CN103086387B - Porous silica microsphere preparation method - Google Patents
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Abstract
The invention discloses a porous silica microsphere preparation method, which comprises: mixing template molecules or a template structure and a completely-vulcanized silicone rubber emulsion, carrying out spray drying, and burning to prepare porous silica microspheres, wherein the solid content in the template molecules or the template structure is 2-50% of the total solid content in the mixed emulsion, the completely-vulcanized silicone rubber emulsion is prepared through carrying out irradiation on an organic silicone polymer emulsion or a copolymer emulsion, a burning temperature is 250-1200 DEG C, and a burning time is 10-600 min. The porous silica microsphere preparation method has characteristics of simpleness and low equipment cost, wherein the formed hole is large.
Description
Technical field
The present invention relates to chemical field, say further, relate to a kind of method of preparing porous silica microballoon.
Background technology
Porous silica microballoon has larger specific surface area, suitable potential of hydrogen and the good character such as thermostability.In a lot of fields, have a wide range of applications.Can be used as Stationary Phase for HPLC, efficient catalytic agent carrier, the toughener of macromolecular material, sorbent material, matting agent, filters and parting material ion-exchange, ink modification, high-grade photo paper surface modification etc.
Widespread use based on porous silica microballoon, its preparation technology is researched and developed widely.Different according to know-why, can be divided three classes: (1) stacked silica bead method; (2) Sol-gel method; (3) spray-drying process.US Patent No. Pat 3782075 and US Pat 3855172 are for porous silica microballoon by stacked silica bead legal system.Porous silica microballoon reciprocal of duty cycle prepared by this method is low, and intensity is limited.German Patent Ger, Pat 2357184 and US Patent No. Pat 3653216, US Pat 3652214 and US Pat4206297 etc. discloses the method for Sol-Gel legal system for porous silica microballoon.Porous silica microballoon size control difficulty prepared by this method, size distribution is wide.Japanese Patent 62275104 and 62143818 has been introduced the method that spray-drying process is prepared porous silica microballoon.This preparation method has relatively high expectations to equipment and technology.Chinese patent 94117706.8 discloses a kind of cell walls with biomass cells or cytolemma as the method for the biological microcapsule of synthesizing porous silicon dioxide microsphere.This method needs suitable shape and big or small biological cell wall or cytolemma, is not suitable at present scale operation.Chinese patent 00122921.4 discloses and a kind ofly by chemical enlargement agent, has reacted, and then through the method for high-temperature roasting dilatation, prepares porous silica carrier.The shape of porous silica microballoon prepared by this method is by being determined by dilatation base shape, and the larger 400～600nm of the aperture ratio after its dilatation.
According to raw materials, can be divided into two large classes: (1) by water glass and sulfuric acid reaction, and make through a series of last handling processes such as aging, acid bubbles; (2) positive silicon ester and template reagent are hydrolyzed the gel that obtains silicon under acidic conditions, and then through ageing, the techniques such as ablation make.
In sum, generally to take water glass or positive silicon ester be silicon raw material to porous silica microballoon.Dry by spraying, or the cell walls of biomass cells or cytolemma do the technology such as template and prepare ball shape structure, and the template molecule then removing wherein obtains porous silica microballoon.In above-mentioned technology, by spray technique, prepare porous silica microballoon high to spray technique requirement, need special spraying equipment.And be subject to the control of cell formation and size can not control flexibly the size of silicon dioxide microsphere and the size in hole by cell walls or the cytolemma template of biomass cells.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of method of preparing porous silica microballoon.Preparation method is simple, and equipment cost is low, and the hole forming is larger.
The object of this invention is to provide a kind of method of preparing porous silica microballoon.
Described method comprises mixes template molecule or structure with full sulphurated siliastic emulsion, after spraying is dried, burns, prepare porous silica microballoon.
Particularly, template molecule or formwork structure are mixed with ultra-fine full sulfureted organic silicon polymkeric substance or copolymer emulsion, obtain stable composite emulsion; Then by spray drying technology, obtain template molecule or structure and full sulfureted organic silicon polymkeric substance or the molecular micron order complex microsphere of multipolymer superfine granule.Finally, the micron order complex microsphere making is burnt and prepares porous silica microballoon under aerobic conditions.
Described full sulphurated siliastic emulsion is that organosilicon polymer or copolymer emulsion make after irradiation, and in described organosilicon polymer or copolymer emulsion, average particle size is less than 1000 nanometers.Can by organosilicon polymer or copolymer emulsion, add or not add crosslinking coagent preferably according to the technology in Chinese patent ZL01801656.1, with energetic ray, irradiate, make the silicon rubber emulsion of its complete cure.Organosilicon polymer or copolymer emulsion used are preferably silicone oil emulsion.The solid content of full sulphurated siliastic emulsion is not limit, and is preferably weight solid content 20～60%.In emulsion, average particle size is less than 1000 nanometers, preferably 50～300 nanometers.Organosilicon polymer or copolymer emulsion and silicone oil emulsion, all can pass through commercially available obtaining.
Template molecule of the present invention requires to have following character: (1) template molecule is at 25 ℃, and under normal pressure, solubleness is greater than the organic molecule of 10 grams/100 grams of water; (2) add this organic molecular species not destroy organosilicon polymer or copolymer emulsion stability; (3), under normal temperature and pressure, this organic molecular species is solid.The organic molecule that template molecule can preferred molecular weight be less than 1000, as organic acid salt, organic amide or organic amine, Sodium Benzoate for example, sodium maleate, Na2EDTA, carbonyl diamine, hexanolactam etc.
Formwork structure of the present invention is divided into following two classes: a class is water miscible liquid or the suspension with following character: (1) solid content is greater than 10%; (2) at normal temperatures and pressures, disperse phase is comprised of solid organic matters; (3) add this emulsion not destroy organosilicon polymer or copolymer emulsion stability;
Another kind of is the organic surface active agent with following character: under (1) normal temperature and pressure, can be uniformly dispersed in water, and solid content is greater than 10%; (2) add this tensio-active agent not destroy organosilicon polymer or copolymer emulsion stability; (3), under normal temperature and pressure, this tensio-active agent is solid.Described organic surface active agent is negatively charged ion, positively charged ion or nonionogenic tenside, anionic for example, sodium laurylsulfonate, nonionogenic tenside polyvinyl alcohol, polyoxyethylene glycol, polyvinylpyrrolidone, and cats product Trimethyllaurylammonium bromide etc.
Every template molecule or formwork structure that meets above condition is all applicable to body series.For example, the organic solid molecule that can be dissolved in organosilicon polymer or copolymer emulsion is done template molecule, Sodium Benzoate for example, sodium maleate etc.; The solid surfactant existing with micella in water is done formwork structure, sodium lauryl sulphate for example, polyoxyethylene glycol, polyvinylpyrrolidone etc.; The full vulcanized rubber emulsion that does not comprise full sulphurated siliastic emulsion, for example entirely vulcanize SBR emulsion, full-sulfurized nitrile rubber emulsion, entirely vulcanize carboxy nitrile rubber emulsion and entirely vulcanize carboxylic styrene-butadiene rubber emulsion, full sulfuration aqueous polyvinyl acetate emulsion, vulcanizes neoprene latex, acrylic ester emulsion etc. entirely, above-mentioned rubber latex solid content is not limit, and is preferably weight solid content 20～60%; In emulsion, the size of rubber particles is less than 500 nanometers, is preferably 50～300 nanometers.
By adding template molecule or formwork structure, can be by the Kong Bian great of porous silica microballoon, thus can prepare the more silicon dioxide microsphere of macropore.Enriched the kind of porous silica microballoon.
Full sulphurated siliastic emulsion and template molecule or structure are mixed to get to stable composite emulsion.The ratio C that solid content in template molecule or formwork structure accounts for all solid contents in composite emulsion is 2～50wt%, is preferably 5～40wt%.
C is defined as follows:
For the tensio-active agent in template molecule or formwork structure, the sample calculation of consumption C, the W1 gram of sodium lauryl sulphate of take is formwork structure, the silicon polymer emulsion of W2 gram of solid content w2% is example, calculates the mass concentration C adding:
For formwork structure, be water miscible liquid or suspension, consumption C sample calculation: the W1 gram of solid content of take vulcanizes SBR emulsion as formwork structure entirely as w1%, and the silicon polymer emulsion of W2 gram of solid content w2% is example, calculates consumption C:
By spray drying technology, prepare micron order complex microsphere.Spray-drying process can be controlled inlet temperature at 100～200 ℃, and temperature out is controlled at 20～80 ℃.
The micron order complex microsphere making, under oxygen exists, is burnt template molecule or formwork structure, and full sulfureted organic silicon polymkeric substance or multipolymer change silicon-dioxide into, thereby have prepared porous silica microballoon.Burning temperature is 250～1200 ℃, is preferably 300～1000 ℃, more preferably 400～800 ℃; The time of burning is 10～600 minutes, preferably 30～300 minutes.Burn the equipment of equipment for conventionally adopting, as retort furnace, fluidized-bed etc.
The hole dimension that adopts porous silica microballoon prepared by the method for the invention is large compared with the hole dimension that does not add the porous silica that template molecule or formwork structure obtain, and preparation method is simple, and required equipment cost is low.The porous silica microballoon making can be used as support of the catalyst, matting agent, and ion-exchange materials etc., have wide Application Areas.
Accompanying drawing explanation
The scanning electron microscope diagram of Fig. 1 embodiment 1 complex microsphere
The scanning electron microscope diagram of the porous silica microballoon that Fig. 2 embodiment 1 obtains
The scanning electron microscope diagram of the porous silica microballoon that Fig. 3 embodiment 9 obtains
The scanning electron microscope diagram of the porous silica microballoon that Fig. 4 embodiment 18 obtains
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1
500 grams of full sulphurated siliastic emulsions (Beijing Chemical Research Institute, solid content 28%) and 200 grams of full sulfuration SBR emulsions (Beijing Chemical Research Institute, solid content 45%), through mechanical stirring blend, are made to stable blending emulsion.Then pass through spray drying process, spray-dryer (Beijing Chemical Research Institute's self-control), 150 ℃ of temperature ins, 60 ℃ of temperature outs, prepare 100 grams of full sulphurated siliastics and full sulfuration styrene-butadiene rubber(SBR) complex microsphere.
Weigh 20 grams of the complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 400 ℃, ablation 300 minutes.Obtain 3.1 grams of porous silica microballoons.Mean pore size 140 nanometers.
Comparison diagram 1 and Fig. 2, visible: in Fig. 1, hole is not seen on the fully sulfurized silicon rubber powder surface before ablation, and obviously there is hole on the ball surface in Fig. 2 after ablation.
Embodiment 2
By 20 grams of ultra-fine full sulphurated siliastics and full sulfuration styrene-butadiene rubber(SBR) micron order complex microsphere (with embodiment 1), in crucible, be put in retort furnace, under air conditions, in 500 ℃, ablation 180 minutes.Obtain 3.2 grams of porous silica microballoons.Mean pore size 124 nanometers.
Embodiment 3
By 20 grams of ultra-fine full sulphurated siliastics and full sulfuration styrene-butadiene rubber(SBR) micron order complex microsphere (with embodiment 1), in crucible, be put in retort furnace, under air conditions, in 800 ℃, ablation 40 minutes.Obtain 3.0 grams of porous silica microballoons.Mean pore size 104 nanometers.
Embodiment 4
By 20 grams of ultra-fine full sulphurated siliastics and full sulfuration styrene-butadiene rubber(SBR) micron order complex microsphere (with embodiment 1), in crucible, be put in retort furnace, under air conditions, in 550 ℃, ablation 240 minutes.Obtain 2.8 grams of porous silica microballoons.Mean pore size 114 nanometers.
Embodiment 5
500 grams of ultra-fine full sulphurated siliastic emulsions and 200 grams of full-sulfurized nitrile rubber emulsions (Beijing Chemical Research Institute, solid content 45%), through mechanical stirring blend, are made to stable blending emulsion.Then pass through spray drying process, spray-dryer (Beijing Chemical Research Institute's self-control), 150 ℃ of temperature ins, 60 ℃ of temperature outs, prepare 110 grams of ultra-fine full sulphurated siliastics and full-sulfurized nitrile rubber micron order complex microsphere.
Weigh 20 grams of the micron order complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 400 ℃, ablation 300 minutes.Obtain 3.2 grams of porous silica microballoons.Mean pore size 137 nanometers.
Embodiment 6
20 grams of full sulphurated siliastics and full-sulfurized nitrile rubber complex microsphere, in (with embodiment 5) crucible, are put in retort furnace, under air conditions, in 500 ℃, ablation 180 minutes.Obtain 3.0 grams of porous silica microballoons.Mean pore size 135 nanometers.
Embodiment 7
500 grams of ultra-fine full sulphurated siliastic emulsions and 200 grams of full sulfuration carboxy nitrile rubber emulsions (Beijing Chemical Research Institute, solid content 45%), through mechanical stirring blend, are made to stable blending emulsion.Then pass through spray drying process, spray-dryer (Beijing Chemical Research Institute's self-control), 150 ℃ of temperature ins, 60 ℃ of temperature outs, prepare 105 grams of ultra-fine full sulphurated siliastics and full-sulfurized nitrile rubber micron order complex microsphere.
Weigh 20 grams of the micron order complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 550 ℃, ablation 240 minutes.Obtain 3.0 grams of porous silica microballoons.Mean pore size 127 nanometers.
Embodiment 8
500 grams of ultra-fine full sulphurated siliastic emulsions and 200 grams of full sulfuration carboxylic styrene-butadiene rubber emulsions (Beijing Chemical Research Institute, solid content 40%), through mechanical stirring blend, are made to stable blending emulsion.Then pass through spray drying process, spray-dryer (Beijing Chemical Research Institute's self-control), 150 ℃ of temperature ins, 60 ℃ of temperature outs, prepare 120 grams of ultra-fine full sulphurated siliastics and full-sulfurized nitrile rubber micron order complex microsphere.
Weigh 20 grams of the micron order complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 550 ℃, ablation 240 minutes.Obtain 2.8 grams of porous silica microballoons.Mean pore size 107 nanometers.
Embodiment 9
500 grams of full sulphurated siliastic emulsions (Beijing Chemical Research Institute, solid content 28%) and 30 grams of Sodium Benzoates, through mechanical stirring blend, are made to stable blending emulsion.Then pass through spray drying process, 150 ℃ of temperature ins, 60 ℃ of temperature outs, prepare 85 grams of full sulphurated siliastics and Sodium Benzoate complex microsphere.
Weigh 20 grams of the complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 400 ℃, ablation 300 minutes.Obtain 2.9 grams of porous silica microballoons.Mean pore size 102 nanometers.
After Fig. 3 shows ablation, microsphere surface is covered with micropore.
Embodiment 10
By 20 grams of full sulphurated siliastics and Sodium Benzoate complex microsphere (with embodiment 9), in crucible, be put in retort furnace, under air conditions, in 500 ℃, ablation 180 minutes.Obtain 3.2 grams of porous silica microballoons.Mean pore size 112 nanometers.
Embodiment 11
By 20 grams of full sulphurated siliastics and Sodium Benzoate complex microsphere (with embodiment 9), in crucible, be put in retort furnace, under air conditions, in 800 ℃, ablation 30 minutes.Obtain 2.8 grams of porous silica microballoons.Mean pore size 98 nanometers.
Embodiment 12
By 20 grams of full sulphurated siliastics and Sodium Benzoate complex microsphere (with embodiment 9), in crucible, be put in retort furnace, under air conditions, in 250 ℃, ablation 180 minutes.Obtain 3.8 grams of porous silica microballoons.Mean pore size 87 nanometers.
Embodiment 13
500 grams of full sulphurated siliastic emulsions (with embodiment 9) and 20 grams of sodium maleates, through mechanical stirring blend, are made to stable blending emulsion.Then pass through spray drying process, 150 ℃ of temperature ins, 60 ℃ of temperature outs, prepare 200 grams of full sulphurated siliastics and sodium maleate complex microsphere.
Weigh 20 grams of the complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 400 ℃, ablation 300 minutes.Obtain 3.0 grams of porous silica microballoons.Mean pore size 95 nanometers.
Embodiment 14
Weigh 20 grams of complex microspheres (with embodiment 13) prepared by full sulphurated siliastic and sodium maleate in crucible, be put in retort furnace, under air conditions, in 500 ℃, ablation 200 minutes.Obtain 3.0 grams of porous silica microballoons.Mean pore size 110 nanometers.
Embodiment 15
500 grams of full sulphurated siliastic emulsions (with embodiment 1) and 10 grams of sodium oxalates (Beijing chemical reagent company limited), through mechanical stirring blend, are made to stable blending emulsion.Then pass through spray drying process, 150 ℃ of temperature ins, 60 ℃ of temperature outs, prepare 195 grams of full sulphurated siliastics and full sulfuration styrene-butadiene rubber(SBR) complex microsphere.
Weigh 20 grams of the complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 550 ℃, ablation 240 minutes.Obtain 4.7 grams of porous silica microballoons.Mean pore size 70 nanometers.
Embodiment 16
500 grams of full sulphurated siliastic emulsions (with embodiment 1) and 10 grams of sodium ethylene diamine tetracetates (Beijing chemical reagent company limited), through mechanical stirring blend, are made to stable blending emulsion.Then pass through spray drying process, 150 ℃ of temperature ins, 60 ℃ of temperature outs, prepare 195 grams of full sulphurated siliastics and full sulfuration styrene-butadiene rubber(SBR) complex microsphere.
Weigh 20 grams of the complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 550 ℃, ablation 240 minutes.Obtain 4.8 grams of porous silica microballoons.Mean pore size 68 nanometers.
Embodiment 17
500 grams of full sulphurated siliastic emulsions (with embodiment 1) and 10 grams of carbonyl diamines (Beijing chemical reagent company limited), through mechanical stirring blend, are made to stable blending emulsion.Then pass through spray drying process, 150 ℃ of temperature ins, 60 ℃ of temperature outs, prepare 186 grams of full sulphurated siliastics and full sulfuration styrene-butadiene rubber(SBR) complex microsphere.
Weigh 20 grams of the complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 550 ℃, ablation 240 minutes.Obtain 3.5 grams of porous silica microballoons.Mean pore size 63 nanometers.
Embodiment 18
500 grams of ultra-fine full sulphurated siliastic emulsions (Beijing Chemical Research Institute, solid content 28%) and 50 grams of sodium lauryl sulphate (Beijing chemical reagents corporation), through mechanical stirring blend, are made to stable blending emulsion.Then by spray drying process, prepare 95 grams of full sulphurated siliastics and sodium lauryl sulphate micron order complex microsphere.
Weigh 20 grams of the micron order complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 400 ℃, ablation 300 minutes.Obtain 3.0 grams of porous silica microballoons.Mean pore size 70 nanometers.
After Fig. 4 shows ablation, microsphere surface is covered with micropore.
Embodiment 19
20 grams of ultra-fine full sulphurated siliastics and sodium lauryl sulphate micron order complex microsphere (with embodiment 18), in crucible, are put in retort furnace, under air conditions, in 500 ℃, ablation 180 minutes.Obtain 2.9 grams of porous silica microballoons.Mean pore size 65 nanometers.
Embodiment 20
By 20 grams of ultra-fine full sulphurated siliastics and sodium lauryl sulphate micron order complex microsphere (with embodiment 18), in crucible, be put in retort furnace, under air conditions, in 800 ℃, ablation 180 minutes.Obtain 2.9 grams of porous silica microballoons.Mean pore size 70 nanometers.
Embodiment 21
20 grams of ultra-fine full sulphurated siliastics and sodium lauryl sulphate micron order complex microsphere (with embodiment 18), in crucible, are put in retort furnace, under air conditions, in 550 ℃, ablation 240 minutes.Obtain 3.0 grams of porous silica microballoons.Mean pore size 64 nanometers.
Embodiment 22
20 grams of ultra-fine full sulphurated siliastics and sodium lauryl sulphate micron order complex microsphere (with embodiment 18), in crucible, are put in retort furnace, under air conditions, in 500 ℃, ablation 60 minutes.Obtain 2.7 grams of porous silica microballoons.Mean pore size 58 nanometers.
Embodiment 23
500 grams of full sulphurated siliastic emulsions (Beijing Chemical Research Institute, solid content 28%) and 49 grams of polyoxyethylene glycol (Beijing chemical reagents corporation, molecular weight 20000), through mechanical stirring blend, are made to stable blending emulsion.Then by spray drying process, prepare 87 grams of full sulphurated siliastics and full-sulfurized nitrile rubber complex microsphere.
Weigh 20 grams of the complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 400 ℃, ablation 300 minutes.Obtain 2.8 grams of porous silica microballoons.Mean pore size 80 nanometers.
Embodiment 24
20 grams of ultra-fine full sulphurated siliastics and polyoxyethylene glycol micrometre composite microsphere (with embodiment 23), in crucible, are put in retort furnace, under air conditions, in 500 ℃, ablation 180 minutes.Obtain 3.0 grams of porous silica microballoons.Mean pore size 68 nanometers.
Embodiment 25
500 grams of ultra-fine full sulphurated siliastic emulsions (Beijing Chemical Research Institute, solid content 28%) and 30 grams of Sodium dodecylbenzene sulfonatees (Beijing chemical reagents corporation), through mechanical stirring blend, are made to stable blending emulsion.Then by spray drying process, prepare 90 grams of full sulphurated siliastics and sodium lauryl sulphate micron order complex microsphere.
Weigh 20 grams of the micron order complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 550 ℃, ablation 240 minutes.Obtain 3.0 grams of porous silica microballoons.Mean pore size 60 nanometers.
Embodiment 26
500 grams of ultra-fine full sulphurated siliastic emulsions (Beijing Chemical Research Institute, solid content 28%) and 15 grams of Trimethyllaurylammonium bromides (Tianjin recovery fine chemistry industry institute), through mechanical stirring blend, are made to stable blending emulsion.Then by spray drying process, prepare 81 grams of full sulphurated siliastics and sodium lauryl sulphate micron order complex microsphere.
Weigh 20 grams of the micron order complex microspheres of above-mentioned preparation in crucible, be put in retort furnace, under air conditions, in 550 ℃, ablation 240 minutes.Obtain 2.8 grams of porous silica microballoons.Mean pore size 58 nanometers.
Comparative example 1
To fill 20 grams of fully sulfurized silicon rubber powders (Beijing Chemical Research Institute, crucible VP601) is put in retort furnace, under air conditions, in 800 ℃, ablation 30 minutes.Obtain 5.2 grams of porous silica microballoons.Mean pore size 55nm.
Comparative example 2
The crucible that fills 20 grams of fully sulfurized silicon rubber powders (with comparative example 1) is put in retort furnace, under air conditions, in 550 ℃, ablation 240 minutes.Obtain 5.8 grams of macroporous silica microspheres.Mean pore size 52nm.
Claims (10)
1. a method of preparing porous silica microballoon, is characterized in that:
Described method is that template molecule or formwork structure are mixed with full sulphurated siliastic emulsion, after spraying is dried, burns, prepares porous silica microballoon,
Wherein said template molecule be under normal temperature and pressure, be solid and solubleness be greater than the organic molecule of 10 grams/100 grams of water;
Described formwork structure for disperse phase be at normal temperatures and pressures water miscible liquid or the suspension by solid organic matters forms and solid content is greater than 10%: or can be uniformly dispersed in water under normal temperature and pressure, and the solid content SOLID ORGANIC tensio-active agent that is greater than 10%;
Described full sulphurated siliastic emulsion is that organic silican polymer emulsion makes after irradiation, and in described full sulphurated siliastic emulsion, average particle size is less than 1000 nanometers;
After solid content in described template molecule or formwork structure accounts for and mixes, in emulsion, the ratio of all solid contents is 2～50%;
The described temperature of burning is 250～1200 ℃; The time of burning is 10～600 minutes.
2. the method for preparing porous silica microballoon as claimed in claim 1, is characterized in that:
In described full sulphurated siliastic emulsion, average particle size is 50～300 nanometers, and solid content is 20～60%.
3. the method for preparing porous silica microballoon as claimed in claim 1, is characterized in that:
Described organic silican polymer emulsion is silicone oil emulsion.
4. the method for preparing porous silica microballoon as claimed in claim 1, is characterized in that:
Described template molecule is the organic molecule that molecular weight is less than 1000.
5. the method for preparing porous silica microballoon as claimed in claim 4, is characterized in that:
Described organic molecule is organic acid salt, organic amide or organic amine.
6. the method for preparing porous silica microballoon as claimed in claim 1, is characterized in that:
Described SOLID ORGANIC tensio-active agent is negatively charged ion, positively charged ion or nonionogenic tenside.
7. the method for preparing porous silica microballoon as claimed in claim 1, is characterized in that:
After solid content in described template molecule or formwork structure accounts for and mixes, in emulsion, the ratio of all solid contents is 5～40%.
8. the method for preparing porous silica microballoon as claimed in claim 1, is characterized in that:
Described formwork structure is not for comprising the full vulcanized rubber emulsion of full sulphurated siliastic emulsion.
9. the method for preparing porous silica microballoon as claimed in claim 1, is characterized in that:
The described temperature of burning is 300～1000 ℃; The time of burning is 30～300 minutes.
10. the method for preparing porous silica microballoon as claimed in claim 9, is characterized in that:
The described temperature of burning is 400～800 ℃.
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