CN109985584A - A kind of preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere - Google Patents
A kind of preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere Download PDFInfo
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- CN109985584A CN109985584A CN201910328755.7A CN201910328755A CN109985584A CN 109985584 A CN109985584 A CN 109985584A CN 201910328755 A CN201910328755 A CN 201910328755A CN 109985584 A CN109985584 A CN 109985584A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
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Abstract
The present invention is a kind of preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere.Method includes the following steps: ultrasonic wave disperses after Nano particles of silicon dioxide, organic solvent and deionized water are mixed, mixed liquor is obtained;By monomer dropping to entering in reaction system, 50~80 DEG C are warming up to, then initiator solution is added dropwise in reaction system;System is naturally cooling to 20~30 DEG C after reaction, using dehydrated alcohol washing reaction product, obtains strawberry shape hybridization compounding microballoon.The present invention extends the method for preparing strawberry shape particle, it has obtained using inorganic particulate silica as core, organic polymer is the strawberry shape hybridization compounding microballoon of surface bulge particle, and without being surface modified to silica core particle, preparation method is simple.
Description
Technical field
Technical solution of the present invention is related to inorganic, organic and polymeric material field, and in particular to a kind of regulatable
Strawberry shape silica-organic hybrid complex microsphere preparation method.
Background technique
Anisotropic particles (asymmetric or anisotropic particles, or Janus particles)
Refer to the particle of shape/chemical composition asymmetry, uneven distribution.Go deep into the development of science and technology with research, people's success
It is prepared for the hybridization compoundings microballoons such as acorn nut shape, strawberry shape, Xue Renzhuan, patch shape.Wherein strawberry shape hybridization compounding microballoon presses its group
At difference, strawberry shape hybrid inorganic-organic complex microsphere (Wang R K, Liu H R, Wang F W.Facile can be divided into
Preparation of Raspberry-Like Superhydrophobic Polystyrene Particles via
Seeded Dispersion Polymerization [J] .Langmuir, 2013,29 (36): 11440-11448.), strawberry shape
Organic-organic hybrid complex microsphere (Wang L, Pan M, Song S, et al.Intriguing Morphology
Evolution from Non-crosslinked Poly(tert-butyl acrylate)Seeds with Polar
Functional Groups in Soap-Free Emulsion Polymerization of Styrene[J]
.Langmuir, 2016,32 (31): 7829-7840.), strawberry shape inorganic-organic hybridization complex microsphere (Reculusa, St é
phane,Céline,Ravaine S,et al.Syntheses of Raspberrylike Silica/Polystyrene
Materials [J] .Chemistry of Materials, 2002,14 (5): 2354-2359.), strawberry shape inorganic-inorganic it is miscellaneous
Change complex microsphere (Li X, He J.In situ Assembly of Raspberry-and Mulberry-Like Silica
Nanospheres toward Antireflective and Antifogging Coatings[J].ACS Applied
Materials&Interfaces,2012,4(4):2204-2211.).Strawberry shape hybridization compounding microballoon is since it is with biggish
The excellent properties such as specific surface area, higher surface roughness, preferable light scattering characteristic and phase separation structure, in catalysis (Kim
M,Heo E,Kim A,et al.Synthesis of Pd/SiO2Nanobeads for Use in Suzuki Coupling
Reactions by Reverse Micelle Sol–gel Process[J].Catalysis Letters,2012,142
(5): 588-593.), template (Qiu Y Y, Xiao M M, Katja L.Fabrication of Nano-Sized Hybrid
Janus Particles from Strawberry-Like Hierarchical Composites[J]
.Macromolecular Chemistry and Physics, 2018:1800267), self assembly (Hong M H, Jeffrey N
A,Ke M W,et al.Magnetically Assisted and Accelerated Self-Assembly of
Strawberry-like Nano/Microparticles[J].Journal of Physical Chemistry B,2006,
110 (40): 19929-19934.), coating (Keonyoung H, Younghun K.Facile Fabrication of
Superamphiphobic Glass Coated with Fluorinated-Silica Nanoparticles[J]
.Materials Letters, 2018,229:213-216.) etc. fields have be widely applied.
At present the preparation method of strawberry shape hybridization compounding particle include: polymerization (Xiao T Z, Yang Y S, Yi J M,
et al.Controllable Synthesis of Raspberry-Like PS–SiO2Nanocomposite Particles
via Pickering Emulsion Polymerization[J].RSC Advances,2018,8(7):3910-3918.)、
Heterogeneous agglomeration method (Jiang W, Grozea C M, Shi Z, et al.Fluorinated Raspberry-like Polymer
Particles for Superamphiphobic Coatings[J].ACS Applied Materials&Interfaces,
2014,6 (4): 2629-2638.), guiding Hydrolyze method (Zhou S Z, Qiao X G.Synthesis of Raspberry-
Like Polymer@Silica Hybrid Colloidal Particles through Biphasic Sol-gel
Process[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,
2018,553:230-236.), template modifies method (Zhang X, Bai L, Lou C, et al.Fabrication and
Morphological Evolution of Inverse Core/Shell Structural Latex Particles of
Poly(vinyl acetate)/Polystyrene by Maleic Anhydride Grafting[J].Colloid and
Polymer Science, 2016,294 (7): 1117-1128.) etc..Although the above method can synthesize strawberry shape particle, close
At method complexity, complex steps.
Summary of the invention
The purpose of the present invention is provide a kind of novel strawberry shape silica-for deficiency present in current techniques
The preparation method of organic hybrid complex microsphere.The ratio and silica that this method passes through appropriate organic solvent and deionized water
The ratio of seed grain and organic monomer is avoided stablizing organic monomer using emulsifier, and is eliminated in advance to silica
The step of particle is surface modified, finally preparing cladding, more completely strawberry shape silica-organic matter hybridization compounding is micro-
Ball.The present invention extends the method for preparing strawberry shape particle, has obtained using inorganic particulate silica as core, organic polymer is
The strawberry shape hybridization compounding microballoon of surface bulge particle, and without being surface modified to silica core particle, preparation side
Method is simple and easy.
The technical scheme is that
A kind of preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere, this method includes following
Step:
(1) ultrasonic wave disperses after mixes Nano particles of silicon dioxide, organic solvent and deionized water, obtains mixed liquor;
Wherein, quality is than Nano particles of silicon dioxide: organic solvent: deionized water=1:35~90:110~180;
(2), which stirs down mixed liquor, is passed through inert gas, is kept for 30~60 minutes;Then by monomer in 1~10min
It is added drop-wise in reaction system, and is warming up to 50~80 DEG C, wherein mass ratio is Nano particles of silicon dioxide: monomer=10:12
~49;
(3) initiator solution is added dropwise in reaction system by 2~10min, and is kept for 2~8 hours, wherein drawing
The quality for sending out agent is the 0.1%~10% of polymerized monomer quality;The concentration of initiator solution is 0.5%~3%;
(4) makes reaction system be naturally cooling to 20~30 DEG C, using dehydrated alcohol washing reaction product, obtains strawberry shape
Hybridization compounding microballoon.
Inert gas in the step (2) is argon gas or nitrogen.
The particle size range of the Nano particles of silicon dioxide is 80~1200nm.
The organic solvent is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, glycerine, 1,4- butanediol, ethylene glycol, poly- second
One of glycol 200.
The ultrasonic power being ultrasonically treated in the step (1) is 100W, and sonication treatment time is 30~60 minutes.
The monomer is styrene, 4- fluorobenzene ethene, aminostyryl, p-chloromethyl styrene or 4-Vinyl phenol
One of.
The initiator was that the initiator is potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, hydrogen peroxide, Asia
At least one of sodium sulphate, sodium hydrogensulfite and ferrous sulfate.
Substantive distinguishing features of the invention are as follows:
Polymerization of the present invention is seeded soap-free emulsion polymerization, stablizes organic monomer without emulsifier, and
Eliminate the step of being surface modified in advance to silicon dioxide granule.Compared to seminar's patent before, " a kind of strawberry shape has
Machine/inorganic hybridization microballoon and its application " (CN106433406A), the present invention are the organic polymers using inorganic particulate as core particle
Object is coated on inorganic particulate.The article and patent delivered compared to other people, we are prepared for inorganic matter silica
For core particle, the strawberry shape hybridization compounding microballoon of Coated with Organic Matter inorganic silicon dioxide, in whole preparation process without using
Emulsifier and without being surface modified in advance to silicon dioxide granule, and we use the mixed of organic solvent and deionized water
It closes liquid to replace in conventional method using deionized water being solvent by solvent, preparation method is simple.
Beneficial effects of the present invention:
(1) preparation method of a kind of regulatable strawberry shape silica-organic hybrid complex microsphere proposed by the present invention,
It is to be grown by seeded soap-free emulsion polymerization method in silicon dioxide granule using inorganic matter Nano particles of silicon dioxide as core particle
Organic polymer finally obtains strawberry shape silica-organic hybrid complex microsphere.Strawberry shape two is prepared compared to conventional method
For silica-organic hybrid complex microsphere, advantage of the invention is that without in advance to silica in whole preparation process
Nanoparticle is surface-treated, and preparation method is simple.
(2) preparation method proposed by the invention is larger to the type inclusiveness of organic polymer, is suitble to a variety of organic poly-
The strawberry shape silicon dioxide-poly styrene hybridization compounding prepared in monomer adduct, such as embodiment 2 using styrene organic monomer
Microballoon, the strawberry shape silicon dioxide-poly 4- fluorobenzene ethene hybridization compounding prepared using 4- fluorobenzene ethene organic monomer in embodiment 3
Microballoon.
(3) solvent that preparation method proposed by the invention uses is the mixed solution of organic solvent and deionized water, is led to
The appropriate ratio for crossing organic solvent and deionized water prepares strawberry shape hybridization compounding microballoon, such as with dehydrated alcohol in embodiment 2
Prepare strawberry shape silicon dioxide-poly styrene hybridization compounding microballoon with the mixed solution of deionized water, wherein dehydrated alcohol with
The ratio of deionized water is 3:7;Strawberry shape titanium dioxide is prepared with the mixed solvent of anhydrous methanol and deionized water in embodiment 4
Silicon-polystyrene hybridization compounding microballoon, wherein the ratio of anhydrous methanol and deionized water is 2:8.Compared to traditional preparation methods
In mostly using deionized water be solvent, and need to be added emulsifier stablize organic monomer for, system proposed by the invention
Preparation Method novelty is feasible.
Detailed description of the invention:
Fig. 1: strawberry shape silica-organic matter hybridization compounding microballoon preparation flow figure;
Fig. 2: partial size is the SEM photograph of the Nano particles of silicon dioxide of 400nm in embodiment 1;
Fig. 3: using dehydrated alcohol and deionized water as solvent in embodiment 1, organic monomer styrene dosage is 200 microlitres
When, prepare the SEM photograph of silicon dioxide-poly styrene;
Fig. 4: using dehydrated alcohol and deionized water as solvent in embodiment 2, organic monomer styrene dosage is 400 microlitres
When, prepare the SEM photograph of silicon dioxide-poly styrene;
Fig. 5: using dehydrated alcohol and deionized water as solvent in embodiment 3, organic monomer 4- fluorobenzene ethene dosage is 400 micro-
When rising, the SEM photograph of silicon dioxide-poly 4- fluorobenzene ethene is prepared;
Fig. 6: using anhydrous methanol and deionized water as solvent in embodiment 4, organic monomer styrene dosage is 400 microlitres
When, prepare the SEM photograph of silicon dioxide-poly styrene;
Case is embodied
Method flow diagram of the present invention is as shown in Fig. 1.Selection silica is core particle, and being scattered in has
In the mixed solution of solvent and deionized water, differential responses monomer and initiator is added, it is straight by seeded soap-free emulsion polymerization
It connects to obtain strawberry shape silica-organic hybrid complex microsphere.Below in conjunction with the attached drawing in case study on implementation of the present invention to this hair
Clear, complete description that technical solution in bright case study on implementation carries out.
Nano particles of silicon dioxide of the present invention is well known materials, takes one of following methods according to demand:
Method one: preparation of the average particle size range in the Nano particles of silicon dioxide of 80~600nm:
It is utilized according to patent CN101691426A- Fink-Hohn synthetic method, by dehydrated alcohol, ammonium hydroxide, distilled water
It sequentially adds in three-necked flask, after mixing evenly, is rapidly added ethyl orthosilicate, wherein mass ratio is ammonium hydroxide: dehydrated alcohol: steaming
Distilled water: gained suspension is transferred to beaker after reacting 8h at room temperature by ethyl orthosilicate=1:1~60:1~5:0.2~10
In, it is volatilized naturally to solvent completely to get silica colloidal crystal template of the average grain diameter within the scope of 80~600nm is arrived, it will
The template mortar grinder obtains Nano particles of silicon dioxide.
Method two: preparation of the average particle size range in the Nano particles of silicon dioxide of 600~1200nm:
According to patent CN101691426A, in silica dioxide nano particle of the preparation average grain diameter within the scope of 80~600nm
In the reaction system of son, after teos hydrolysis is complete, the ammonium hydroxide, dehydrated alcohol, steaming of identical quality proportioning are added again
Distilled water and ethyl orthosilicate repeat 1~4 time, after teos hydrolysis is complete, suspension are removed and is stood, certainly to solvent
So volatilization completely to get to average particle size range 600~1200nm silica colloidal crystal template, by the template mortar
Grinding obtains Nano particles of silicon dioxide.
Embodiment 1: micro- as the strawberry shape silicon dioxide-poly styrene hybridization compounding of solvent using dehydrated alcohol and deionized water
Ball
(1) preparation of 400nm silicon dioxide granule
It is utilized according to patent CN101691426A- Fink-Hohn synthetic method is being furnished with electric stirring at room temperature
140g dehydrated alcohol is sequentially added in the there-necked flask of 500mL, the ammonium hydroxide that 30g mass fraction is 25%, 30.5g distilled water, stirring
After uniformly, 20.6g ethyl orthosilicate is added into there-necked flask rapidly, reacts at room temperature 8h.Gained suspension is transferred in beaker,
It volatilizees naturally to solvent completely to get the silica colloidal crystal template for being 400nm to average grain diameter, template is placed in mortar
Grinding, can be obtained Nano particles of silicon dioxide.
Fig. 2 is obtained with 450 electronic scanner microscope of model FEI Nano SEM scanning 400nm silicon dioxide granule
Photo, by figure it can be seen that preparation silicon dioxide granule size it is more uniform.
(2) synthesis of strawberry shape hybridization compounding microballoon
It is anhydrous that 10.2mL is added in four-hole bottle in Nano particles of silicon dioxide obtained in the step (1) for taking 0.15g dry
Four-hole bottle is placed in ultrasonic cleaning instrument, 1h is ultrasonically treated under 100W power, by reaction system by ethyl alcohol and 23.8mL deionized water
It is transferred to equipped with being stirred in churned mechanically oil bath pan, after revolving speed is 300rpm and is passed through argon gas 30min, with every 3 seconds one
The styrene monomer (St) of 200 μ L (i.e. 0.1818g) is added in the speed of drop, after being warming up to 70 DEG C, is added with the speed of every 3 seconds one drops
Entering potassium peroxydisulfate (KPS) aqueous solution that 2mL mass fraction is 1%, reacts 7h, reaction is naturally cooling to 20~30 DEG C after stopping,
2 times are washed with 6000rpm centrifugation and with dehydrated alcohol to get strawberry shape silicon dioxide-poly styrene hybridization compounding microballoon is arrived.
Fig. 3 is with 450 electron scanning electron-microscope scanning strawberry shape silicon dioxide-poly styrene of model FEI Nano SEM
The photo that hybridization compounding microballoon obtains, the strawberry shape silicon dioxide-poly styrene being evenly coated as seen from the figure are miscellaneous
Change complex microsphere.
Embodiment 2: micro- as the strawberry shape silicon dioxide-poly styrene hybridization compounding of solvent using dehydrated alcohol and deionized water
Ball
(1) preparation of 400nm Nano particles of silicon dioxide is the same as step (1) in embodiment one;
(2) 10.2mL is added in four-hole bottle in Nano particles of silicon dioxide obtained in the step (1) for taking 0.15g dry
Four-hole bottle is placed in ultrasonic cleaning instrument, is ultrasonically treated 1h under 100W power, will react by dehydrated alcohol and 23.8mL deionized water
System is transferred to equipped with being stirred in churned mechanically oil bath pan, after revolving speed is 300rpm and is passed through argon gas 30min, with every 3
The styrene monomer of 400 μ L (i.e. 0.3636g) is added in the speed of one drop of second, after being warming up to 70 DEG C, is added with the speed of every 3 seconds one drops
Entering potassium peroxydisulfate (KPS) reactant aqueous solution 7h that 2mL mass fraction is 1%, reaction is naturally cooling to 20~30 DEG C after stopping, with
6000rpm centrifugation simultaneously washs 2 times with dehydrated alcohol to get strawberry shape silicon dioxide-poly styrene hybridization compounding microballoon is arrived.
Fig. 4 is with 450 electron scanning electron-microscope scanning strawberry shape silicon dioxide-poly styrene of model FEI Nano SEM
It is miscellaneous to have obtained the complete strawberry shape silicon dioxide-poly styrene of cladding as seen from the figure for the photo that hybridization compounding microballoon obtains
Change complex microsphere.
Embodiment 3: multiple as the strawberry shape silicon dioxide-poly 4- fluorobenzene ethene hydridization of solvent using dehydrated alcohol and deionized water
The preparation of microballoon (1) 400nm Nano particles of silicon dioxide is closed with step (1) in embodiment one;
(2) 10.2mL is added in four-hole bottle in Nano particles of silicon dioxide obtained in the step (1) for taking 0.15g dry
Four-hole bottle is placed in ultrasonic cleaning instrument, is ultrasonically treated 1h under 100W power, will react by dehydrated alcohol and 23.8mL deionized water
System is transferred to equipped with being stirred in churned mechanically oil bath pan, after revolving speed is 300rpm and is passed through argon gas 30min, with every 3
The 4- fluorostyrene monomers of 400 μ L (i.e. 0.4096g) are added in the speed of one drop of second, after being warming up to 70 DEG C, with the speed of every 3 seconds one drops
Potassium peroxydisulfate (KPS) reactant aqueous solution 7h that 2mL mass fraction is 1% is added in degree, and reaction is naturally cooling to 20~30 after stopping
DEG C, 2 times are washed with 6000rpm centrifugation and with dehydrated alcohol to get strawberry shape silicon dioxide-poly 4- fluorobenzene ethene hybridization compounding is arrived
Microballoon.
Fig. 5 is with 450 electron scanning electron-microscope scanning strawberry shape silicon dioxide-poly 4- fluorobenzene of model FEI Nano SEM
The photo that ethylene hybridization compounding microballoon obtains has obtained the complete strawberry shape hybridization compounding microballoon of cladding as seen from the figure.
Embodiment 4: micro- as the strawberry shape silicon dioxide-poly styrene hybridization compounding of solvent using anhydrous methanol and deionized water
Ball
(1) preparation of 400nm Nano particles of silicon dioxide is the same as step (1) in embodiment one;
(2) Nano particles of silicon dioxide obtained in the step (1) for taking 0.15g dry in four-hole bottle, be added 6.8mL without
Four-hole bottle is placed in ultrasonic cleaning instrument, 1h is ultrasonically treated under 100W power, by reactant by water methanol and 27.2mL deionized water
System is transferred to equipped with being stirred in churned mechanically oil bath pan, after revolving speed is 300rpm and is passed through argon gas 30min, with every 3 seconds
The speed of one drop is added the styrene monomer of 400 μ L (i.e. 0.3636g) and 1mL mass fraction is added with the speed of every 3 seconds one drops
For 2% potassium peroxydisulfate (KPS) aqueous solution, after being warming up to 50 DEG C, 1mL mass fraction is added as 1% with the speed of every 3 seconds one drops
Aqueous solution of sodium bisulfite react 7h, reaction stop after being naturally cooling to 20~30 DEG C, be centrifuged with 6000rpm and use anhydrous second
Alcohol washs 2 times to get strawberry shape silicon dioxide-poly styrene hybridization compounding microballoon is arrived.
Fig. 6 is with 450 electron scanning electron-microscope scanning strawberry shape silicon dioxide-poly styrene of model FEI Nano SEM
The photo that hybridization compounding microballoon obtains has obtained coating as seen from the figure more completely strawberry shape hybridization compounding microballoon.
Unaccomplished matter of the present invention is well-known technique.
Claims (7)
1. a kind of preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere, it is characterized in that this method packet
Include following steps:
(1) ultrasonic wave disperses after mixes Nano particles of silicon dioxide, organic solvent and deionized water, obtains mixed liquor;Its
In, quality is than Nano particles of silicon dioxide: organic solvent: deionized water=1:35~90:110~180;
(2), which stirs down mixed liquor, is passed through inert gas, is kept for 30~60 minutes;Then monomer is added dropwise in 1~10min
To entering in reaction system, and it is warming up to 50~80 DEG C, wherein mass ratio is Nano particles of silicon dioxide: monomer=10:12~
49;
(3) initiator solution is added dropwise in reaction system by 2~10min, and holding 2~8 hours, wherein initiator
Quality be polymerized monomer quality 0.1%~10%;The concentration of initiator solution is 0.5%~3%;
(4) makes reaction system be naturally cooling to 20~30 DEG C, using dehydrated alcohol washing reaction product, obtains strawberry shape hydridization
Complex microsphere.
2. the preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere as described in claim 1, special
Sign is that the inert gas in the step (2) is argon gas or nitrogen.
3. the preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere as described in claim 1, special
Sign is that the particle size range of the Nano particles of silicon dioxide is 80~1200nm.
4. the preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere as described in claim 1, special
Sign is that the organic solvent is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, glycerine, 1,4- butanediol, ethylene glycol, polyethylene glycol
One of 200.
5. the preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere as described in claim 1, special
Sign is that the ultrasonic power being ultrasonically treated in the step (1) is 100W, and sonication treatment time is 30~60 minutes.
6. the preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere as described in claim 1, special
Sign be the monomer be in styrene, 4- fluorobenzene ethene, aminostyryl, p-chlorostyrene or 4-Vinyl phenol one
Kind.
7. the preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere as described in claim 1, special
Sign is that the initiator described in the initiator was is potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, hydrogen peroxide, sulfurous acid
At least one of sodium, sodium hydrogensulfite and ferrous sulfate.
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