up with surface
Flutter structure nano silicon dioxide microsphere.
In step (1) of the present invention, the mixing of the silicon source and deionized water carries out under agitation, and the stirring turns
Speed is 200~300rpm；It preferably, is 200rpm, 250rpm, 300rpm.
In step (1) of the present invention, the mixed temperature is 15~30 DEG C；It preferably, is room temperature (20 DEG C), 30 DEG C.
In step (1) of the present invention, the mixed time is 1~3 hour；Preferably, it is 1~2 hour；Further preferably
Ground is 2 hours.
In step (1) of the present invention, the silicon source includes esters of silicon acis (including but not limited to methyl silicate, silester, silicic acid
Propyl ester etc.), silane coupling agent (including but not limited to gamma-aminopropyl-triethoxy-silane (KH550), γ-(the third oxygen of 2,3- epoxy)
Propyl trimethoxy silicane (KH560), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), γ-mercapto propyl three
Ethoxysilane (KH580), γ-mercaptopropyl trimethoxysilane (KH590), vinyltriethoxysilane (KH151), ethylene
Base trimethoxy silane (KH171) etc.) one of or it is a variety of；Preferably, it is silester (TEOS).
In step (1) of the present invention, the volume ratio of the silicon source and deionized water: 1: 50≤VSilicon source∶VH2O≤1:5；Preferably,
It is 1: 5,1: 10,1: 50 or 3: 50.
In step (2) of the present invention, the revolving speed of the stirring is 200rmp~300rmp；Be preferably, 200rpm,
250rpm、300rpm。
In step (2) of the present invention, the mixed temperature is 15~30 DEG C；Preferably, it is room temperature (20 DEG C).
In step (2) of the present invention, the mixed time is 1~3 hour；Preferably, it is 2 hours.
In step (2) of the present invention, the small molecule surface reactive material, for small organic molecule that is miscible with water and not dissociating
Substance；Its molecular formula is R-X, wherein R is alkyl；X is hydroxyl, ketone group, aldehyde radical etc..
Wherein, the small molecule organic compound includes alcohol, aldehyde, ketone etc.；It preferably, is the alkylol containing C1-C4；Further
It preferably, is methanol (CH3OH), ethyl alcohol (C2H5OH), isopropanol ((CH3)2CHOH), sec-butyl alcohol (CH3CH2CH(OH)CH3), uncle
Butanol ((CH3)3COH one of) or a variety of；It is further preferred that being ethyl alcohol.
In step (2) of the present invention, the small molecule surface reactive material can be, but not limited to be that analysis is pure.
In step (2) of the present invention, the small molecule surface reactive material and silicon source/H2The volume ratio of O emulsion be 1: 2~
8:5；It preferably, is 3: 5~8: 5；It is further preferred that being 10: 11,32: 33,50: 33.
In step (2) of the present invention, the silicon source is in silicon source/R-X/H2Concentration in O mixed liquor is 0.05~0.5M；It is preferred that
Ground is 0.05~0.42M；It is further preferred that being 0.05M, 0.19M, 0.36M.
In step (3) of the present invention, the reaction carries out under the conditions of 20~60 DEG C；It preferably, is 20 DEG C~40 DEG C, 40 DEG C
~60 DEG C；It is further preferred that being room temperature (20 DEG C), 40 DEG C or 60 DEG C.
In step (3) of the present invention, the time of the reaction is 2~5 hours；Preferably, it is 3 hours.
In step (3) of the present invention, the reaction carries out under agitation, and the revolving speed of the stirring is 200~300rpm；
It preferably, is 200rpm, 250rpm, 300rpm.
In step (3) of the present invention, the basic catalyst is alkalescent catalyst, is selected from ammonium hydroxide, Na2CO3,NaAc；It is preferred that
Ground is ammonium hydroxide；It is further preferred that being the ammonia spirit of 28% (mass fraction).
In step (3) of the present invention, silicon source/R-X/H that step (2) obtain is added in basic catalyst2In O mixed liquor, open
Dynamic reaction.Concentration of the basic catalyst in entire reaction system is 0.2~2.0mol/L；Preferably, 0.2mol/L,
0.3mol/L, 0.4~1.5mol/L, 2.0mo1/L.It is further preferred that the concentration of ammonia-catalyzed agent is in entire reaction system
0.4~1.5mol/L；It is further preferred that the concentration of ammonia-catalyzed agent be 0.44mol/L, 0.59mol/L, 0.74mol/L,
1.48mol/L。
In step (3) of the present invention, it is preferable that be added before catalyst reacted, first by the silicon source of step (2) preparation/
R-X/H2O mixed liquor is heated to reaction temperature, and keeps the temperature 15min~25min；Preferably, 15min or 25min is kept the temperature.
In step (4) of the present invention, the certain temperature is 15~30 DEG C；It preferably, is room temperature (20 DEG C), 30 DEG C.
In step (4) of the present invention, the revolving speed of the stirring is 200~300rpm；Be preferably, 200rpm, 250rpm,
300rpm。
In step (4) of the present invention, the volume and silicon dioxide gel (a) volume ratio of the ammonium hydroxide of addition are 3: 1~6: 1；It is excellent
Selection of land is 17: 5,50: 11,11: 2.
In step (4) of the present invention, the concentration of the ammonium hydroxide is 3.5%~2.5%；Preferably, for 3.3%, 2.8%,
3.0%.
In step (4) of the present invention, certain reaction time is 8~12 hours；Preferably, it is 10 hours.
In step (5) of the present invention, described be separated by solid-liquid separation includes centrifuge separation, spray drying, cryospray drying；It is preferred that
Ground, for centrifuge separation.
In step (5) of the present invention, the condition that is centrifugated in the separation of solid and liquid are as follows: revolving speed can be 8000rmp or more；
It preferably, is 8000~15000rmp；It is further preferred that for 8000rmp, 9000rmp, 10000rmp, 12000rmp,
13000rmp、15000rmp。
In step (5) of the present invention, the temperature being centrifugated in the separation of solid and liquid is 20~30 DEG C；It preferably, is room temperature
(25℃)。
In step (5) of the present invention, the time being centrifugated in the separation of solid and liquid is 10~30min；Preferably, it is
10min、20min、30min。
It can also include using organic solvent to preparation after being centrifugated in the separation of solid and liquid in step (5) of the present invention
There is the step of surface topology nano silica microsphere is washed；Preferably, first with deionized water to table
Face topological structure nano silicon dioxide microsphere washs 3 times, then with ethanol washing 3 times.
In the present invention, preparation method condition is different, and the surface topology nano silica microsphere being prepared is different,
But it is uniform using the surface topology nano silica microsphere size that specified conditions of the invention are prepared, it can prepare
Surface topology nano silica microsphere particle size range between 100~250nm (e.g., can be 103nm,
110nm, 115nm, 122nm, 225nm, 227nm, 250nm), the silicon dioxide microsphere has surface topology (as implemented
The silicon dioxide microsphere TEM figure that example 1~7 obtains, is shown in Fig. 1~7).
Have surface topology nano silica micro- the invention also provides prepared by the preparation method
Ball.
Wherein, the partial size with surface topology nano silica microsphere is 100-250nm；Preferably, it is
103nm、110nm、115nm、122nm、225nm、227nm、250nm。
The invention also provides it is described have surface topology nano silica microsphere absorption, catalyst carrier,
Application in the fields of biomedicine such as targeted drug delivery, pharmaceutical carrier, genophore, contrast agent, treatment of cancer.
Preparation method provided by the invention with surface topology nano silica microsphere compared to the prior art,
It has the advantage that
(1) present invention, which mainly does solvent preparation with aqueous medium, has surface topology nano silica microsphere, does not make
It with surfactant, can effectively lower production cost, reduce pollutant emission.
(2) present invention is in classicsOn the basis of method, have that method is simple, mild condition, granular size are controllable and
React the features such as of large quantities.
(3) prepared by the present invention that there is surface topology nano silica microsphere to have in terms of absorption, catalysis extensively
Application prospect, and the side such as biomedicines such as the targeting conveying in drug, pharmaceutical carrier, genophore, contrast agent, treatment of cancer
Face has extensive potential application.
Detailed description of the invention
Fig. 1 is the TEM figure with surface topology nano silica microsphere prepared by embodiment 1.
Fig. 2 is the TEM figure with surface topology nano silica microsphere prepared by embodiment 2.
Fig. 3 is the TEM figure with surface topology nano silica microsphere prepared by embodiment 3.
Fig. 4 is the TEM figure with surface topology nano silica microsphere prepared by embodiment 4.
Fig. 5 is the TEM figure with surface topology nano silica microsphere prepared by embodiment 5.
Fig. 6 is the TEM figure with surface topology nano silica microsphere prepared by embodiment 6.
Fig. 7 is the TEM figure with surface topology nano silica microsphere prepared by embodiment 7.
Specific embodiment
In conjunction with following specific embodiments and attached drawing, the present invention is described in further detail, protection content of the invention
It is not limited to following embodiment.Without departing from the spirit and scope of the invention, those skilled in the art it is conceivable that change
Change and advantage is all included in the present invention, and using appended claims as protection scope.Implement process of the invention,
Condition, reagent, experimental method etc. are among the general principles and common general knowledge in the art in addition to what is specifically mentioned below,
There are no special restrictions to content by the present invention.
Ethyl alcohol used in following embodiment, silester, ammonium hydroxide are all that analysis is pure, and water is deionized water.
Embodiment 1: it under 20 DEG C of room temperature and stirring condition, by 50ml water and 1ml TEOS injection 250mL conical flask, stirs
Mix (revolving speed 300rmp) 2 hours；40ml ethyl alcohol is added into conical flask, (revolving speed 300rmp) 2 is stirred under the conditions of 20 DEG C of room temperature
Hour, the concentration of TEOS is 0.05M；28% ammonia spirit of mass fraction is added into conical flask, reaches the concentration of ammonia
0.44mol/L reacts 2h under the conditions of stirring (revolving speed 200rmp), and 3.3% ammonia spirit of certain volume is added thereto and (is added
Ammonium hydroxide volume is 17 with former sol volume ratio: 5), reacting 12 hours, reaction obtains silicon dioxide gel.In 20 DEG C of conditions of room temperature
Under silicon dioxide gel is centrifuged (revolving speed 15000rmp, time 30min), ethanol washing 3 times, average grain can be obtained
Diameter 103nm surface topology silicon dioxide microsphere of uniform size (see Fig. 1).
Embodiment 2: it under 20 DEG C of room temperature and stirring condition, by 30ml water and 3ml TEOS injection 250mL conical flask, stirs
Mix (revolving speed 300rmp) 2 hours；40ml ethyl alcohol is added into conical flask, (revolving speed 300rmp) 2 is stirred under the conditions of 20 DEG C of room temperature
Hour, the concentration of TEOS is 0.19M；28% ammonia spirit of mass fraction is added into conical flask, reaches the concentration of ammonia
1.48mol/L reacts 2h under the conditions of stirring (revolving speed 250rmp), and 2.8% ammonia spirit of certain volume is added thereto and (is added
Ammonium hydroxide volume is 50 with former sol volume ratio: 11), reacting 11 hours, reaction obtains silicon dioxide gel.In 20 DEG C of items of room temperature
(revolving speed 5000rmp, time 10min) silicon dioxide gel, ethanol washing 3 are centrifuged to silicon dioxide gel under part
It is secondary, average grain diameter 250nm silicon dioxide microsphere of uniform size can be obtained (see Fig. 2).
Embodiment 3: it under 20 DEG C of room temperature and stirring condition, by 25ml water and 5ml TEOS injection 250mL conical flask, stirs
Mix (revolving speed 300rmp) 2 hours；35ml ethyl alcohol is added into conical flask, (revolving speed 300rmp) 2 is stirred under the conditions of 20 DEG C of room temperature
Hour, the concentration of TEOS is 0.36M；28% ammonia spirit of mass fraction is added into conical flask, reaches the concentration of ammonia
1.48mol/L after reacting 2h under the conditions of stirring (revolving speed 300rmp), 2.8% ammonia spirit of certain volume is added thereto and (adds
Entering ammonium hydroxide volume with former sol volume ratio is 50: 11), reacting 10 hours, obtain silicon dioxide gel.In 20 DEG C of conditions of room temperature
Under silicon dioxide gel is centrifuged (revolving speed 4000rmp, time 20min), ethanol washing 3 times, average grain can be obtained
Diameter 225nm silicon dioxide microsphere of uniform size (see Fig. 3).
Embodiment 4: it under 20 DEG C of room temperature and stirring condition, by 50ml water and 3ml TMOS injection 250mL conical flask, stirs
Mix (revolving speed 300rmp) 2 hours；28ml ethyl alcohol is added into conical flask, (revolving speed 300rmp) 2 is stirred under the conditions of 20 DEG C of room temperature
Hour, the concentration of TMOS is 0.15M；28% ammonia spirit of mass fraction is added into conical flask, reaches the concentration of ammonia
0.59mol/L reacts 2h under the conditions of stirring (revolving speed 200rmp), and 3.0% ammonia spirit of certain volume is added thereto and (is added
Ammonium hydroxide volume is 11 with former sol volume ratio: 2), reacting 10 hours, obtain silicon dioxide gel.It is right under the conditions of 20 DEG C of room temperature
(revolving speed 13000rmp, time 30min) is centrifuged in silicon dioxide gel, and ethanol washing 3 times, average grain diameter can be obtained
110nm silicon dioxide microsphere of uniform size (see Fig. 4).
Embodiment 5: it under 20 DEG C of room temperature and stirring condition, by 30ml water and 3ml TEOS injection 150mL conical flask, stirs
Mix (revolving speed 300rmp) 2 hours；32ml mixed alkoxide solution (methanol: the tert-butyl alcohol=1: 1v/v) is added into conical flask, in room temperature
(revolving speed 300rmp) is stirred under the conditions of 20 DEG C 2 hours, the concentration of TEOS is 0.21M；Mass fraction 28% is added into conical flask
Ammonia spirit makes the concentration of ammonia reach 0.44mol/L, reacts 2h under the conditions of stirring (revolving speed 200rmp), one is added thereto
Determining 3.0% ammonia spirit of volume, (it is 11 that ammonium hydroxide volume, which is added, with former sol volume ratio: 2), reacting 10 hours, obtain titanium dioxide
Silica solution.(revolving speed 6000rmp, 20min), ethanol washing are centrifuged to silicon dioxide gel under the conditions of 20 DEG C of room temperature
3 times, average grain diameter 115nm silicon dioxide microsphere of uniform size can be obtained (see Fig. 5).
Embodiment 6: it under 20 DEG C of room temperature and stirring condition, by 30ml water and 3ml TEOS injection 250mL conical flask, stirs
Mix (revolving speed 300rmp) 2 hours；40ml ethyl alcohol is added into conical flask, (revolving speed 300rmp) 2 is stirred under the conditions of 20 DEG C of room temperature
Hour, the concentration of TEOS is 0.19M.After mixed liquor is placed in 40 DEG C of constant temperature 15min, 28% ammonia spirit of mass fraction is added,
So that the concentration of ammonia is reached 0.74mol/L, reacts 1.5h under the conditions of stirring (revolving speed 250rmp), certain volume is added thereto
(it is 50 that ammonium hydroxide volume is added with former sol volume ratio to 2.8% ammonia spirit: 11), reacting 12 hours, it is molten to obtain silica
Glue.(revolving speed 10000rmp, time 20min) is centrifuged to silicon dioxide gel under the conditions of 20 DEG C of room temperature, ethyl alcohol is washed
It washs 3 times, average grain diameter 227nm silicon dioxide microsphere of uniform size can be obtained (see Fig. 6).
Embodiment 7: it under 20 DEG C of room temperature and stirring condition, by 30ml water and 3ml TEOS injection 250mL conical flask, stirs
Mix (revolving speed 300rmp) 2 hours；40ml ethyl alcohol is added into conical flask, (revolving speed 300rmp) 2 is stirred under the conditions of 20 DEG C of room temperature
Hour, the concentration of TEOS is 0.19M.After mixed liquor is placed in 60 DEG C of constant temperature 25min, 28% ammonia spirit of mass fraction is added,
So that the concentration of ammonia is reached 0.59mol/L, reacts 1h under the conditions of stirring (revolving speed 300rmp), certain volume is added thereto
(it is 50 that ammonium hydroxide volume is added with former sol volume ratio to 2.8% ammonia spirit: 11), reacting 11 hours, it is molten to obtain silica
Glue.(revolving speed 13000rmp, time 20min) is centrifuged to silicon dioxide gel under the conditions of 20 DEG C of room temperature, ethyl alcohol is washed
It washs 3 times, average grain diameter 122nm silicon dioxide microsphere of uniform size can be obtained (see Fig. 7).
Protection content of the invention is not limited to above embodiments.Without departing from the spirit and scope of the invention, originally
Field technical staff it is conceivable that variation and advantage be all included in the present invention, and with appended claims be protect
Protect range.
Claims (14)
1. a kind of preparation method with surface topology nano silica microsphere, which is characterized in that this method include with
Lower step:
(1) silicon source is mixed with deionized water, obtains silicon source/H2O emulsion；
(2) under agitation, silicon source/H small molecule surface reactive material and the step (1) obtained2O emulsion carries out
Mixing, obtains silicon source/R-X/H of clear2O mixed liquor；
(3) under certain temperature, stirring condition, silicon source/R-X/H that the step (2) obtains is added in basic catalyst2O mixed liquor
In, certain time is reacted, silicon dioxide gel (a) is obtained；
(4) under certain temperature, stirring condition, ammonia spirit is added in the silicon dioxide gel (a) that the step (3) obtains,
Certain time is reacted, silicon dioxide gel (b) is obtained；
(5) silicon dioxide gel (b) obtained to step (4) is separated by solid-liquid separation, is washed, and obtains described having surface topology
Structure nano silicon dioxide microsphere.
2. as described in claim 1 with the preparation method of surface topology nano silica microsphere, which is characterized in that
In step (1), the silicon source is mixed with deionized water to be carried out under agitation, and the revolving speed of the stirring is 200~300rpm；
And/or the mixed temperature is 15~30 DEG C；And/or the mixed time is 1~3 hour.
3. as described in claim 1 with the preparation method of surface topology nano silica microsphere, which is characterized in that
In step (1), the silicon source includes one or both of esters of silicon acis, silane coupling agent.
4. as described in claim 1 with the preparation method of surface topology nano silica microsphere, which is characterized in that
In step (1), the volume ratio of the silicon source and deionized water are as follows: 1: 50≤VSilicon source∶VH2O≤1∶5。
5. as described in claim 1 with the preparation method of surface topology nano silica microsphere, which is characterized in that
In step (2), the revolving speed of the stirring is 200~300rpm；And/or the mixed temperature is 15~30 DEG C；And/or institute
The time for stating mixing is 1~3 hour.
6. as described in claim 1 with the preparation method of surface topology nano silica microsphere, which is characterized in that
In step (2), the small molecule surface reactive material is small molecule organic compound that is miscible with water and not dissociating, and structural formula is
R-X, wherein R is alkyl；X is hydroxyl, ketone group, aldehyde radical.
7. as described in claim 1 with the preparation method of surface topology nano silica microsphere, which is characterized in that
In step (2), the small molecule surface reactive material and silicon source/H2The volume ratio of O emulsion is 1: 2~8: 5.
8. as described in claim 1 with the preparation method of surface topology nano silica microsphere, which is characterized in that
In step (3), the reaction temperature is 20~60 DEG C；And/or the time of the reaction is 2~5 hours；And/or it is described anti-
It should carry out under agitation, the revolving speed of the stirring is 200~300rpm.
9. as described in claim 1 with the preparation method of surface topology nano silica microsphere, which is characterized in that
In step (3), the basic catalyst is alkalescent catalyst, the concentration of the alkalescent catalyst be 0.2mol/L~
2.0mol/L。
10. having the preparation method of surface topology nano silica microsphere as described in claim 1, feature exists
In in step (4), the temperature is 15~30 DEG C；The revolving speed of the stirring is 200~300rpm；The body that ammonium hydroxide is added
Long-pending and silicon dioxide gel volume ratio is 3: 1~6:1；The concentration of the ammonium hydroxide is 3.5%~2.5%；The time of the reaction
It is 8~12 hours.
11. having the preparation method of surface topology nano silica microsphere as described in claim 1, feature exists
In in step (5), described be separated by solid-liquid separation includes that centrifuge separation, spray drying and cryospray are dry.
12. having the preparation method of surface topology nano silica microsphere as described in claim 1, feature exists
In in step (5), the washing is first to be washed with deionized 3 times, then washed 3 times with dehydrated alcohol.
13. as what described in any item methods of claim 1~12 were prepared has surface topology nanometer titanium dioxide
Silicon microballoon.
14. having surface topology nano silica microsphere in absorption, catalytic carrier, drug as claimed in claim 13
Targeting conveying, pharmaceutical carrier, genophore, contrast agent, the application in treatment of cancer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910508292.2A CN110203936B (en) | 2019-06-12 | 2019-06-12 | Nano silicon dioxide microsphere with surface topological structure and preparation method thereof |
Applications Claiming Priority (1)
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| CN108341414A (en) * | 2017-01-22 | 2018-07-31 | 华东师范大学 | A kind of uniform silicon dioxide microsphere and its preparation method and application |
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