CN106882811A - A kind of sea urchin shape bivalve layer hollow microsphere and preparation method thereof - Google Patents
A kind of sea urchin shape bivalve layer hollow microsphere and preparation method thereof Download PDFInfo
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Abstract
A kind of sea urchin shape bivalve layer hollow microsphere and preparation method thereof, by polystyrene/silica dioxide core-shell particles ultrasonic disperse in absolute ethyl alcohol, then the ethanol solution of butyl titanate is added dropwise, 2h~4h is reacted at 75 DEG C~85 DEG C, many core-shell particles of polystyrene/silica dioxide/titanium dioxide are obtained；The many core-shell particles calcinings of polystyrene/silica dioxide/titanium dioxide that will be obtained, obtain bivalve layer hollow silica/titanium dioxide microballoon sphere；By bivalve layer hollow silica/titanium dioxide microballoon sphere ultrasonic disperse in the mixed solution of glycerine and absolute ethyl alcohol, butyl titanate is subsequently adding, is stirred, be transferred in reactor, 7h~12h is reacted under the conditions of 140 DEG C~220 DEG C, sea urchin shape bivalve layer hollow microsphere is obtained；Sea urchin shape bivalve layer hollow microsphere prepared by the present invention not only has relatively low thermal conductivity factor, while having extraordinary absorption to UVA in ultraviolet and UVB.
Description
Technical field
The invention belongs to field of nanometer material technology, more particularly to a kind of sea urchin shape bivalve layer hollow microsphere and preparation method thereof.
Background technology
Insulation material is incubated mechanism and is divided into isolation-type, reflection-type and radial pattern according to it.Current insulation material is mainly utilized
Inorganic particulate plays effect of heat insulation, i.e. reflection-type coating to the shielding of ultraviolet light and near infrared light and reflex；Except this
Outside, more also using aeroge or hollow glass microbead etc. can the low material of thermal conductivity factor such as stored air it is heat-insulated to rise
Function, i.e. isolation-type paint.However, single reflection-type coating or isolation-type paint are respectively provided with limitation in actual applications
Property.Some researchers are obtained by the way that multiple material is combined and have isolation-type concurrently and have the insulation material of reflection-type again, but such
Method easily produces consistency problem.Meanwhile, destruction of the ultraviolet to material has become current research persons are in the urgent need to solution
Problem certainly, multifunction has turned into realizes economic maximized major way, if revesting insulation by certain means
It is material some special functions, such as uvioresistant, antibacterial, antistatic, then have to the range of application for widening such thermal insulation coatings
Good facilitation.
Hollow silica is that a kind of thermal conductivity factor is extremely low and material with good chemical stability, is widely used in surpassing
The fields such as acoustic imaging, medicament slow release, catalysis and heavy metal adsorption.Used as a kind of typical semi-conducting material, it prohibits titanium dioxide
Bandwidth is larger (3.2eV), with stronger infrared-reflecting power, good, nontoxic chemical stability, low cost and pollution-free.
Meanwhile, rutile titanium dioxide has good absorbability to UVA, and anatase titanium dioxide has well to UVB
Absorbability.
The content of the invention
It is an object of the invention to provide a kind of sea urchin shape bivalve layer hollow microsphere and preparation method thereof, using party's legal system
Standby sea urchin shape bivalve layer hollow microsphere hypostracum is silica, outer shell is rutile titanium dioxide, nano surface rod
It is anatase titanium dioxide, and the microballoon has excellent heat-insulating property, while having preferably resistance energy to UVA and UVB
Power.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of sea urchin shape bivalve layer hollow microsphere, comprises the following steps：
(1) then polystyrene/silica dioxide core-shell particles ultrasonic disperse is added dropwise butyl titanate in absolute ethyl alcohol
Ethanol solution, at 75 DEG C~85 DEG C react 2h~4h, product is centrifuged and washed, obtain polystyrene/titanium dioxide
The many core-shell particles of silicon/titanium dioxide；The many core-shell particles calcinings of polystyrene/silica dioxide/titanium dioxide that will be obtained, obtain double
Shell hollow silica/titanium dioxide microballoon sphere；Wherein, the matter of polystyrene/silica dioxide core-shell particles and butyl titanate
Amount is than being 1:2.75~1:8.27；
(2) it is bivalve layer hollow silica/titanium dioxide microballoon sphere ultrasonic disperse is molten in the mixing of glycerine and absolute ethyl alcohol
In liquid, be subsequently adding butyl titanate, stir, be transferred in reactor, under the conditions of 140 DEG C~220 DEG C react 7h~
12h, centrifuge washing, drying obtain sea urchin shape bivalve layer hollow microsphere；Wherein, in step (2) bivalve layer hollow silica/
The ratio of titanium dioxide microballoon sphere and butyl titanate is (0.05g~0.4g)：(1mL~5mL).
Further improvement of the invention is that the ethanol solution of butyl titanate is butyl titanate in step (1)
It is 1 with absolute ethyl alcohol mass ratio:100 solution.
The present invention is further improved, polystyrene/silica dioxide core-shell particles and absolute ethyl alcohol in step (1)
Than being (0.03g~0.09g)：(15mL~24mL).
Further improvement of the invention is that reaction is entered under the stirring that rotating speed is 300~400r/min in step (1)
Capable.
Of the invention further improvement is that the temperature of calcining is 850 DEG C~1000 DEG C in step (1), the time be 3h~
5h。
The present invention is further improved, bivalve layer hollow silica/titanium dioxide microballoon sphere and glycerine in step (2)
Ratio be (0.05g~0.4g)：(5g~15g).
Further improvement of the invention is that the ratio of glycerine and absolute ethyl alcohol is (5g~15g) in step (2)：(20mL~
35mL)。
Of the invention further improvement be, the power of ultrasound is 200~500W in step (2), the time be 10min~
20min；The speed of stirring is 300~450rpm in step (2), and the time is 15min~30min.
Further improvement of the invention is that polystyrene/silica dioxide core-shell particles are prepared by procedure below：Will be poly-
Phenylethylene micro ball emulsion is added in the mixed solution of distilled water and isopropanol, and pH is to value 9.5~10.6 for regulation, is mixed
Thing；Tetraethyl orthosilicate is added dropwise to mixing species, drop finishes after 5h~8h is stirred at 40 DEG C~60 DEG C, product centrifuge washing is done
It is dry, obtain polystyrene/silica dioxide core-shell particles.
Further improvement of the invention is that the ratio of polystyrene microsphere emulsion and distilled water is 15mL~26mL：18mL
The ratio of~24mL, polystyrene microsphere emulsion and tetraethyl orthosilicate is 15mL~26mL：1.0g~2.3g, distilled water and isopropanol
Ratio be 18mL~24mL：75mL~84mL；PH value to 9.5~10.6 is adjusted using ammoniacal liquor.
A kind of sea urchin shape bivalve layer hollow microsphere, the hollow microsphere hypostracum is silica, and outer shell is rutile-type
Titanium dioxide, length has anatase titanium dioxide nanometer rods on outer shell, and the length of nanometer rods is 100nm~1 μm.
The present invention relative to prior art, with following beneficial effect：
(1) present invention is with polystyrene microsphere as template, in its Surface coating layer of silicon dioxide, then using colloidal sol-solidifying
Again in its Surface coating layer of titanium dioxide, high-temperature calcination removes template to glue method, while so that the titanium dioxide of outer layer is converted into
Rutile-type；Finally with above-mentioned bivalve layer hollow microsphere as template, sharp titanium is grown in outer layer titanium dioxide surface using hydro-thermal method
Ore deposit type titanium dioxide nano-rod, obtains sea urchin shape bivalve layer hollow microsphere.The sea urchin shape bivalve layer prepared using the method is hollow
Microballoon, outer shell is rutile titanium dioxide, nano surface rod is anatase titanium dioxide, therefore has to UVA and UVB
Good resistivity, its absorption to ultraviolet is up to 83.4%.
(2) the sea urchin shape bivalve layer hollow microsphere prepared using the method, it is extremely low that its hollow structure can store thermal conductivity factor
Air, itself thermal conductivity factor of hypostracum silica it is relatively low with good barrier property；Outer shell titanium dioxide is near red
The presence that outside line has good reflecting properties, surface titanium dioxide nanometer rods can further increase the storage capacity of air and improve
Reflecting properties, its thermal conductivity factor can be reduced to 0.051W/ (mk), and light reflectivity is up to 99.6%.
(3) present invention prepares sea urchin shape bivalve layer using hard template method with the method that sol-gal process and hydro-thermal method are combined
Hollow microsphere, product morphology is regular, size uniformity.
(4) the sea urchin shape bivalve layer hollow microsphere prepared by the present invention is made up of outer shell and hypostracum, and outer shell is sharp
Titanium ore type titanium dioxide nano-rod, rutile titanium dioxide, hypostracum is silica, outermost Detitanium-ore-type titanium dioxide
A length of 100nm~1 μm of rod of titanium nanometer rods.The microballoon has relatively low thermal conductivity factor again with infrared reflection energy higher
Power, is that a kind of isolation-type that has concurrently has a thermal insulation material of reflection-type again, while the titanium dioxide and table of outer shell rutile-type
The nano titanium oxide rod of face Detitanium-ore-type has absorbability higher to the UVA in ultraviolet and UVB.
Brief description of the drawings
Fig. 1 is the SEM photograph of polystyrene/silica dioxide core-shell particles.
Fig. 2 is the SEM photograph of bivalve layer hollow silica/titanium dioxide microballoon sphere.
Fig. 3 is that the multiplication factor of sea urchin shape bivalve layer hollow microsphere is 70000 times of SEM photograph.
Fig. 4 is that the multiplication factor of sea urchin shape bivalve layer hollow microsphere is 4000 times of SEM photograph.
Specific embodiment
Below by specific embodiment a kind of preparation method of layer hollow microsphere in sea urchin shape bivalve of the present invention is done into
One step explanation.
Embodiment 1
(1) 15mL polystyrene microsphere emulsions are measured, with 18mL distilled water and 75mL isopropanols, then using ammoniacal liquor
Regulation pH value is added dropwise 1g tetraethyl orthosilicates to 9.5 with glue head dropper, and about 2min drops finish, then in machinery under 40 DEG C, 300r/min
Stirring 5h, product is centrifuged and wash 1~3 time with isopropanol, and 4h is dried in 50 DEG C of baking ovens, obtain particle diameter be 50nm~
The polystyrene/silica dioxide core-shell particles of 500nm.
(2) 0.03g polystyrene/silica dioxide core-shell particles are weighed, (power of ultrasound is 500W to ultrasound, and the time is
10min) it is dispersed in 15mL absolute ethyl alcohols, the absolute ethyl alcohol that the butyl titanate that 24mL mass concentrations are 1% is added dropwise therewith is molten
Liquid, after completion of dropping, 4h is reacted at 300r/min, 75 DEG C, and product is centrifuged, and with absolute ethanol washing 1~3 time, is obtained
The many core-shell particles of polystyrene/silica dioxide/titanium dioxide, many nucleocapsids of polystyrene/silica dioxide/titanium dioxide that will be obtained
Particle calcines 5h under the conditions of 850 DEG C, obtains bivalve layer earth silicon/titanic oxide.Bivalve layer earth silicon/titanic oxide
Outer shell is rutile titanium dioxide, and hypostracum is titanium dioxide；Wherein, metatitanic acid in the ethanol solution of butyl titanate
Four butyl esters are 1 with the mass ratio of absolute ethyl alcohol:100.
(3) 0.2g bivalves layer hollow silica/titanium dioxide microballoon sphere, 5g glycerine and 20mL absolute ethyl alcohols ultrasound are weighed
Dispersion 10min, is subsequently adding 1mL butyl titanates, at 300 rpm magnetic agitation 15min, is transferred to polytetrafluoroethyl-ne alkene reaction
In kettle, 12h is reacted under the conditions of 140 DEG C, centrifuge washing is dried, obtain sea urchin shape bivalve layer hollow microsphere.
Embodiment 2
(1) 22mL polystyrene microsphere emulsions are measured, with 21mL distilled water and 81mL isopropanols, then using ammoniacal liquor
Regulation pH value is added dropwise 1.4g tetraethyl orthosilicates to 10.0 with glue head dropper, and about 2min drops finish, then under 50 DEG C, 300r/min
Mechanical agitation 5h, product is centrifuged and is washed 1~3 time with isopropanol, and 6h is dried in 40 DEG C of baking ovens, obtains particle diameter for 50nm
The polystyrene/silica dioxide core-shell particles of~500nm.
(2) 0.09g polystyrene/silica dioxide core-shell particles are weighed, (power of ultrasound is 200W to ultrasound, and the time is
20min) it is dispersed in 18mL absolute ethyl alcohols, the absolute ethyl alcohol that the butyl titanate that 24mL mass concentrations are 1% is added dropwise therewith is molten
Liquid, after completion of dropping, 3h is reacted at 300r/min, 75 DEG C, and product is centrifuged, and with absolute ethanol washing 1~3 time, is obtained
The many core-shell particles of polystyrene/silica dioxide/titanium dioxide, many nucleocapsids of polystyrene/silica dioxide/titanium dioxide that will be obtained
Particle calcines 3h under the conditions of 900 DEG C, obtains the bivalve layer earth silicon/titanic oxide that outer shell is rutile-type.Wherein titanium
Butyl titanate and the mass ratio of absolute ethyl alcohol are 1 in the ethanol solution of sour four butyl esters:100.
(3) 0.3g bivalves layer hollow silica/titanium dioxide microballoon sphere, 11g glycerine and 30mL absolute ethyl alcohols are weighed super
Sound disperses 10min, is subsequently adding 2mL butyl titanates, at 450 rpm magnetic agitation 15min, is transferred to polytetrafluoroethylene (PTFE) anti-
Answer in kettle, 11h is reacted under the conditions of 160 DEG C, centrifuge washing is dried, obtain sea urchin shape bivalve layer hollow microsphere.
Embodiment 3
(1) 24mL polystyrene microsphere emulsions are measured, with 22mL distilled water and 82mL isopropanols, then using ammoniacal liquor
Regulation pH value is added dropwise 1.8g tetraethyl orthosilicates to 10.1 with glue head dropper, and about 3min drops finish, then in 60 DEG C, under 300r/min
Mechanical agitation 6h, product is centrifuged and is washed 1~3 time with isopropanol, and 4h is dried in 60 DEG C of baking ovens, obtains particle diameter for 50nm
The polystyrene/silica dioxide core-shell particles of~500nm.
(2) 0.07g polystyrene/silica dioxide core-shell particles are weighed, (power of ultrasound is 300W to ultrasound, and the time is
15min) it is dispersed in 21mL absolute ethyl alcohols, the absolute ethyl alcohol that the butyl titanate that 24mL mass concentrations are 1% is added dropwise therewith is molten
Liquid, after completion of dropping, 3h is reacted at 300r/min, 80 DEG C, and product is centrifuged, and with absolute ethanol washing 1~3 time, is obtained
The many core-shell particles of polystyrene/silica dioxide/titanium dioxide, many nucleocapsids of polystyrene/silica dioxide/titanium dioxide that will be obtained
Particle calcines 3h under the conditions of 900 DEG C, obtains the bivalve layer earth silicon/titanic oxide that outer shell is rutile-type.Wherein titanium
Butyl titanate and the mass ratio of absolute ethyl alcohol are 1 in the ethanol solution of sour four butyl esters:100.
(3) 0.4g bivalves layer hollow silica/titanium dioxide microballoon sphere, 12g glycerine and 32mL absolute ethyl alcohols are weighed super
Sound disperses 10min, is subsequently adding 2mL butyl titanates, and magnetic agitation 15min, is transferred to polytetrafluoroethylene (PTFE) anti-under 400rpm
Answer in kettle, 10h is reacted under the conditions of 180 DEG C, centrifuge washing is dried, obtain sea urchin shape bivalve layer hollow microsphere.
Embodiment 4
(1) 26mL polystyrene microsphere emulsions are measured, with 24mL distilled water and 84mL isopropanols, then using ammoniacal liquor
Regulation pH value is added dropwise 2.3g tetraethyl orthosilicates to 10.6 with glue head dropper, and about 5min drops finish, then under 60 DEG C, 300r/min
Mechanical agitation 8h, product is centrifuged and is washed 1~3 time with isopropanol, and 4h is dried in 70 DEG C of baking ovens, obtains particle diameter for 50nm
The polystyrene/silica dioxide core-shell particles of~500nm.
(2) 0.09g polystyrene/silica dioxide core-shell particles are weighed, (power of ultrasound is 400W to ultrasound, and the time is
15min) it is dispersed in 24mL absolute ethyl alcohols, the absolute ethyl alcohol that the butyl titanate that 24mL mass concentrations are 1% is added dropwise therewith is molten
Liquid, after completion of dropping, 3h is reacted at 400r/min, 80 DEG C, and product is centrifuged, and with absolute ethanol washing 1~3 time, is obtained
The many core-shell particles of polystyrene/silica dioxide/titanium dioxide, many nucleocapsids of polystyrene/silica dioxide/titanium dioxide that will be obtained
Particle calcines 3h under the conditions of 1000 DEG C, obtains the bivalve layer earth silicon/titanic oxide that outer shell is rutile-type.Wherein titanium
Butyl titanate and the mass ratio of absolute ethyl alcohol are 1 in the ethanol solution of sour four butyl esters:100.
(3) 0.4g bivalves layer hollow silica/titanium dioxide microballoon sphere, 15g glycerine and 34mL absolute ethyl alcohols are weighed super
Sound disperses 10min, adds 5mL butyl titanates, and magnetic agitation 15min, is transferred to ptfe autoclave under 350rpm
In, 7h is reacted under the conditions of 220 DEG C, centrifuge washing is dried, and obtains sea urchin shape bivalve layer hollow microsphere.
Embodiment 5
(1) 26mL polystyrene microsphere emulsions are measured, with 24mL distilled water and 84mL isopropanols, then using ammoniacal liquor
Regulation pH value is added dropwise 2.3g tetraethyl orthosilicates to 10.6 with glue head dropper, and about 5min drops finish, then under 60 DEG C, 300r/min
Mechanical agitation 8h, product is centrifuged and is washed 1~3 time with isopropanol, and 4h is dried in 70 DEG C of baking ovens, obtains particle diameter for 50nm
The polystyrene/silica dioxide core-shell particles of~500nm.
(2) 0.09g polystyrene/silica dioxide core-shell particles are weighed, (power of ultrasound is 500W to ultrasound, and the time is
10min) it is dispersed in 24mL absolute ethyl alcohols, the absolute ethyl alcohol that the butyl titanate that 24mL mass concentrations are 1% is added dropwise therewith is molten
Liquid, after completion of dropping, 3h is reacted at 400r/min, 80 DEG C, and product is centrifuged, and with absolute ethanol washing 1~3 time, is obtained
The many core-shell particles of polystyrene/silica dioxide/titanium dioxide, many nucleocapsids of polystyrene/silica dioxide/titanium dioxide that will be obtained
Particle calcines 3h under the conditions of 1000 DEG C, obtains the bivalve layer earth silicon/titanic oxide that outer shell is rutile-type.Wherein titanium
Butyl titanate and the mass ratio of absolute ethyl alcohol are 1 in the ethanol solution of sour four butyl esters:100.
(3) 0.05g bivalves layer hollow silica/titanium dioxide microballoon sphere, 5g glycerine and 20mL absolute ethyl alcohols are weighed super
Sound disperses 20min, adds 5mL butyl titanates, and magnetic agitation 15min, is transferred to ptfe autoclave at 300 rpm
In, 8h is reacted under the conditions of 200 DEG C, centrifuge washing is dried, and obtains sea urchin shape bivalve layer hollow microsphere.
The structure of sea urchin shape bivalve layer hollow microsphere is obtained in of the invention：The hollow microsphere hypostracum is silica,
Outer shell is rutile titanium dioxide, and length has anatase titanium dioxide nanometer rods on outer shell, and the length of nanometer rods is
100nm~1 μm.
Fig. 1 is the SEM photograph of polystyrene/silica dioxide core-shell particles, it can be seen that core-shell particles compound with regular structure, the grain
Footpath is homogeneous.Fig. 2 is the SEM photograph of bivalve layer hollow silica/titanium dioxide microballoon sphere, it can be seen that typical hollow knot is presented
Structure, and hypostracum is different from outer shell consistency, is two kinds of different materials.Fig. 3 and Fig. 4 is sea urchin shape bivalve layer hollow microsphere
SEM photograph, it can be seen that titanium dioxide nano-rod is uniform in hollow silica/titanium dioxide microballoon sphere superficial growth, is formed
Sea urchin shape bivalve layer hollow microsphere.Table 1 is the performance of the sea urchin shape bivalve layer hollow microsphere prepared using the present invention, it is known that its
Heat-insulating property and uv absorption property are very excellent.
The performance of the sea urchin shape bivalve of table 1 layer hollow microsphere
Preparation method of the invention：1) with polystyrene microsphere as template, in its Surface coating layer of silicon dioxide；2) adopt
With sol-gel process again in its Surface coating layer of titanium dioxide, high-temperature calcination removes template, while so that the titanium dioxide of outer layer
Titanium is converted into rutile-type；3) with above-mentioned bivalve layer hollow microsphere as template, given birth in outer layer titanium dioxide surface using hydro-thermal method
Anatase titanium dioxide nanometer rods long, obtain sea urchin shape bivalve layer hollow microsphere.Sea urchin shape bivalve layer prepared by the method
Hollow microsphere not only has relatively low thermal conductivity factor, while having extraordinary absorption to UVA in ultraviolet and UVB.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And any equivalent conversion taken technical solution of the present invention, it is claim of the invention and is covered.
Claims (10)
1. the preparation method of a kind of sea urchin shape bivalve layer hollow microsphere, it is characterised in that comprise the following steps：
(1) by particle diameter for 50nm~500nm polystyrene/silica dioxide core-shell particles ultrasonic disperse in absolute ethyl alcohol, so
The ethanol solution of butyl titanate is added dropwise afterwards, 2h~4h is reacted at 75 DEG C~85 DEG C, product is centrifuged and washed, obtain
The many core-shell particles of polystyrene/silica dioxide/titanium dioxide；The many nucleocapsids of polystyrene/silica dioxide/titanium dioxide that will be obtained
Particle is calcined, and obtains bivalve layer hollow silica/titanium dioxide microballoon sphere；Wherein, polystyrene/silica dioxide core-shell particles with
The mass ratio of butyl titanate is 1:2.75~1:8.27；
(2) by bivalve layer hollow silica/titanium dioxide microballoon sphere ultrasonic disperse in the mixed solution of glycerine and absolute ethyl alcohol,
Butyl titanate is subsequently adding, is stirred, be transferred in reactor, 7h~12h is reacted under the conditions of 140 DEG C~220 DEG C, from
Heart washing, dry, acquisition sea urchin shape bivalve layer hollow microsphere；Wherein, layer hollow silica/titanium dioxide in bivalve in step (2)
The ratio of titanium microballoon and butyl titanate is (0.05g~0.4g)：(1mL~5mL).
2. a kind of preparation method of layer hollow microsphere in sea urchin shape bivalve according to claim 1, it is characterised in that step
(1) ethanol solution of butyl titanate is butyl titanate and absolute ethyl alcohol mass ratio is 1 in:100 solution.
3. a kind of preparation method of layer hollow microsphere in sea urchin shape bivalve according to claim 1, it is characterised in that step
(1) ratio of polystyrene/silica dioxide core-shell particles and absolute ethyl alcohol is (0.03g~0.09g) in：(15mL~24mL).
4. a kind of preparation method of layer hollow microsphere in sea urchin shape bivalve according to claim 1, it is characterised in that step
(1) reaction is carried out under the stirring that rotating speed is 300~400r/min in；In step (1) temperature of calcining for 850 DEG C~
1000 DEG C, the time is 3h~5h.
5. a kind of preparation method of layer hollow microsphere in sea urchin shape bivalve according to claim 1, it is characterised in that step
(2) ratio of bivalve layer hollow silica/titanium dioxide microballoon sphere and glycerine is (0.05g~0.4g) in：(5g~15g).
6. a kind of preparation method of layer hollow microsphere in sea urchin shape bivalve according to claim 1, it is characterised in that step
(2) ratio of glycerine and absolute ethyl alcohol is (5g~15g) in：(20mL~35mL).
7. a kind of preparation method of layer hollow microsphere in sea urchin shape bivalve according to claim 1, it is characterised in that step
(2) power of ultrasound is 200~500W in, and the time is 10min~20min；In step (2) speed of stirring for 300~
450rpm, the time is 15min~30min.
8. a kind of preparation method of layer hollow microsphere in sea urchin shape bivalve according to claim 1, it is characterised in that polyphenyl second
Alkene/silica core shell particles are prepared by procedure below：Polystyrene microsphere emulsion is added to distilled water and isopropanol
In mixed solution, regulation pH value obtains mixture to 9.5~10.6；Tetraethyl orthosilicate is added dropwise to mixing species, drop finishes after 40
DEG C~60 DEG C at stir 5h~8h, product centrifuge washing is dried, obtain polystyrene/silica dioxide core-shell particles.
9. a kind of preparation method of layer hollow microsphere in sea urchin shape bivalve according to claim 8, it is characterised in that polyphenyl second
The ratio of alkene microballoon emulsion and distilled water is 15mL~26mL：18mL~24mL, polystyrene microsphere emulsion and tetraethyl orthosilicate
Than being 15mL~26mL：1.0g~2.3g；The ratio of distilled water and isopropanol is 18mL~24mL：75mL~84mL；Using ammoniacal liquor
Adjust pH value to 9.5~10.6.
10. a kind of sea urchin shape bivalve layer hollow microsphere that in 1-9 according to claim prepared by any one method, its feature exists
In the hollow microsphere hypostracum is silica, and outer shell is rutile titanium dioxide, and length has Detitanium-ore-type two on outer shell
TiOx nano rod, and the length of nanometer rods is 100nm~1 μm.
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