CN106317425B - A method of organic inorganic hybridization hollow nanospheres are prepared by ultrasound - Google Patents
A method of organic inorganic hybridization hollow nanospheres are prepared by ultrasound Download PDFInfo
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Abstract
The invention discloses the nanospheres and purposes of a kind of method and acquisition that organic inorganic hybridization hollow nanospheres are prepared by ultrasound.This method has the feature that system is simple, easy to operate, reproducible, time-consuming is short, yield is big.The organic-inorganic hollow nanospheres particle diameter distribution prepared by the method is uniform, size is less than 100nm, surface is smooth, inner hollow, shell is made of silicon-containing polymer, for organic-inorganic hybrid structure, hydrophilic and oleophylic characteristic is had both, is strictly limited in nanoscale field especially suitable for the size to hollow ball.
Description
Technical field
The present invention relates to a kind of preparation methods of organic inorganic hybridization hollow nanospheres, in particular to a kind of to pass through ultrasound system
The method of standby organic inorganic hybridization hollow nanospheres.
Background technique
Hollow microsphere density is low, specific surface area is high and its chamber portion can accommodate guest materials of different nature, wide
It is general to be applied to the fields such as catalyst, pharmaceutical carrier, heat-barrier material.The preparation method of hollow microsphere is broadly divided into two classes at present：
The first kind is first to prepare microsphere template, then further prepares the microballoon of core-shell structure, removes mould finally by certain method
Plate obtains hollow microsphere.Such methods mainly include Permeation Swelling method, self-assembly method and template.By this method, often
It can prepare that size is controllable, hollow microsphere of uniform particle diameter.But there is also biggish defects for this method, by taking template as an example, pass through
Template prepares hollow microsphere and needs previously prepared polymer or inorganic template, increase workload in preparation process and at
This.And also need to remove removing template by the method calcined or etched later, a large amount of manpower and time are not only expended in this way, also
Easily cause collapsing and reuniting for microballoon.Therefore such methods are not particularly suited for industrialization large scale preparation hollow microsphere.
The preparation method of another kind of hollow microsphere be realized by collosol and gel in situ or polymerization to water, oil or
The direct cladding of gas, one of the most common are interfacial emulsion polymerizations.The process of interfacial emulsion polymerization relates generally to：First will
Two kinds of immiscible solvents mix (usually water oil systems) according to a certain ratio, and a certain amount of emulsifier and assistant for emulsifying agent is added,
Then stable lotion (oil-in-water type or water-in-oil type) is formed under the action of shearing and ultrasound, if at this time in oil-water interfaces
Cause the polymerization reaction of polymerized monomer or the solgel reaction of inorganic precursor, so that oil-water interfaces are converted into solid
Shell has just been made the internal microspheres with solid for being coated with oily perhaps water and has been removed inside microballoon by the method for removing or evaporating
Oil or water, hollow microsphere has just been made.This method is easy to operate, reproducible, is suitable for large scale preparation hollow microsphere.But
It is, to form stable lotion, to generally require to introduce a large amount of emulsifier and assistant for emulsifying agent to stablize oil-water interfaces, these emulsifications
The removal of agent is more difficult (some researches show that pass through 7 presence for remaining to detect surfactant of washing), easily to microballoon
Subsequent use impacts.To avoid largely using emulsifier and assistant for emulsifying agent, people have invented Pickering emulsion polymerization
Method, it is simply that surfactant is substituted using solids, to stablize oil-water interfaces.Pickering emulsion polymerization
Method had not only remained the characteristics of conventional emulsion polymerizations method, but also had that non-environmental-pollution, required emulsifier be less, stability
Well equal peculiar advantages.However, Pickering emulsion polymerization has very high selectivity to solids, it is well known that particle
Can wettability of the surface play vital influence to form Pickering lotion.The water oil of solids in general
Contact angle θ<It is relative hydropathic particle at 90 °, surface is largely spontaneously wet out by water, and easily prepares oil-in-water using such solids
Type Pickering lotion；Conversely, for θ>90 ° of solids then can be used for preparing water-in-oil type Pickering lotion.
It is noted that surface is easily mutually soaked by single water phase or oil when solids are more hydrophilic or oleophylic, thus
Oil-water interfaces can not be adsorbed on to form stable Pickering lotion.However, having both hydrophilic and oil-wet behavior solids
It is actually rare, the application range of Pickering emulsion polymerization is just greatly defined in this way.In general, pass through these sides
Microballoon size distribution prepared by method is uneven (in micron random distribution from tens nanometers to tens).
In view of the above-mentioned problems, we study previous in propose a kind of preparation method of new hydridization hollow microsphere.
I.e. by introducing nanoparticle of the surface with silicone hydroxyl or titanium hydroxyl, to promote silane coupling agent (such as 3- isobutene acyl-oxygen
Propyl trimethoxy silicane, TPM) hydrolysis, and inhibit the polycondensation of its hydrolysate simultaneously, so that the primary hydrolysis of TPM
Product has the structure and function of emulsifier, these primary hydrolysates meeting oil emulsion aqueous systems form stable oil-in-water cream
Liquid causes silane coupling agent in the free radical polymerization of oil-water interfaces by the way that initiator (such as potassium peroxydisulfate, KPS) is added, can make
Obtain hydridization hollow microsphere.This method, which avoids, introduces a large amount of emulsifier and assistant for emulsifying agent, but needs pre-hydrolysis process, extends
Preparation time, and the hydridization hollow microsphere partial size prepared is unable to satisfy certain fields at sub-micron rank (300~400 nanometers)
Demand to hydridization hollow nanospheres (less than 100 nanometers).
For these reasons, the hydridization hollow nanospheres that a kind of system is simple, operation is simple, time-consuming is short, yield is big are developed
Preparation method it is very necessary.
Summary of the invention
It is an object of the invention to overcome the above-mentioned prior art, provide that a kind of system is simple, operation is simple, time-consuming
The preparation method of the organic inorganic hybridization hollow nanospheres short, yield is big.Above-mentioned preparation method is reproducible, simple process, green
Color is pollution-free, is suitable for large-scale industrial production, and with the obvious advantage compared with common method.
The present invention adopts the following technical scheme that：
A method of organic inorganic hybridization hollow nanospheres being prepared by ultrasound, described method includes following steps：
(1) prepare following components：Water, pH adjusting agent, silane coupling agent and oily phase；
(2) component in mixing step (1) obtains mixed system, is ultrasonically treated；
(3) radical initiator initiated polymerization is added；
(4) washing obtains the organic inorganic hybridization hollow nanospheres.
Preferably, preparation-obtained nanosphere size is less than 100nm, inner hollow, and shell is made of silicon-containing polymer.
According to the present invention, the nanosphere shell has the inorganic network of Si-O-Si, while having having after double-bond polymerization
Chain section part, is connected between inorganic network and organic segment by chemical bond, is organic-inorganic hybrid structure.
The above method is related to preparing organic inorganic hybridization hollow nanospheres by ultrasonication, is prepared by the method
The particle diameter distribution of organic inorganic hybridization hollow nanospheres is uniform, and size is less than 100nm, and surface is smooth, and inner hollow, shell is by containing
Silicon polymer composition is organic-inorganic hybrid structure, has both hydrophilic and oleophylic characteristic.
Preferably, the pH adjusting agent is alkali；More preferable inorganic base；More preferably ammonium hydroxide.
Preferably, the pH of the mixed system is between 7.0~14.0, and more preferable pH is between 9.4~10.0.
Preferably, the silane coupling agent is the silane coupling agent with double bond structure；More preferably with double bond structure
Alkoxy silane coupling agent；More preferable 3- methacryloyl oxygen propyl trimethoxy silicane.
Preferably, the volume ratio of the silane coupling agent and water is 1:20~1:2000；Preferably 1:100~1:800.
Preferably, the oil is mutually esters, such as C1-6Carboxylic acid C1-8Alkyl esters, still more preferably butyl acetate, acetic acid are different
One of propyl ester, isobutyl acetate, isoamyl acetate etc. are a variety of, such as can be isoamyl acetate.
Preferably, the oil is mutually 1 with the volume ratio of silane coupling agent:1~10:1；More preferably 2:1~5:1.
Preferably, in step (2), the power of the ultrasound is 1~104Between MHz, more preferable 50~150MHz.
Preferably, the ultrasonic time is between 1min~10h, more preferable 3~20min.
Preferably, the temperature when ultrasound is 0~80 DEG C, more preferable 15~30 DEG C.
Preferably, in step (3), the radical initiator is water-soluble free radical initiator；More preferably persulfuric acid
Potassium.
Preferably, in step (3), polymeric reaction temperature is higher than 55 DEG C；More preferable 60~80 DEG C.
Preferably, the polymerization reaction time in the step (3) is 8~24 hours；More preferably 12~14 hours.
The present invention also provides following technical solutions：
A kind of organic inorganic hybridization hollow nanospheres prepared by the preparation method, wherein the nanosphere ruler
Very little to be less than 100nm, inner hollow, shell is made of silicon-containing polymer.
The particle diameter distribution of the organic inorganic hybridization hollow nanospheres is uniform, and size is less than 100nm, and surface is smooth, is organic
Inorganic hybrid structure has both hydrophilic and oleophylic characteristic.
According to the present invention, the nanosphere shell has the inorganic network of Si-O-Si, while having having after double-bond polymerization
Chain section part, is connected between inorganic network and organic segment by chemical bond, is organic-inorganic hybrid structure.
The present invention also provides the purposes of above-mentioned organic inorganic hybridization hollow nanospheres, especially suitable for the ruler to hollow ball
It is very little to be strictly limited in nanoscale field.
Involved in the present invention by ultrasound prepare organic inorganic hybridization hollow nanospheres method and product have with
Lower advantage：
1. preparation method of the present invention is interfacial emulsion polymerization, it is hollow that organic inorganic hybridization is prepared by ultrasound
Nanosphere.This method has the feature that system is simple, easy to operate, reproducible, time-consuming is short, yield is big.
2. prepared organic inorganic hybridization hollow nanospheres according to the present invention, size is in 100nm hereinafter, particle diameter distribution phase
To uniform, compared with the hollow microsphere of other methods preparation, partial size is more uniform, and size more meets nanoscale, particularly suitable
In the field for needing hollow nanospheres.The hollow nanospheres shell is machine inorganic hybrid structure, the amphiphilic with hydrophilic and oleophilic
Characteristic greatly increases its scope of application.
3. method of the present invention adopts water as decentralized medium, green non-pollution.
4. of the present invention compared with the previously proposed method that particle of the surface with silicone hydroxyl or titanium hydroxyl is added
Method significantly shortens preparation time, and prepared hollow ball partial size is smaller (less than 100 nanometers).
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of organic inorganic hybridization hollow nanospheres obtained in embodiment 1.
Specific embodiment
As described above, the invention discloses a kind of method for preparing organic inorganic hybridization hollow nanospheres by ultrasound, institute
The method of stating includes the following steps：
(1) prepare following components：Water, pH adjusting agent, silane coupling agent and oily phase；
(2) component in mixing step (1) obtains mixed system, is ultrasonically treated；
(3) radical initiator initiated polymerization is added；
(4) washing obtains the organic inorganic hybridization hollow nanospheres.
The method is a kind of interfacial emulsion polymerization, and the hollow nanometer of organic inorganic hybridization in the present invention is made by ultrasound
Ball.Specifically, the step (2) can be：
Water is added, pH adjusting agent is added, obtains mixed liquor；Silane coupling agent and oil are added to above-mentioned system, ultrasound,
Under the action of ultrasound, silane coupling agent hydrolysis forms the structure of the hydrophilic other end oleophylic in one end, has the function of emulsifier, energy
Oil in system is mutually emulsified, so that system be made to be converted into stable emulsion oil-in-water；
Alternatively, silane coupling agent and oily phase is added, the mixed liquor of water and pH adjusting agent is added, ultrasound, in the work of ultrasound
Under, silane coupling agent hydrolysis forms the structure of the hydrophilic other end oleophylic in one end, has the function of emulsifier, can will be in system
Oil mutually emulsify, so that system be made to be converted into stable emulsion oil-in-water.
That is, the present invention realizes the mistake for being converted into emulsifier of the silane coupling agent by the method for ultrasound
Journey.Compared with conventional emulsion polymerizations method, the introducing of emulsifier and assistant for emulsifying agent is avoided；It polymerize with Pickering interfacial emulsion
Method is compared, and extraneous solids particle is avoided；With the previously proposed side that particle of the surface with silicone hydroxyl or titanium hydroxyl is added
Method is compared, and the used time is shorter, and prepared microspherulite diameter is smaller.In addition, hollow sphere partial size prepared by the method according to the present invention
It is nanoscale and uniform particle sizes.
Below in conjunction with drawings and examples, the present invention is described in further detail.Original used in following embodiments
Material, unless otherwise specified, can be commercially available.
Ultrasonic device used in following methods is able to satisfy ultrasonic power needed for invention without particular/special requirement.
Embodiment 1
Raw material uses 3- methacryloyl oxygen propyl trimethoxy silicane (TPM), isoamyl acetate, ammonium hydroxide and water, initiator
For potassium peroxydisulfate.At room temperature, 40mL pure water is taken, adjusts its pH value to 10 using ammonium hydroxide.Then, by 0.2mL TPM and 0.6mL second
Isoamyl valerate is added separately in above-mentioned system, at room temperature ultrasound (100MHz) 15min.Lead to later nitrogen deoxygenation 30 minutes, rises
Temperature is added 10mg potassium peroxydisulfate and causes polymerization, polymerization reaction continues 12 hours to 70 DEG C.Gained lotion is centrifugated, second is used
After alcohol cleans 3 times, organic inorganic hybridization hollow nanospheres can be obtained.
It disperses above-mentioned organic inorganic hybridization hollow nanospheres in ethyl alcohol, transmission electron microscope sample is made, observe particle shape
Looks.As shown in Figure 1, the organic inorganic hybridization hollow nanospheres partial size is less than 100 nanometers, particle diameter distribution is uniform, has cavity
Structure.
The hollow nanospheres are made of silicon-containing polymer, and the shell of hollow nanospheres has the inorganic network of Si-O-Si, together
When with organic segment part after double-bond polymerization, be connected between inorganic network and organic segment by chemical bond, be organic nothing
Machine hybrid structure, the amphiphilic nature with hydrophilic and oleophilic.
Embodiment 2
Raw material uses 3- methacryloyl oxygen propyl trimethoxy silicane (TPM), isoamyl acetate, ammonium hydroxide and water, initiator
For potassium peroxydisulfate.At room temperature, 60mL pure water is taken, adjusts its pH value to 9.4 using ammonium hydroxide.Then, by 0.2mL TPM and 0.6mL
Isoamyl acetate is added separately in above-mentioned system, at room temperature ultrasound (100MHz) 15min.Lead to later nitrogen deoxygenation 30 minutes,
70 DEG C are warming up to, 10mg potassium peroxydisulfate is added and causes polymerization, polymerization reaction continues 10 hours.Gained lotion is centrifugated, is used
After ethyl alcohol cleans 3 times, organic inorganic hybridization hollow nanospheres can be obtained.
It disperses above-mentioned organic inorganic hybridization hollow nanospheres in ethyl alcohol, transmission electron microscope sample is made, observe particle shape
Looks.Similar with shown in Fig. 1, for the organic inorganic hybridization hollow nanospheres partial size less than 100 nanometers, particle diameter distribution is uniform, has
Cavity structure.
The hollow nanospheres are made of silicon-containing polymer, and the shell of hollow nanospheres has the inorganic network of Si-O-Si, together
When with organic segment part after double-bond polymerization, be connected between inorganic network and organic segment by chemical bond, be organic nothing
Machine hybrid structure, the amphiphilic nature with hydrophilic and oleophilic.
Protection scope of the present invention is not limited only to above-described embodiment.According to the present disclosure, those skilled in the art
Member will be recognized in the case where not departing from technical characteristic given by technical solution of the present invention and range, implement to the above
Example makes many change and modification and belongs to protection scope of the present invention.
Claims (17)
1. a kind of method for preparing organic inorganic hybridization hollow nanospheres by ultrasound, described method includes following steps：
（1）Prepare following components：Water, pH adjusting agent, silane coupling agent and oily phase；
The volume ratio of the silane coupling agent and water is 1:20~1:2000；
The oil is mutually C1-6Carboxylic acid C1-8Alkyl esters；
The oil is mutually 1 with the volume ratio of silane coupling agent:1~10:1；
The silane coupling agent is the silane coupling agent with double bond structure；
The pH adjusting agent is alkali；
（2）Mixing step（1）In component obtain mixed system, be ultrasonically treated；
The power of the ultrasound is 1 ~ 104Between MHz；
The ultrasonic time is between 1 min ~ 10h；
Temperature when the described ultrasound is 0 ~ 80 DEG C；
The pH of the mixed system is between 9.4~10.0；
Under the action of ultrasound, silane coupling agent hydrolysis forms the structure of the hydrophilic other end oleophylic in one end, the function with emulsifier
Can, the oil in system can mutually be emulsified, so that system be made to be converted into stable emulsion oil-in-water；
（3）Radical initiator initiated polymerization is added；
（4）Washing, obtains the organic inorganic hybridization hollow nanospheres；Preparation-obtained nanosphere size less than 100 nm,
Inner hollow, shell are made of silicon-containing polymer；The nanosphere shell has the inorganic network of Si-O-Si, while having double
Organic segment part after key polymerization, is connected between inorganic network and organic segment by chemical bond, is organic inorganic hybridization knot
Structure.
2. the method according to claim 1, wherein the pH adjusting agent is inorganic base.
3. according to the method described in claim 2, it is characterized in that, the pH adjusting agent is ammonium hydroxide.
4. the method according to claim 1, wherein the silane coupling agent is the alkoxy with double bond structure
Silane coupling agent.
5. according to the method described in claim 4, it is characterized in that, the silane coupling agent is 3- methacryloyl oxygen propyl group front three
Oxysilane.
6. method according to claim 1-5, which is characterized in that the volume ratio of the silane coupling agent and water is
1:100~1:800.
7. method according to claim 1-5, which is characterized in that the oil is mutually butyl acetate, isopropyl acetate
One of ester, isobutyl acetate, isoamyl acetate are a variety of.
8. the method according to the description of claim 7 is characterized in that the oil is mutually isoamyl acetate.
9. method according to claim 1-5, which is characterized in that the volume ratio of the oil phase and silane coupling agent
It is 2:1~5:1.
10. method according to claim 1-5, which is characterized in that step（2）In, the power of the ultrasound is
50~150 MHz；
The ultrasonic time is 3 ~ 20 min；
Temperature when the described ultrasound is 15 ~ 30 DEG C.
11. method according to claim 1-5, which is characterized in that step（3）In, the radical initiator
For water-soluble free radical initiator.
12. according to the method for claim 11, which is characterized in that the radical initiator is potassium peroxydisulfate.
13. method according to claim 1-5, which is characterized in that step（3）In, polymeric reaction temperature is higher than
55℃。
14. according to the method for claim 13, which is characterized in that step（3）In, polymeric reaction temperature is 60~80 DEG C.
15. method according to claim 1-5, which is characterized in that the step（3）In polymerization reaction time
It is 8~24 hours.
16. according to the method for claim 15, which is characterized in that the step（3）In polymerization reaction time be 12~
14 hours.
17. a kind of organic inorganic hybridization hollow nanospheres being prepared by the described in any item methods of claim 1-16,
It is characterized in that, preparation-obtained nanosphere size is made of less than 100 nm, inner hollow, shell silicon-containing polymer；It is described
Shell has the inorganic network of Si-O-Si, while having organic segment part after double-bond polymerization, inorganic network and organic segment
Between by chemical bond be connected, be organic-inorganic hybrid structure.
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