CN100506369C - Method for preparing surface patterned SiO2 hollow microsphere - Google Patents
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- CN100506369C CN100506369C CNB2006100426601A CN200610042660A CN100506369C CN 100506369 C CN100506369 C CN 100506369C CN B2006100426601 A CNB2006100426601 A CN B2006100426601A CN 200610042660 A CN200610042660 A CN 200610042660A CN 100506369 C CN100506369 C CN 100506369C
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Abstract
The invention relates to a method for preparing silica dioxide hollow microsphere with pattern on surface, comprising process of preparing mixed surface active agent, composite mould oil phase, emulsion, water phase, cogelled, swelling cogelled, mixing liquid of tetraethoxysilane and skellysolve C, silica dioxide high molecular compound microsphere with pattern on surface. The invention is characterized by rational design, feasible process, simple operation, easy controllable of thickness of silica dioxide shell and short reaction time. The prepared silica dioxide hollow microsphere with pattern on surface is characterized by large specific surface area, smaller quantity, and wide application on biological medicine, damping of vibration, carrying catalyst, fast concentration and separation, sensing technology, environmental protection and ocean mining.
Description
Technical field
The invention belongs to chemistry or physical method technical field, be specifically related to the manufacturing of the microcapsules or the microballoon of colloid chemistry.
Background technology
The SiO 2 hollow microsphere material has the special nature that is different from the preparation of other method, and for example surface modificability is strong and easily separated etc., therefore becomes a big class material that is widely used in colloid and the material science.A lot of about SiO 2 hollow microsphere preparation method's report both at home and abroad, mainly contain following two kinds of methods, promptly prepare the core/shell type complex microsphere earlier, and then remove inner high score daughter nucleus through calcining or dissolving; Perhaps, obtain the tiny balloon material by self-assembly method directly by being template with the molecule self-assembly.These two kinds of methods respectively have its pluses and minuses.For example adopt the synthetic tiny balloon material operation of the method for removing the high score daughter nucleus various, but its controllable size; Adopting the molecule self-assembly is template, and preparation section is simple, but because the poor stability of self-assembly, and be difficult for forming the single type particle, and dispersed bad.Relevant research report is as follows, for example, Mann research group adopts simple method, at room temperature, with the softex kw is template, makes the SiO2 tiny balloon of order mesoporous shell structurre by the hydrolysis under alkali condition of the positive silane of tetraethoxy.People such as Sommerdi jk are at EO
76-PO
29-EO
76In/butanols/ethanol/water quaternary system, pass through Na
2SiO
3Hydrolysis has been synthesized by the huge porous hollow SiO of laminate granular accumulation formation under acid condition
2Microballoon.Its design feature is hollow SiO
2Microballoon is by little SiO
2Microballoon is piled up and is formed.The core/shell type complex microsphere obtains after high-temperature calcination that the report of SiO 2 hollow microsphere material is as follows, and Miller etc. are template with the polystyrene, after its surface is modified with amido or amphion, pass through Na
2SiO
3Hydrolysis under weak basic condition and obtain polystyrene/SiO
2Complex microsphere.Behind the polymer of high-temperature calcination internal layer, obtain hollow SiO
2Microballoon.Molvinger etc. are template with the large biological molecule shitosan, at acetic acid/H
2Add the positive silane of tetraethoxy in the O mixed liquor, obtain hollow SiO by the control experiment condition
2Microballoon.This microballoon shell is by pure SiO
2Form.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming of above-mentioned SiO 2 hollow microsphere material preparation method, provide a kind of reasonable in design, feasible process, easy and simple to handle, the reaction time short, the preparation method of reacted surface patterned silicon dioxide tiny balloon at normal temperatures.
Solving the problems of the technologies described above the technical scheme that is adopted is that this preparation method comprises the steps:
1, preparation mixed surfactant
Si Ban-80 is hybridly prepared into mixed surfactant for 5:1 by weight with Tween-80.
2, the synthetic template oil phase of preparation
The mixed surfactant of step 1 preparation is joined in the there-necked flask that fills normal heptane, and mixed surfactant and normal heptane are by weight be hybridly prepared into synthetic template oil phase for 1:115～130.
3, preparation emulsion
The synthetic template oil phase of step 2 preparation is put into there-necked flask, stir with mixer, mixing speed is 360～400 rev/mins, feeds N with 2～3ml/ minute flow velocity
2,, make emulsion 18～30 ℃ of scope internal emulsifications 40～60 minutes.
4, preparation water
With N, N '-methylene diene acid amides, ammonium persulfate, N-N-isopropylacrylamide mix for 1:1.17:28.3 in molar ratio, stir, and make solution A.Acrylic acid and NaOH are that 23% the PAA aqueous solution is solution B for 1:0.3～1 is mixed with concentration in molar ratio.Solution A and solution B by volume for 6:1 mixes, are imported till nitrogen to oxygen arranged, make water.
5, preparation copolymerization microgel
By volume for 1:10 makes mixed liquor, with the mixer stirring, mixing speed is 360～400 rev/mins, stirs 15 minutes with the emulsion of the water of step 4 preparation and step 3 preparation.The 4.76% tetramethylethylenediamine aqueous solution of mixeding liquid volume 1/154 is joined in the mixed solution, reacted 3～4 hours, generate the copolymerization microgel, incline and remaining reactant liquor, the copolymerization microgel is alternately washed 5～6 times with acetone and secondary water, wash 3～4 times again with acetone at last and removed fully, dry naturally, make sand-like P (NIPAM-co-20%AA) the copolymerization microgel of white up to the adsorbed water of copolymerization microgel.
6, the copolymerization microgel of preparation swelling
By weight for 1:11 is that 28% ammoniacal liquor evenly mixes with copolymerization microgel and concentration, placed 12 hours, make its abundant swelling, make P (NIPAM-co-20%AA) the copolymerization microgel of swelling.
7, the mixed liquor of preparation positive silane of tetraethoxy and normal heptane
The positive silane of tetraethoxy and normal heptane are mixed and made into by volume the mixed liquor of positive silane of tetraethoxy and normal heptane for 1:4.
8, preparation surface patterned SiO 2 high molecular composite microsphere
The swelling copolymerization microgel of step 6 preparation is joined in 40 minutes the deposition oil phase of emulsification, the deposition oil phase is that Si Ban-80 is mixed and made into for 1:160 by weight with normal heptane, at normal temperatures, stir with mixer, mixing speed is 600 rev/mins, drip positive silane of tetraethoxy and the normal heptane mixed liquors that step 7 prepares with constant pressure funnel with 7～8 droplets/minute, reacted 2～12 hours, generate SiO 2 high molecular composite microsphere, remaining reactant liquor inclines, alternately wash SiO 2 high molecular composite microsphere 6～7 times with secondary water and acetone, washing 3～4 times again with acetone is at last removed fully up to the adsorbed water of SiO 2 high molecular composite microsphere, naturally dry, make P (the NIPAM-co-20%AA)/SiO of white
2Complex microsphere.
9, preparation surface patterned SiO 2 hollow microsphere
P (NIPAM-co-20%AA)/SiO with step 8 preparation
2Complex microsphere is placed in the Muffle furnace, under the air atmosphere, is warming up to 300～550 ℃ continuously, calcines 3～5 hours, naturally cools to room temperature, makes white surface patterned silicon dioxide tiny balloon.
The present invention is in the synthetic template oil phase processing step 2 of preparation, and mixed surfactant and normal heptane are preferably by weight be hybridly prepared into synthetic template oil phase for 1:120～125.In the processing step 3 of preparation emulsion, preferred emulsifying temperature is 20～25 ℃.In preparation aqueous process step 4, acrylic acid and NaOH are preferred to be that to be mixed with concentration be 23% the PAA aqueous solution in 1:0.6～0.8 in molar ratio.In preparation surface patterned SiO 2 high molecular composite microsphere processing step 8, the preferred time of preferred reaction is 4～10 hours.In preparation surface patterned SiO 2 hollow microsphere processing step 9, preferred calcination temperature is 350～500 ℃, calcines 4～5 hours.
The present invention is in the synthetic template oil phase processing step 2 of preparation, and mixed surfactant and normal heptane are that 1:122 is hybridly prepared into synthetic template oil phase by optimum weight ratio.In emulsifying process step 3, the optimum emulsification temperature is 25 ℃.In preparation aqueous process step 4, the optimum mole ratio of acrylic acid and NaOH is that to be mixed with concentration be 23% the PAA aqueous solution to 1:0.6.In processing step 8, optimum response is 6 hours.In processing step 9, optimum calcinating temperature is 400 ℃, and best calcination time is 4 hours.
Adopting the surface patterned SiO 2 hollow microsphere of the present invention's preparation, is by nanoscale SiO
2The tightly packed formation of bead.This special structure makes SiO
2Great specific surface that tiny balloon has simultaneously and relative little quality can effectively be controlled SiO by adjusting reaction time
2The thickness of microballoon shell, fields such as this tiny balloon can and separate at biomedical, the damping of suction ripple, catalyst loading, fast enriching, sensing technology, environmental protection, marine mining obtain to use widely.The present invention compares with prior preparation method, has reasonable in design, feasible process, simple to operate, SiO
2Shell thickness is easy to advantages such as control, reaction time weak point.
Description of drawings
Fig. 1 is the electron scanning micrograph that adopts the surface patterned SiO 2 hollow microsphere of the embodiment of the invention 1 preparation.
Fig. 2 is the electron scanning micrograph that Fig. 1 surface local amplifies.
Fig. 3 adopts under the reaction condition of embodiment 1, reacts 2 hours, and the complex microsphere of preparation is at 3 hours SiO 2 hollow microsphere of 550 ℃ of calcinings, the electron scanning micrograph after the Mechanical Crushing.
Fig. 4 is the electron scanning micrograph that Fig. 3 surface local amplifies.
Fig. 5 adopts under the reaction condition of embodiment 1, reacts 6 hours, and the complex microsphere of preparation is at 3 hours SiO 2 hollow microsphere of 550 ℃ of calcinings, the electron scanning micrograph after the Mechanical Crushing.
Fig. 6 is the electron scanning micrograph that Fig. 5 shell surface local amplifies.
Fig. 7 adopts under the reaction condition of embodiment 1, reacts 12 hours, and the complex microsphere of preparation is at 3 hours SiO 2 hollow microsphere of 550 ℃ of calcinings, the electron scanning micrograph after the Mechanical Crushing.
Fig. 8 is the electron scanning micrograph that Fig. 7 shell surface local amplifies.
Fig. 9 adopts under the reaction condition of embodiment 1, and the complex microsphere of preparation is at 300 ℃, 400 ℃, 550 ℃ calcinings 4 hours SiO 2 hollow microsphere, pure SiO
2The FFIR curve map.
Figure 10 is the full-automatic X-x ray diffraction collection of illustrative plates that adopts the SiO 2 hollow microsphere of the embodiment of the invention 1 preparation.
The specific embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Embodiment 1
Present embodiment has provided the preparation method of surface patterned SiO 2 hollow microsphere, and its processing step is as follows:
1, preparation mixed surfactant
Si Ban-80 is hybridly prepared into mixed surfactant for 5:1 by weight with Tween-80.
2, the synthetic template oil phase of preparation
The mixed surfactant of step 1 preparation is joined in the there-necked flask that fills normal heptane, and mixed surfactant and normal heptane are by weight be hybridly prepared into synthetic template oil phase for 1:122.
3, preparation emulsion
The synthetic template oil phase of step 2 preparation is put into there-necked flask, stir with mixer, mixing speed is 360～400 rev/mins, feeds N with 2～3ml/ minute flow velocity
2,, make emulsion 25 ℃ of emulsifications 40～60 minutes.
4, preparation water
With N, N '-methylene diene acid amides, ammonium persulfate, N-N-isopropylacrylamide mix for 1:1.17:28.3 in molar ratio, stir, and are mixed with solution A.Acrylic acid and NaOH are that 23% the PAA aqueous solution is solution B for 1:0.6 is mixed with concentration in molar ratio.Solution A and solution B by volume for 6:1 mixes, are imported till nitrogen to oxygen arranged, make the water that cumulative volume is 7mL.
5, preparation copolymerization microgel
The water of step 4 preparation is joined in the emulsion of 70mL, stir with mixer, mixing speed is 360～400 rev/mins, add 4.76% tetramethylethylenediamine aqueous solution 0.5mL after 15 minutes, reacted 3～4 hours, generate the copolymerization microgel, incline and remaining reactant liquor, the copolymerization microgel is alternately washed 5～6 times with acetone and secondary water, washing 3～4 times again with acetone is at last removed fully up to the adsorbed water of copolymerization microgel, naturally dry, make sand-like P (NIPAM-co-20%AA) the copolymerization microgel of white.
6, the copolymerization microgel of preparation swelling
Adding concentration is 28% 2.3g ammonia spirit in the copolymerization microgel 0.2g of step 5 preparation, places 12 hours, makes its abundant swelling, makes P (NIPAM-co-20%AA) the copolymerization microgel of swelling.
7, the mixed liquor of preparation positive silane of tetraethoxy and normal heptane
The positive silane of the tetraethoxy of 1.0mL and normal heptane are mixed and made into the positive silane of tetraethoxy that total amount is 5.0mL and the mixed liquor of normal heptane.
8, preparation surface patterned SiO 2 high molecular composite microsphere
The swelling copolymerization microgel of step 6 preparation is joined in 40 minutes the deposition oil phase of emulsification, the deposition oil phase is that Si Ban-80 is mixed and made into for 1:160 by weight with normal heptane, at 20 ℃, stir with mixer, mixing speed is 600 rev/mins, drip positive silane of tetraethoxy and the normal heptane mixed liquors that step 7 prepares with constant pressure funnel with 7～8 droplets/minute, reacted 6 hours, generate SiO 2 high molecular composite microsphere, remaining reactant liquor inclines, alternately wash SiO 2 high molecular composite microsphere 6～7 times with secondary water and acetone, washing 3～4 times again with acetone is at last removed fully up to the adsorbed water of SiO 2 high molecular composite microsphere, naturally dry, make P (the NIPAM-co-20%AA)/SiO of white
2Complex microsphere.
9, preparation surface patterned SiO 2 hollow microsphere
P (NIPAM-co-20%AA)/SiO with step 8 preparation
2Complex microsphere is placed in the Muffle furnace, under the air atmosphere, is warming up to 400 ℃ continuously, calcines 4 hours, naturally cools to room temperature, makes white surface patterned silicon dioxide tiny balloon.
Embodiment 2
In the processing step 2 of present embodiment, mixed surfactant is touched leaf fat mutually with normal heptane by weight being hybridly prepared into for 1:115 to synthesize.In step 3, emulsifying temperature is 18 ℃.In the processing step 4, the mol ratio of acrylic acid and NaOH is that to be mixed with concentration be 23% the PAA aqueous solution to 1:0.3.In processing step 8, the reaction time is 2 hours.In processing step 9, the temperature of calcining is 300 ℃, and the time of calcining is 5 hours.Other processing step is identical with embodiment 1.
Embodiment 3
In the processing step 2 of present embodiment, mixed surfactant is touched leaf fat mutually with normal heptane by weight being hybridly prepared into for 1:130 to synthesize.In step 3, emulsifying temperature is 30 ℃.In the processing step 4, the mol ratio of acrylic acid and NaOH is that to be mixed with concentration be 23% the PAA aqueous solution to 1:1.In processing step 8, the reaction time is 12 hours.In processing step 9, the temperature of calcining is 550 ℃, and the time of calcining is 3 hours.Other processing step is identical with embodiment 1.
In order to determine the processing step of the best of the present invention, the inventor has carried out a large amount of laboratory research tests, and various test situation are as follows:
1, the reaction time is to the influence of SiO 2 hollow microsphere shell thickness
It with concentration 25～28% ammoniacal liquor 2.5mL swelling copolymerization microgel, join in 40 minutes the deposition oil phase of emulsification, the deposition oil phase is that Si Ban-80 is mixed and made into for 1:160 by weight with normal heptane, with 600 rev/mins, in reaction temperature is to contain positive silane of 1.0mL tetraethoxy and normal heptane mixed liquor 5.0mL with 7～8 droplets/minute droppings under 20 ℃, after dripping, under other conditionally complete is identical, reacted respectively 2 hours, 6 hours, 12 hours, generate SiO 2 high molecular composite microsphere.SiO 2 high molecular composite microsphere is made surface patterned SiO 2 hollow microsphere 550 ℃ of calcinings 3 hours, and the shell that can be observed tiny balloon after the Mechanical Crushing has very big variation.Reacted 2 hours, the SiO 2 hollow microsphere of 550 ℃ of calcinings preparation in 3 hours has than the shell layer through this microballoon of sem observation, sees Fig. 3, and local amplification is formed by nanometer young waiter in a wineshop or an inn silicon oxide ball fluff packing, sees Fig. 4.Reacted 6 hours, the SiO 2 hollow microsphere of 550 ℃ of calcinings preparation in 3 hours with the sem observation tiny balloon than silicon dioxide microsphere shell thick than reaction 2 hours, see Fig. 5, the local amplification by the little silica spheres of nanometer is tightly packed forms, and sees Fig. 6.Reacted 12 hours, 550 ℃ of calcinings 3 hours, the silicon dioxide microsphere of preparation utilizes the sem observation shell than 6 hours thick of reaction, sees Fig. 7, and the local silicon dioxide microsphere that amplifies is seen Fig. 8 by tightly packed formation of the little silica spheres of nanometer.
Result of the test shows: under identical reaction condition, along with the prolongation in reaction time, the complex microsphere of generation is through high-temperature calcination, and the electron scanning micrograph of the SiO 2 hollow microsphere that obtains after the Mechanical Crushing is observed microballoon shell thickening gradually.The present invention prepares that the reaction time is chosen as 2～12 hours in the step of preparation process of surface patterned SiO 2 hollow microsphere.
2, calcining heat is to the influence of silicon dioxide microsphere
P (the NIPAM-co-20%AA)/SiO of preparation in 6 hours is answered in negate
2Three parts of each 10mg of complex microsphere, identical down at other conditionally complete, in Muffle furnace, under the air atmosphere, be warming up to 300 ℃, 400 ℃, 550 ℃ calcinings 4 hours respectively continuously, naturally cool to room temperature.SiO 2 high molecular composite microsphere is after 300 ℃ of calcinings, be shown as sphere under the light microscope, but the copolymerization microgel of the microballoon inside of this moment is not also removed fully, test with Fourier transformation infrared spectrometer, the silicon dioxide microsphere surface is contained than polyhydroxy, sees the infrared spectrum curve a among Fig. 9; 400 ℃ of calcinings of SiO 2 high molecular composite microsphere were shown as sphere under the light microscope after 4 hours, tested with Fourier transformation infrared spectrometer, the result of its infrared spectrum shows, under this temperature, the macromolecule microgel has all divided to be taken off, and sees the infrared spectrum curve b among Fig. 9; SiO 2 high molecular composite microsphere was 550 ℃ of calcinings 4 hours, the SiO 2 hollow microsphere of preparation, test with Fourier transformation infrared spectrometer, its infrared spectrum curve is seen the infrared spectrum curve c among Fig. 9, infrared spectrum curve a, infrared spectrum curve b, infrared spectrum curve c compare with the infrared spectrum curve d of pure silicon dioxide (the infrared spectrum curve d among Fig. 9), and infrared spectrum curve b, infrared spectrum curve c and infrared spectrum curve d are approaching.The SiO 2 hollow microsphere of analyzing 400 ℃ of calcinings preparation in 4 hours with full-automatic X-x ray diffractometer x is consistent with the standard card of silica tetragonal crystal system, sees Figure 10.SiO 2 high molecular composite microsphere through 750 ℃ of microballoons after finishing thermogravimetric analysis, is observed under light microscope, and most of silicon dioxide microsphere is spherical to be kept.
Result of the test shows: SiO 2 high molecular composite microsphere prepared under identical reaction condition is after calcining, the macromolecule microgel all decomposes, silicon dioxide microsphere gradually becomes the pure silicon dioxide tiny balloon with the rising of calcining heat, consider economic problems, it is 300～550 ℃ that the present invention selects calcining heat.
In order to verify beneficial effect of the present invention, the inventor adopts the surface patterned SiO 2 hollow microsphere of the embodiment of the invention 1 preparation, use SEM, Fourier transformation infrared spectrometer, full-automatic X-x ray diffractometer x to carry out observation experiment, various test situation are as follows:
Observe article: surface patterned SiO 2 hollow microsphere.
Laboratory apparatus: SEM, model are XL-20, are produced by Britain Philips company; Fourier transformation infrared spectrometer, model are EQUINX55, are produced by German Brucher company; Full-automatic X-x ray diffractometer x, model is D/MAX-III, is produced by Japanese Rigalcu company.
1, observes
By the SEM using method surface patterned SiO 2 hollow microsphere that adopts the embodiment of the invention 1 preparation is observed.
2, test
Method of testing by Fourier transformation infrared spectrometer, full-automatic X-x ray diffractometer x is tested surface patterned SiO 2 hollow microsphere.
3, observed result
With sem observation to pattern see Fig. 1, test with Fourier transformation infrared spectrometer, the infrared curve of being drawn is seen the infrared spectrum curve b among Fig. 9, tests with full-automatic X-x ray diffractometer x, and the X-ray diffraction graph of being drawn is seen Figure 10.
The sem observation SiO 2 hollow microsphere is spherical in shape, structural integrity, and monodispersity is good, and about diameter 30 μ m, the SiO 2 hollow microsphere surface is by tightly packed formation of many uniform little nano silicon balls.The infrared spectrum curve is at 3446cm
-1More weak hydroxyl stretching vibration peak appears, at 1092cm
-1And 805cm
-1Feature asymmetric stretching vibration peak and stretching vibration peak that very strong Si-O-Si occurs.X-ray diffraction graph is 22 °, 28.4 °, 31.42 °, 36.16 ° etc. at 2 θ and locates to have occurred SiO
2The strong diffraction maximum of feature, these diffracted signals and tetragonal crystal system SiO
2The diffraction maximum [JCPDS, 11-0695] of lattice plane such as (101), (111), (102), (200) consistent, the surface patterned SiO 2 hollow microsphere that obtains after 400 ℃ of calcinings and the crystal formation of tetragonal crystal system silica are close.
Claims (3)
1, a kind of preparation method of surface patterned SiO 2 hollow microsphere is characterized in that this preparation method comprises the steps:
(1) preparation mixed surfactant
Si Ban-80 is hybridly prepared into mixed surfactant for 5:1 by weight with Tween-80;
(2) the synthetic template oil phase of preparation
The mixed surfactant of step (1) preparation is joined in the there-necked flask that fills normal heptane, and mixed surfactant and normal heptane are by weight be hybridly prepared into synthetic template oil phase for 1:115～130;
(3) preparation emulsion
The synthetic template oil phase of step (2) preparation is put into there-necked flask, stir with mixer, mixing speed is 360～400 rev/mins, feeds N with 2～3ml/ minute flow velocity
2,, make emulsion 18～30 ℃ of scope internal emulsifications 40～60 minutes;
(4) preparation water
With N, N '-methylene diene acid amides, ammonium persulfate, N-N-isopropylacrylamide mix for 1:1.17:28.3 in molar ratio, stir, and make solution A; Acrylic acid and NaOH are that 23% the PAA aqueous solution is solution B for 1:0.3～1 is mixed with concentration in molar ratio; Solution A and solution B by volume for 6:1 mixes, are imported till nitrogen to oxygen arranged, make water;
(5) preparation copolymerization microgel
By volume for 1:10 makes mixed liquor, with the mixer stirring, mixing speed is 360～400 rev/mins, stirs 15 minutes with the emulsion of the water of step (4) preparation and step (3) preparation; The 4.76% tetramethylethylenediamine aqueous solution of mixeding liquid volume 1/154 is joined in the mixed solution, reacted 3～4 hours, generate the copolymerization microgel, incline and remaining reactant liquor, the copolymerization microgel is alternately washed 5～6 times with acetone and secondary water, wash 3～4 times again with acetone at last and removed fully, dry naturally, make sand-like P (NIPAM-co-20%AA) the copolymerization microgel of white up to the adsorbed water of copolymerization microgel;
(6) the copolymerization microgel of preparation swelling
By weight for 1:11 is that 28% ammoniacal liquor evenly mixes with copolymerization microgel and concentration, placed 12 hours, make its abundant swelling, make P (NIPAM-co-20%AA) the copolymerization microgel of swelling;
(7) mixed liquor of preparation positive silane of tetraethoxy and normal heptane
The positive silane of tetraethoxy and normal heptane are mixed and made into by volume the mixed liquor of positive silane of tetraethoxy and normal heptane for 1:4;
(8) preparation surface patterned SiO 2 high molecular composite microsphere
The swelling copolymerization microgel of step (6) preparation is joined in 40 minutes the deposition oil phase of emulsification, the deposition oil phase is that Si Ban-80 is mixed and made into for 1:160 by weight with normal heptane, at normal temperatures, stir with mixer, mixing speed is 600 rev/mins, drip positive silane of tetraethoxy and the normal heptane mixed liquors that step 7 prepares with constant pressure funnel with 7～8 droplets/minute, reacted 2～12 hours, generate SiO 2 high molecular composite microsphere, remaining reactant liquor inclines, alternately wash SiO 2 high molecular composite microsphere 6～7 times with secondary water and acetone, washing 3～4 times again with acetone is at last removed fully up to the adsorbed water of SiO 2 high molecular composite microsphere, naturally dry, make P (the NIPAM-co-20%AA)/SiO of white
2Complex microsphere;
(9) preparation surface patterned SiO 2 hollow microsphere
P (NIPAM-co-20%AA)/SiO with step (8) preparation
2Complex microsphere is placed in the Muffle furnace, under the air atmosphere, is warming up to 300～550 ℃ continuously, calcines 3～5 hours, naturally cools to room temperature, makes white surface patterned silicon dioxide tiny balloon.
2, according to the preparation method of the described surface patterned SiO 2 hollow microsphere of claim 1, it is characterized in that: in the synthetic template oil phase processing step (2) of preparation, mixed surfactant and normal heptane are wherein by weight be hybridly prepared into synthetic template oil phase for 1:120～125; In the processing step (3) of preparation emulsion, wherein emulsifying temperature is 20～25 ℃; In preparation aqueous process step (4), acrylic acid and NaOH wherein are that to be mixed with concentration be 23% the PAA aqueous solution in 1:0.6～0.8 in molar ratio; In preparation surface patterned SiO 2 high molecular composite microsphere processing step (8), wherein the reaction time is 4～10 hours; In preparation surface patterned SiO 2 hollow microsphere processing step (9), wherein calcining heat is 350～500 ℃, calcines 4～5 hours.
3, according to the preparation method of the described surface patterned SiO 2 hollow microsphere of claim 1, it is characterized in that: in the synthetic template oil phase processing step (2) of preparation, mixed surfactant synthesizes template oil phase by wherein wt than being hybridly prepared into for 1:122 with normal heptane; In emulsifying process step (3), wherein emulsifying temperature is 25 ℃; In preparation aqueous process step (4), the mol ratio of acrylic acid and NaOH is 23% the PAA aqueous solution for 1:0.6 is mixed with concentration wherein; In processing step (8), wherein reaction is 6 hours; In processing step (9), wherein calcining heat is 400 ℃, and calcination time is 4 hours.
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| 表面图案化CuS-P（NIPAM-co-AA）复合微球的制备和表征. 杨菊香，房喻，白超良等.科学通报，第49卷第18期. 2004 |
| 表面图案化CuS-P（NIPAM-co-AA）复合微球的制备和表征. 杨菊香，房喻，白超良等.科学通报，第49卷第18期. 2004 * |
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