CN105860080B - A kind of monodispersed red blood cell shape polysiloxanes nano-particle and preparation method thereof - Google Patents
A kind of monodispersed red blood cell shape polysiloxanes nano-particle and preparation method thereof Download PDFInfo
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Abstract
A kind of monodispersed red blood cell shape polysiloxanes nano-particle and preparation method thereof, the solid or hollow structure that the nano-particle shows a monodisperse distribution, grain size are 0.2~10 μm, and shape is in flat hemisphere, and pit is presented at flat hemispheroidal center.Preparation method is to regard the dissolving of emulsifier, Organic Alcohol and inorganic salts as water phase in deionized water using the mixture of a kind of silane monomer or a variety of silane monomers as oil phase；After mixing by 100 parts by weight of water phase and 5 80 parts by weight of oil phase, heating and cooling processing is carried out, alkaline solution is added, solid nano-particle can be obtained；Solid nano-particle hydrothermal treatment, drying obtain hollow nano-particle.The uniform particle sizes of the nano-particle, show a monodisperse distribution, large specific surface area；Without using any template in preparation process, process is simple, is not required to remove removing template by way of calcining or chemical etching again, greatly reduces manufacturing cost, can meet the needs in different application field.
Description
Technical field
The present invention relates to a kind of polysiloxanes nano-particle and its technology of preparing, more particularly to a kind of monodispersed red blood cell
Shape polysiloxanes nano-particle and preparation method thereof, belongs to technical field of chemical material preparation.
Background technology
In recent years, more and more extensive concern has been obtained to the research of polysiloxanes nanoparticle, because polysiloxanes has
Have high intensity, heat resistance, weatherability, non-toxic and tasteless, small-size effect, easily dispersion, quantum tunneling effect the features such as, coating,
The various aspects such as paint, cosmetics, papermaking, nano-form and medicine are all used widely.Meanwhile hollow polysiloxanes is received
The research of rice particle is also increasingly extensive.Because hollow polysiloxanes has high-specific surface area, high intensity, heat-resisting weather-proof, nontoxic nothing
The features such as taste, high absorption property, in slow releasing carrier of medication, sorbing material, catalytic carrier, light material, heat preserving and insulating material, change
The various aspects such as the fields such as cosmetic are obtained for extensive research.
There are many preparation methods for polysiloxanes nano-particle.It is single that Kolb was found that prepared by sol-gel process in 1956 for the first time
Disperse SiO2Method, however the appearance of poly-dispersed particles is resulted in the reason of reaction speed.Until nineteen sixty-eightWith
Fink is in document " Controlled growth of monodisperse silica spheres in the micron
size range.Colloid Interface Sci,1968,26:More system is carried out in 62-69 " to Kolb methods to grind
Study carefully, by the way that system parameters are studied and adjusted, has obtained monodisperse spherical of the grain size between 0.05-2 μ ms
Particle.However, during the catalyst such as addition ammonium hydroxide are condensed, the condensation degree and concentration of hydrolysate are to influence nucleation
Principal element, the difference of nucleation density directly results in the grain size of final particle, because the of short duration of nucleation process results in most
The shortcomings of whole particle is not easy to repeat, and grain size foresight is poor, complex steps；So Dong Peng et al. is in document " Preparation
of three-dimensionally ordered inorganic/organic Bi-contimious composite
Proton condueting membranes.Chemistry of Materials, 2005,17 (24) are drawn in 5880-5883 "
External Ludox is entered as core seeds, as the substitute of the core of the spontaneous production of system, to propose sowing
Method, this method can be such that particle diameter range is accurately controlled within 1 μm, the particle diameter distribution deviation ratio obtainedMethod is more preferable, and the particle morphology that seeding method obtains is still spherical shape.Addition rule is the effect used in catalyst
Under, hydrogeneous polysiloxanes and the polysiloxanes containing vinyl are subjected to hydrosilylation, to generate polysiloxanes grain
Son, pattern are also spherical.Kikuchi et al. " Recovery of microsPherical silicone resin
Particle. [P] .JP4202226,1992 " are prepared for the Silicone particles that grain size is 600nm, pattern using addition process
It is spherical.Hydrolytic condensation rule is that alkoxy silane is first passed through hydrolysis, then carries out catalyzing and condensing by adding acid or alkali
Crosslinking generates polysiloxanes microballoon, and the microspherulite diameter that this method is obtained is between 0.01-100 μm.Wei Peng is in document
“Method for producing spherical silicone resin fine particle.[P]
.JP2001294670,2001 " middle use methyltrimethoxysilane are monomer, are prepared for grain size between 0.5-20 μm
Polysiloxanes microballoon.From the current study, either seeding method, sol-gel process, or other preparation methods are all
Expect the parameters by change system, reach the controllable preparation to generating particle, controllable content includes whether monodisperse, is
No particle size is controllable.These reactions are all based in aqueous solution is hydrolyzed what condensation generated to silane, due to interfacial tension
Effect and thermodynamical equilibrium presence, the particle obtained is all spherical.It is also rare at present can be in the feelings without using template
The report of the solid Silicone particles of monodispersed red blood cell pattern is largely obtained under condition.
There are many preparation methods for hollow polysiloxanes nano-particle.Such as hard template method, soft template method and from sacrificial mold
Plate method etc..Document " Nanometric hollow spheres made of MSU-X-type mesoporous
silica.Journal of Materials Chemistry,2002,12(5):1553-1556. " empty using phonochemistry synthesis
Core structure, collision of the bubble from sound wave whirlpool can be containing ethyl orthosilicate and surfactants by ultrasonic facility
Hollow ball is synthesized in aqueous solution." Silica particles in the document of Barbe et al.:A novel drug-delivery
system.Advanced Materials,2004,16(21):1959-1966. " has synthesized tiny balloon in emulsion, institute
Microreactor is exactly drop.Chen et al. is in document " Preparation of hollow silica nanospheres
by surface-initiated atom transfer radical polymerization on polymer latex
templates.Advanced Functional Materials,2005,15(1):It is free using atom transfer in 113-117 "
The method of base is modified template, introduces function group；Functional group and monomer polymerize to form shell material in interface, synthesis
Tiny balloon.Document " Direct preparation of silica hollow spheres in a water in oil
emulsion system:The effect of pH and viscosity.Journal of Non-crystalline
Solids,2006,352(21-22):2230-2235. " is reported makees template with CTAB, by adjusting solution concentration and pH value,
Nano level tiny balloon can be gone out in slightly soluble liquid.Wang et al. " Creation of Interior Space,
Architecture of Shell Structure,and Encapsulation of Functional Materials for
Mesoporous SiO2Spheres.Chemistry of Materials,2011,23(22):4886-4899 " Ostwald
Ripening ageing methods have carried out the preparation of mesoporous hollow microsphere under hydrothermal conditions.Wang et al. is in document " Hollow
mesoporous silica spheres synthesized with cationic and anionic mixed
surfactant as templates.Materials Letters,2015.142:269-272. " middle using improvedMethod obtains tiny balloon using Surfactant CTAB/SDS as dual mould plate at room temperature.
From at present to the research of hollow Silicone particles from the point of view of, hard template and soft template method are still to prepare hollow poly- silicon
The main stream approach of oxygen alkane particle, but gradually tendency is easy to remove in the system for being relatively easy to obtain for the selection of template, meanwhile,
The favor of researcher is more exposed to from sacrifice template.But, the hollow granule of polysiloxanes either passes through tangible template
Method or certainly sacrifice template, shape is spherical shape, this is also due to the condition of the thermodynamical equilibrium in preparation process
It determines.Also rare report shows easily obtain monodispersed red blood cell shape without using template at present
Polysiloxanes hollow-core construction.
Invention content
The object of the present invention is to provide a kind of monodispersed red blood cell shape polysiloxanes nano-particle and preparation method thereof, with
Solve the technological deficiency that polysiloxanes nano-particle pattern in the prior art is single, preparation process need to use template.
Technical scheme is as follows：
A kind of monodispersed red blood cell shape polysiloxanes nano-particle, it is characterised in that：The nano-particle is in monodisperse point
The solid or hollow structure of cloth, grain size are 0.2~10 μm, and shape is in flat hemisphere, are presented at flat hemispheroidal center recessed
Hole, the 1/10~9/10 of a diameter of flat hemisphere planar diameter of pit, the shape of pit is flat hemispherical, the centre of sphere of pit with
The centre of sphere of nano-particle is located at on Radius.
The shell of the hollow-core construction nano-particle is single layer or bilayer.
A kind of method of the red blood cell shape polysiloxanes nano-particle of monodisperse solid construction provided by the invention, feature
It is that this method carries out as follows：
1) oil phase and water phase are prepared：Using the mixture of a kind of silane monomer or a variety of silane monomers as oil phase, will emulsify
Agent, Organic Alcohol and inorganic salts dissolve is used as water phase in deionized water, and deionized water is 100 parts by weight in water phase, and emulsifier is
0-4 parts by weight, Organic Alcohol are 0-4 parts by weight, and inorganic salts are 0-6 parts by weight；
2) heating and cooling are handled：100 parts by weight of water phase and oil phase 5-80 parts by weight are uniformly mixed, are then cooled to -50 DEG C
~0 DEG C of section is kept for 5-10 minutes, then mixed liquor is taken out, and is kept for 5~10 minutes after being warming up to 20 DEG C~90 DEG C；
3) by heating and cooling treated mixed liquor is added while stirring at 20 DEG C~90 DEG C alkaline solution, 1~4h is reacted
Afterwards, the red blood cell shape polysiloxanes nano-particle of solid construction is obtained after cleaning.
A kind of method of the red blood cell shape polysiloxanes nano-particle of monodisperse hollow structure provided by the invention, feature
It is that this method carries out as follows：
1) oil phase and water phase are prepared：Using the mixture of a kind of silane monomer or a variety of silane monomers as oil phase, will emulsify
Agent, Organic Alcohol and inorganic salts dissolve is used as water phase in deionized water, and deionized water is 100 parts by weight in water phase, and emulsifier is
0-4 parts by weight, Organic Alcohol are 0-4 parts by weight, and inorganic salts are 0-6 parts by weight；
2) heating and cooling are handled：Oil phase 5-80 parts by weight and 100 parts by weight of water phase are uniformly mixed, are then cooled to -50 DEG C
~0 DEG C of section is kept for 5-10 minutes, then mixed liquor is taken out, and is kept for 5~10 minutes after being warming up to 20 DEG C~90 DEG C；
3) by heating and cooling treated mixed liquor is added while stirring at 20 DEG C~90 DEG C alkaline solution, 1~4h is reacted
Afterwards, the red blood cell shape polysiloxanes nanoparticle dispersion liquid of solid construction is obtained；
4) the red blood cell shape polysiloxanes nanoparticle dispersion liquid of gained solid construction is placed in water heating kettle, at 120 DEG C
At~220 DEG C place 4~for 24 hours, after cleaning i.e. obtain hollow red blood cell shape polysiloxanes hallow nanoparticles.
Preferably, silane monomer of the present invention is methyl orthosilicate, ethyl orthosilicate, sodium metasilicate, methacryl
Oxygroup propyl trimethoxy silicane, mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, ethylenediamine propyl triethoxy
Silane, hexamethyldisiloxane trim,ethylchlorosilane, ten difluoro heptyl propyl trimethoxy silicanes, methyltriethoxysilane,
In aminopropyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dodecyl triethoxysilane,
Vinyltriethoxysilane or vinyltrimethoxysilane.
Preferably, Organic Alcohol of the present invention is methanol, ethyl alcohol, cyclohexanol, ethylene glycol, cyclohexanol, glycerine, fourth two
One or more of alcohol, n-butanol and isobutanol.
Preferably, inorganic salts of the present invention are sodium chloride, potassium chloride, zinc chloride, sodium sulphate, ammonium hydrogen carbonate, acetic acid
One or more of sodium and sodium thiosulfate.
Preferably, emulsifier of the present invention is polyvinylpyrrolidone, block polyether, polyvinyl alcohol, dodecyl
Sodium sulfonate, neopelex, cetyl trimethylammonium bromide, in sorbester p18, sorbester p17, Tween 80 and polysorbate60
It is one or more of.
Preferably, alkaline solution of the present invention is ammonium hydroxide, sodium hydrate aqueous solution, potassium hydroxide aqueous solution and hydrogen-oxygen
Change one or more of calcium aqueous solution.
Compared with prior art, the present invention haing the following advantages and high-lighting effect：Without using appointing in preparation process
What template, experimental procedure is simple, need not remove removing template again by the mode of calcining or chemical etching, greatly reduce system
Standby cost；Emulsifier can be added and also be added without, therefore the residue problem of emulsifier is not present in use；Only by catalysis
Polycondensation reaction and subsequent hydro-thermal process, you can obtain the polysiloxanes nanoparticle of monodispersed red blood cell shape hollow-core construction
Son overcomes in existing preparation method, and due to the effect of interface tension, the preparation of polysiloxanes hallow nanoparticles is only
The limitation of spherical particle can be obtained；The use of emulsifier not necessarily condition in the present invention, obtained monodispersed red blood cell
The hollow Silicone particles grain size of shape is in 0.2~10 μ m；The monodispersed red blood cell shape hollow-core construction particle of gained produces
Rate is high；The red blood cell shape hollow-core construction particle of gained can be the polysiloxanes of one-component or the poly- silica of compounding ingredients
Alkane can meet the needs in different application field；Other materials is not mixed in the preparation for obtaining polysiloxanes hollow granule, therefore
It is not interfered in fields such as slow releasing carrier of medication, sorbing material, catalytic carrier, light material, heat preserving and insulating material, cosmetics
Use.
Description of the drawings
Fig. 1 is the transmission electron microscope picture for the hollow Silicone particles that embodiment 1 obtains.
Fig. 2 is the transmission electron microscope picture for the hollow Silicone particles that embodiment 2 obtains.
Fig. 3 is the scanning electron microscopic picture for the solid Silicone particles that embodiment 3 obtains.
Specific implementation mode
The present invention is described further with reference to the accompanying drawings and examples.
As shown in Figure 1, a kind of monodispersed red blood cell shape polysiloxanes provided by the invention receives nano-particle, the nanoparticle
The solid or hollow structure that son shows a monodisperse distribution, grain size are 0.2~10 μm, and shape is in flat hemisphere, flat hemispheroidal
Presentation pit at center, the 1/10~9/10 of a diameter of flat hemisphere planar diameter of pit, the shape of pit is flat hemispherical,
The centre of sphere of pit and the centre of sphere of nano-particle are located at on Radius.If the nano-particle of hollow-core construction, shell has single layer
Or double-layer structure.
Its specific process step is as follows：
A kind of method of the red blood cell shape polysiloxanes nano-particle of monodisperse solid construction provided by the invention, this method
It carries out as follows：
1) oil phase and water phase are prepared：Using the mixture of a kind of silane monomer or a variety of silane monomers as oil phase, will emulsify
Agent, Organic Alcohol and inorganic salts dissolve is used as water phase in deionized water, and deionized water is 100 parts by weight in water phase, and emulsifier is
0-4 parts by weight, Organic Alcohol are 0-4 parts by weight, and inorganic salts are 0-6 parts by weight；
2) heating and cooling are handled：100 parts by weight of water phase and oil phase 5-80 parts by weight are uniformly mixed, are then cooled to -50 DEG C
~0 DEG C of section is kept for 5-10 minutes, then mixed liquor is taken out, and is kept for 5~10 minutes after being warming up to 20 DEG C~90 DEG C；
3) by heating and cooling treated mixed liquor is added while stirring at 20 DEG C~90 DEG C alkaline solution, 1~4h is reacted
Afterwards, the red blood cell shape polysiloxanes nano-particle (as shown in Figure 3) of monodisperse solid construction is obtained after cleaning.
A kind of method of the red blood cell shape polysiloxanes nano-particle of monodisperse hollow structure provided by the invention, this method
It carries out as follows：
1) oil phase and water phase are prepared：Using the mixture of a kind of silane monomer or a variety of silane monomers as oil phase, will emulsify
Agent, Organic Alcohol and inorganic salts dissolve is used as water phase in deionized water, and deionized water is 100 parts by weight in oil phase, and emulsifier is
0-4 parts by weight, Organic Alcohol are 0-4 parts by weight, and inorganic salts are 0-6 parts by weight；
2) heating and cooling are handled：Oil phase 5-80 parts by weight and 100 parts by weight of water phase are uniformly mixed, are then cooled to -50 DEG C
~0 DEG C of section is kept for 5-10 minutes, then mixed liquor is taken out, and is kept for 5~10 minutes after being warming up to 20 DEG C~90 DEG C；
3) by heating and cooling treated mixed liquor is added while stirring at 20 DEG C~90 DEG C alkaline solution, 1~4h is reacted
Afterwards, the red blood cell shape polysiloxanes nanoparticle dispersion liquid of solid construction is obtained；
4) gained red blood cell shape polysiloxanes nanoparticle dispersion liquid is placed in water heating kettle, is transferred at 120 DEG C~220 DEG C
Set 4~for 24 hours, obtain the hollow polysiloxanes hallow nanoparticles of red blood cell shape after cleaning.
In above-mentioned technical proposal, the silane monomer is methyl orthosilicate, ethyl orthosilicate, sodium metasilicate, metering system
Acryloxypropylethoxysilane trimethoxy silane, mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, three ethoxy of ethylenediamine propyl
Base silane, hexamethyldisiloxane trim,ethylchlorosilane, ten difluoro heptyl propyl trimethoxy silicanes, methyltriethoxy silane
Alkane, aminopropyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dodecyl triethoxysilane
In, vinyltriethoxysilane or vinyltrimethoxysilane；The Organic Alcohol is methanol, ethyl alcohol, cyclohexanol, second two
One or more of alcohol, cyclohexanol, glycerine, butanediol, n-butanol and isobutanol；The inorganic salts are sodium chloride, chlorine
Change one or more of potassium, zinc chloride, sodium sulphate, ammonium hydrogen carbonate, sodium acetate and sodium thiosulfate；The emulsifier is poly-
Vinylpyrrolidone, block polyether, polyvinyl alcohol, dodecyl sodium sulfate, neopelex, cetyl trimethyl
Ammonium bromide, one or more of sorbester p18, sorbester p17, Tween 80 and polysorbate60.
Below by several specific embodiments, the present invention is further illustrated.
Embodiment 1：
1) oil phase and water phase are prepared：Take vinyltriethoxysilane：7.5 parts by weight are as oil phase, by 4 parts by weight
NaCl, which is dissolved in the deionized water of 100 parts by weight, forms water phase, and oil phase is added in water phase, mixed liquor is placed in refrigerator,
- 5 DEG C are cooled to, keeps the temperature 10 minutes, then takes out and is heated to 50 DEG C, keep the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：Obtained mixed liquor is heated to 80 degree, stirring
2h obtains translucent precursor solution, and the sodium hydroxide 7ml solution of 1mol/L is added at this time, and the reaction was continued, and 4h obtains single point
Scattered red blood cell shape polysiloxanes nano-particle.
3) gained red blood cell shape polysiloxanes nanoparticle dispersion liquid is reacted into 12h as in water heating kettle at 160 DEG C,
The hollow polysiloxanes hallow nanoparticles of red blood cell shape are obtained after cleaning.
Embodiment 2
1) oil phase and water phase are prepared：Take vinyltrimethoxysilane:5 parts by weight are as oil phase, by the poly- second of 4 parts by weight
Alkene pyrrolidone, 0.5 parts by weight NaCl are dissolved in the water of 100 parts by weight and form water phase, and oil phase is added in water phase, will be mixed
Liquid is placed in refrigerator, is cooled to 0 DEG C, keeps the temperature 10 minutes, is then taken out and is heated to 90 degree, keeps the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：Obtained mixed liquor is heated to 90 degree, stirring
2h obtains translucent precursor solution, and the potassium hydroxide 3ml solution of 1mol/L is added at this time, and the reaction was continued, and 2h obtains single point
Scattered red blood cell shape polysiloxanes nano-particle.
3) by gained red blood cell shape polysiloxanes nanoparticle dispersion liquid as in water heating kettle, being reacted at 180 DEG C for 24 hours,
The hollow polysiloxanes hallow nanoparticles of red blood cell shape are obtained after cleaning.
Embodiment 3
1) oil phase and water phase are prepared：Take vinyltriethoxysilane：10 parts by weight take 100 parts by weight to go as oil phase
Oil phase is added in water phase by ionized water as water phase, and mixed liquor is placed in refrigerator, is cooled to -3 DEG C, keeps the temperature 6 minutes, and
It takes out afterwards and is heated to 20 degree, keep the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：When liquid to be mixed reaches room temperature, 2h is stirred, is obtained
Translucent precursor solution, is added the potassium hydroxide solution 5ml of 1mol/L at this time, and the reaction was continued 2h obtains monodispersed red thin
Born of the same parents' shape polysiloxanes nano-particle.
Embodiment 4
1) oil phase and water phase are prepared：Take vinyltriethoxysilane：1.5 parts by weight, sodium metasilicate：1.5 parts by weight, methyl
Triethoxysilane：3.5 parts by weight, aminopropyl triethoxysilane:1.5 parts by weight are mixed to get oil phase, by 0.5 parts by weight
Dodecyl sodium sulfate, which is dissolved in the water of 100 parts by weight, forms water phase, and oil phase is added in water phase, mixed liquor is placed in refrigerator
In, -2 DEG C are cooled to, keeps the temperature 10 minutes, then takes out and is heated to 60 degree, keep the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：Obtained mixed liquor is heated to 80 degree, stirring
2h obtains translucent precursor solution, and the sodium hydroxide 5ml solution of 1mol/L is added at this time, and the reaction was continued, and 2h obtains single point
Scattered red blood cell shape polysiloxanes nano-particle.
3) gained red blood cell shape polysiloxanes nanoparticle dispersion liquid is reacted into 8h, clearly as in water heating kettle at 200 DEG C
The hollow polysiloxanes hallow nanoparticles of red blood cell shape are obtained after washing.
Embodiment 5
1) oil phase and water phase are prepared：Take dodecyl triethoxysilane：15.5 parts by weight, hexamethyldisiloxane front three
Base chlorosilane：14.5 parts by weight, methyltriethoxysilane：18.5 parts by weight, vinyltriethoxysilane：13.5 weight
Part, aminopropyl triethoxysilane:18 parts by weight are mixed to get oil phase, by the polyvinylpyrrolidone of 0.5 parts by weight, 0.5 weight
Amount part ethyl alcohol, 0.5 parts by weight potassium chloride are dissolved in the water of 100 parts by weight and form water phase, and oil phase is added in water phase, will be mixed
Liquid is placed in refrigerator, is cooled to -5 DEG C, keeps the temperature 10 minutes, is then taken out and is heated to 50 degree, keeps the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：Obtained mixed liquor is heated to 50 degree, stirring
2h obtains translucent precursor solution, and the sodium hydroxide 4ml solution of 0.5mol/L is added at this time, and the reaction was continued, and 2h obtains list
The red blood cell shape polysiloxanes nano-particle of dispersion.
3) gained red blood cell shape polysiloxanes nanoparticle dispersion liquid is reacted into 12h as in water heating kettle at 220 DEG C,
The hollow polysiloxanes hallow nanoparticles of red blood cell shape are obtained after cleaning.
Embodiment 6
1) oil phase and water phase are prepared：Prepare oil phase and water phase：Take dodecyl triethoxysilane：1.5 parts by weight, methyl
Triethoxysilane：2.5 parts by weight, vinyltriethoxysilane：1.5 parts by weight, aminopropyl triethoxysilane:2.6 weight
Amount part is mixed to get oil phase, by the cetyl trimethylammonium bromide of 0.5 parts by weight, the methanol of 0.5 parts by weight, 0.5 parts by weight
Potassium chloride be dissolved in the water of 100 parts by weight and form water phase, oil phase is added in water phase, mixed liquor is placed in refrigerator, is dropped
Temperature keeps the temperature 10 minutes to -30 DEG C, then takes out and is heated to 20 degree, keeps the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：Obtained mixed liquor is stirred into 2h at room temperature,
Translucent precursor solution is obtained, the sodium hydroxide solution 5ml of 1.5mol/L is added at this time, the reaction was continued, and 2h obtains monodisperse
Red blood cell shape polysiloxanes nano-particle.
3) by gained red blood cell shape polysiloxanes nanoparticle dispersion liquid as in water heating kettle, being reacted at 120 DEG C for 24 hours,
The hollow polysiloxanes hallow nanoparticles of red blood cell shape are obtained after cleaning.
Embodiment 7
1) oil phase and water phase are prepared：Prepare oil phase and water phase：Take aminopropyl triethoxysilane：1.5 parts by weight, methyl three
Ethoxysilane：0.5 parts by weight, vinyltriethoxysilane：1.5 parts by weight, phenyl triethoxysilane:1.5 parts by weight
It is mixed to get oil phase, the sorbester p17 of 1 parts by weight, 0.25 parts by weight Tween 80 are dissolved in the water of 100 parts by weight and form water phase, it will
Oil phase is added in water phase, and mixed liquor is placed in refrigerator, is cooled to -35 DEG C, keeps the temperature 10 minutes, is then taken out and is heated to 20
Degree keeps the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：Obtained mixed liquor is reacted into 2h at normal temperatures,
Translucent precursor solution is obtained, the potassium hydroxide solution 2ml of the sodium hydroxide 1ml and 0.5mol/L of 1mol/L are added at this time,
Continue stirring 2h and obtains monodispersed red blood cell shape polysiloxanes nano-particle.
Embodiment 8
1) oil phase and water phase are prepared：Take vinyltriethoxysilane：3.5 parts by weight, phenyl triethoxysilane:2.5
Parts by weight, methyltriethoxysilane：1.5 parts by weight, aminopropyl triethoxysilane:1.5 parts by weight are mixed to get oil phase, will
The dodecyl sodium sulfate of 0.5 parts by weight, which is dissolved in the water of 100 parts by weight, forms water phase, and oil phase is added in water phase, will be mixed
It closes liquid to be placed in refrigerator, is cooled to -5 DEG C, keep the temperature 10 minutes, then take out and be heated to 50 degree, keep the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：Obtained mixed liquor is heated to 70 degree, stirring
2h obtains translucent precursor solution, and the potassium hydroxide solution of the sodium hydroxide 2ml and 0.5mol/L of 0.5mol/L are added at this time
3ml, the reaction was continued, and 2h obtains monodispersed red blood cell shape polysiloxanes nano-particle.
3) gained red blood cell shape polysiloxanes nanoparticle dispersion liquid is reacted into 15h as in water heating kettle at 210 DEG C,
The hollow polysiloxanes hallow nanoparticles of red blood cell shape are obtained after cleaning.
Embodiment 9
1) oil phase and water phase are prepared：Take vinyltriethoxysilane：1.5 parts by weight, sodium metasilicate：2.5 parts by weight, methyl
Triethoxysilane：1.5 parts by weight, aminopropyl triethoxysilane:1.5 parts by weight are mixed to get oil phase, by 0.5 parts by weight
Polyvinylpyrrolidone, which is dissolved in the water of 100 parts by weight, forms water phase, and oil phase is added in water phase, mixed liquor is placed in refrigerator
In, -2 DEG C are cooled to, keeps the temperature 10 minutes, then takes out and is heated to 50 degree, keep the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：Obtained mixed liquor is stirred into 2h at 50 DEG C, is obtained
To translucent precursor solution, the sodium hydroxide solution of 1mol/L is added at this time, the reaction was continued, and that 2h obtains is monodispersed red thin
Born of the same parents' shape polysiloxanes nano-particle.
3) by gained red blood cell shape polysiloxanes nanoparticle dispersion liquid as in water heating kettle, being reacted at 170 DEG C for 24 hours,
The hollow polysiloxanes hallow nanoparticles of red blood cell shape are obtained after cleaning.
Embodiment 10
1) oil phase and water phase are prepared：Take vinyltriethoxysilane：3.5 parts by weight, sodium metasilicate：1.8 parts by weight, phenyl
Triethoxysilane：1.5 parts by weight, aminopropyl triethoxysilane:2.5 parts by weight are mixed to get oil phase, by 0.5 parts by weight
Cetyl trimethylammonium bromide, 6 parts by weight sodium chloride be dissolved in 100 parts by weight water and form water phase, oil phase is added to water
Mixed liquor is placed in refrigerator by Xiang Zhong, is cooled to -5 DEG C, keeps the temperature 10 minutes, is then taken out and is heated to 50 degree, keeps the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：Obtained mixed liquor is heated to 80 degree, stirring
2h obtains translucent precursor solution, and the sodium hydroxide solution 3ml of 1.5mol/L is added at this time, and the reaction was continued, and 2h obtains list
The red blood cell shape polysiloxanes nano-particle of dispersion.
3) gained red blood cell shape polysiloxanes nanoparticle dispersion liquid is reacted into 14h as in water heating kettle at 180 DEG C,
The hollow polysiloxanes hallow nanoparticles of red blood cell shape are obtained after cleaning.
Embodiment 11
1) oil phase and water phase are prepared：Take vinyltriethoxysilane：1.5 parts by weight, vinyltrimethoxysilane：
1.5 parts by weight, methyltriethoxysilane：1.5 parts by weight, aminopropyl triethoxysilane:0.5 parts by weight are mixed to get oil
The polyvinylpyrrolidone of 0.5 parts by weight, 0.8 parts by weight glycerine, 0.5 parts by wt NaCl are dissolved in 100 parts by weight water by phase
Middle formation water phase, oil phase is added in water phase, mixed liquor is placed in refrigerator, is cooled to -5 DEG C, is kept the temperature 10 minutes, is then taken
Go out to be heated to 30 degree, keeps the temperature 10 minutes.
2) monodispersed red blood cell shape polysiloxanes nano-particle is prepared：Obtained mixed liquor is stirred into 2h at 30 degree, is obtained
To translucent precursor solution, the potassium hydroxide solution of 0.5mol/L is added at this time, the reaction was continued, and that 2h obtains is monodispersed red
Cell shape polysiloxanes nano-particle.
3) gained red blood cell shape polysiloxanes nanoparticle dispersion liquid is reacted into 4h, clearly as in water heating kettle at 200 DEG C
The hollow polysiloxanes hallow nanoparticles of red blood cell shape are obtained after washing.
Claims (8)
1. a kind of method preparing monodispersed red blood cell shape polysiloxanes nano-particle, it is characterised in that this method is by following step
It is rapid to carry out：
1) oil phase and water phase are prepared：Using the mixture of a kind of silane monomer or a variety of silane monomers as oil phase, by emulsifier, have
Machine alcohol and inorganic salts dissolve is used as water phase in deionized water, and deionized water is 100 parts by weight in water phase, and emulsifier is 0-4 weights
Part is measured, Organic Alcohol is 0-4 parts by weight, and inorganic salts are 0-6 parts by weight；
2) heating and cooling are handled：100 parts by weight of water phase and oil phase 5-80 parts by weight are uniformly mixed, are then cooled to -50 DEG C~0 DEG C
Section is kept for 5-10 minutes, then mixed liquor is taken out, and is kept for 5~10 minutes after being warming up to 20 DEG C~90 DEG C；
3) by heating and cooling treated mixed liquor is added while stirring at 20 DEG C~90 DEG C alkaline solution, after reacting 1~4h, clearly
Obtaining the red blood cell shape polysiloxanes nano-particle of solid construction after washing, the grain size of the nano-particle of the solid construction is 0.2~
10 μm, shape is in flat hemisphere, and pit is presented at flat hemispheroidal center, a diameter of flat hemisphere planar diameter of pit
1/10~9/10, the shape of pit is flat hemispherical, and the centre of sphere of pit and the centre of sphere of nano-particle are located at on Radius.
2. a kind of method preparing monodispersed red blood cell shape polysiloxanes nano-particle, it is characterised in that this method is by following step
It is rapid to carry out：
1) oil phase and water phase are prepared：Using the mixture of a kind of silane monomer or a variety of silane monomers as oil phase, by emulsifier, have
Machine alcohol and inorganic salts dissolve is used as water phase in deionized water, and deionized water is 100 parts by weight in water phase, and emulsifier is 0-4 weights
Part is measured, Organic Alcohol is 0-4 parts by weight, and inorganic salts are 0-6 parts by weight；
2) heating and cooling are handled：Oil phase 5-80 parts by weight and 100 parts by weight of water phase are uniformly mixed, are then cooled to -50 DEG C~0 DEG C
Section is kept for 5-10 minutes, then mixed liquor is taken out, and is kept for 5~10 minutes after being warming up to 20 DEG C~90 DEG C；
3) by heating and cooling, treated that mixed liquor is added while stirring at 20 DEG C~90 DEG C that alkaline solution obtains after reacting 1~4h
To the red blood cell shape polysiloxanes nanoparticle dispersion liquid of solid construction；
4) the red blood cell shape polysiloxanes nanoparticle dispersion liquid of gained solid construction is placed in water heating kettle, 120 DEG C~220
At DEG C place 4~for 24 hours, after cleaning i.e. obtain the red blood cell shape polysiloxanes nano-particle of hollow-core construction；The hollow-core construction is received
The grain size of rice corpuscles is 0.2~10 μm, and shape is in flat hemisphere, and pit, the diameter of pit are presented at flat hemispheroidal center
It is the 1/10~9/10 of flat hemisphere planar diameter, the shape of pit is flat hemispherical, the centre of sphere of pit and the ball of nano-particle
The heart is located at on Radius.
3. a kind of method preparing monodispersed red blood cell shape polysiloxanes nano-particle according to claim 2, special
Sign is：The shell of the red blood cell shape polysiloxanes nano-particle of hollow-core construction is single layer or bilayer.
4. according to a kind of method preparing monodispersed red blood cell shape polysiloxanes nano-particle as claimed in claim 1 or 2,
It is characterized in that：The silane monomer is methyl orthosilicate, ethyl orthosilicate, sodium metasilicate, methacryloxypropyl front three
Oxysilane, mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, ethylenediaminepropyltriethoxysilane, hexamethyl
Disiloxane trim,ethylchlorosilane, ten difluoro heptyl propyl trimethoxy silicanes, methyltriethoxysilane, three ethoxy of aminopropyl
Base silane, phenyltrimethoxysila,e, phenyl triethoxysilane, dodecyl triethoxysilane, vinyl triethoxyl
Silane or vinyltrimethoxysilane.
5. according to a kind of method preparing monodispersed red blood cell shape polysiloxanes nano-particle as claimed in claim 1 or 2,
It is characterized in that：The Organic Alcohol be methanol, ethyl alcohol, cyclohexanol, ethylene glycol, cyclohexanol, glycerine, butanediol, n-butanol and
One or more of isobutanol.
6. according to a kind of method preparing monodispersed red blood cell shape polysiloxanes nano-particle as claimed in claim 1 or 2,
It is characterized in that：The inorganic salts are sodium chloride, potassium chloride, zinc chloride, sodium sulphate, ammonium hydrogen carbonate, sodium acetate and thiosulfuric acid
One or more of sodium.
7. according to a kind of method preparing monodispersed red blood cell shape polysiloxanes nano-particle as claimed in claim 1 or 2,
It is characterized in that：The emulsifier is polyvinylpyrrolidone, block polyether, polyvinyl alcohol, dodecyl sodium sulfate, dodecane
Base benzene sulfonic acid sodium salt, cetyl trimethylammonium bromide, one or more of sorbester p18, sorbester p17, Tween 80 and polysorbate60.
8. according to a kind of method preparing monodispersed red blood cell shape polysiloxanes nano-particle as claimed in claim 1 or 2,
It is characterized in that：The alkaline solution is in ammonium hydroxide, sodium hydrate aqueous solution, potassium hydroxide aqueous solution and calcium hydroxide aqueous solution
One or more.
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| CN1557862A (en) * | 2004-01-14 | 2004-12-29 | 浙江大学 | Preparation method of polyorganosiloxane hollow microsphere molecular box |
| CN102209747A (en) * | 2009-05-21 | 2011-10-05 | 竹本油脂株式会社 | Hollow irregular fine particles, method for producing same, cosmetic raw material containing hollow irregular fine particles, and resin composition |
| CN102604102A (en) * | 2012-03-30 | 2012-07-25 | 山东大学 | Preparation method of polysilsesquioxane hollow microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557862A (en) * | 2004-01-14 | 2004-12-29 | 浙江大学 | Preparation method of polyorganosiloxane hollow microsphere molecular box |
| CN102209747A (en) * | 2009-05-21 | 2011-10-05 | 竹本油脂株式会社 | Hollow irregular fine particles, method for producing same, cosmetic raw material containing hollow irregular fine particles, and resin composition |
| CN102604102A (en) * | 2012-03-30 | 2012-07-25 | 山东大学 | Preparation method of polysilsesquioxane hollow microspheres |
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