CN1772363A - Template process of preparing hollow ball and composite hollow ball - Google Patents
Template process of preparing hollow ball and composite hollow ball Download PDFInfo
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- CN1772363A CN1772363A CN 200410009774 CN200410009774A CN1772363A CN 1772363 A CN1772363 A CN 1772363A CN 200410009774 CN200410009774 CN 200410009774 CN 200410009774 A CN200410009774 A CN 200410009774A CN 1772363 A CN1772363 A CN 1772363A
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Abstract
The present invention belongs to the field of hollow material preparing technology, and is especially the preparation process of hollow ball of inorganic matter, metal, organic matter and composite structure with hollow polymer ball as template. The present invention prepares composite hollow ball through combining hollow polymer ball template with sol-gel, deposition reaction, oxidation-reduction process and through forced interface process or surface deposition process; and obtain hollow ball of inorganic matter, metal and organic matter through high temperature sintering or selective solvent extraction to eliminate template polymer. The control of hollow ball structure and size and the compounding of several kinds of matters may be realized through controlling reactant activity, material feeding mode, reactant concentration and circulating reaction process. The hollow ball has excellent dispersivity, high strength and size stability. The present invention also relates to the application of these hollow structure materials.
Description
Technical field
The invention belongs to hollow structure material field, particularly is the method for template for preparing inorganic matter, metal, organic matter hollow ball and composite construction hollow ball with the polymer hollow ball.
Background technology
The hollow structure spheroid is a kind of functional material with special construction, and hollow ball all has great application prospect in fields such as catalysis, medicine conveying, artificial cell, light filler, insulating materials, dielectric materials, photonic crystals.Preparing this class material by the nucleocapsid structure colloidal particle is a kind of method commonly used.The shell of another kind of (or several) material on a kind of particle surface coats or reacts, thus give particle new characteristic.For example, shell matter can change surface charge, the surface reaction characteristic of colloidal particle and strengthen its stability and dispersed.In addition, can introduce material charged, magnetic, that catalysis characteristics is arranged, optically active, conduction as required on colloidal particle surface, thereby give particle with functional.
At present, the method for preparing nucleocapsid structure mainly comprises following two aspects: (1) surface reaction; (2) surface deposition.The U.S.
By after coupling agent treatment is carried out on the inorganic particulate surface, add divinylbenzene and radical initiator Deng the people again, prepared colloidal particle (H.T.Oyama, R.Sprycha, A.Zelenev, the E. of the nucleocapsid structure of polydivinylbenezene coated inorganic thing
, " Coating of Uniform Inorganic Particles with Polymers ", J.ColloidPolym.Sci.1993,160,298-303; R.Sprycha, H.T.Oyama, A.Zelenev, E.
, " Characterization of Polymer-coated Silica Particlesby Microelectrophoresis ", Colloid Polym.Sci.1995,273,693-670).The research group of Britain Armes has prepared the colloidal particle (C.Barthet that electric polypyrrole, electrically conductive polyaniline coat polystyrene, S.P.Armes, S.F.Lascelles, S.Y.Luk, H.M.E.Stanley, " Synthesis and Characterization of Micrometer-SizedPolyaniline-Coated Polystyrene Latexs ", Langmuir 1998,14,2032-2041).When the content of polypyrrole or polyaniline is about 8wt%, just can reach the conductance suitable with body.The absorption layer by layer of polyelectrolyte is a kind of very effective method of preparation nucleocapsid structure colloidal particle.The polyelectrolyte of opposite charges is adsorbed to the colloidal particle surface layer by layer, repeats repeatedly, just can prepare the colloidal particle that polyelectrolyte coats.Germany Caruso etc. are template with the diffusing polystyrene colloid particle of monomer, by the layer upon layer electrostatic self assembly, prepared the colloidal particle that polyvinyl ammonium chloride and kayexalate coat, wherein every absorption one deck polyelectrolyte, the average diameter of colloidal particle increases 1.5nm approximately.Silica, titanium dioxide, tri-iron tetroxide and argent, the golden nanometer particle that they also will have an electric charge by electrostatic adsorption is assembled into the surface of polystyrene colloid particle, colloidal particle (the F.Caruso that has prepared nucleocapsid structure, " Hollow Capsules Processing through ColloidalTemplating and Self-Assembly ", Chem.Eur.J.2000,6,413-419; F.Caruso, M.Spasova, A.Susha, M.Giersig, R.A.Caruso, " MagneticNanocomposite Particles and Hollow Spheres Constructed by a SequentialLayering Approach ", Chem.Mater.2001,13,109-116; F.Caruso, X.Y.Shi, R.A.Caruso, A.Susha, " Hollow Titania Spheres From LayeredPrecursor Deposition on Sacrificial Colloidal Core Particles ", Adv.Mater.2001,13,740-744).The advantage of self assembly layer by layer: the thickness of polymeric layer can carry out meticulous adjusting according to the number of adsorption layer; The colloidal particle of different sizes and shape all can be used as the layer assembly that template is carried out polyelectrolyte.Shortcoming is: eccentric cleaning is removed polyelectrolyte remaining in the system repeatedly; Obtaining certain thickness polymeric layer must be through self assembly repeatedly; Can not assemble for uncharged polymer.China Yang Zhen loyalty etc. utilizes partly sulfonated monodisperse polystyrene bead to be template, pass through collosol and gel, surface aggregate obtains core-shell particles, the stoning processing obtains inorganic, organic or its compound hollow microsphere, this method advantage is can regulate cavity size and shell thickness simultaneously by control sulfonation layer thickness, the sulfonation layer provides a hydrophilic layer and positive charge in addition, be beneficial to inorganic precursor, charged monomer and polymer are in absorption of sulfonation layer and reaction, help forming continuous light slip case body, and improved the utilization rate (Z.Z.Yang of precursor, Z.W.Niu, Y.F.Lu, Z.B.Hu, C.C.Han, " Templatedsysnthesis of inorganic hollow spheres with a tunable cavity size ontocore-shell gel particles ", Angew.Chem.Int.Ed.Engl.2003,42,1943-194; Z.W.Niu, Z.Z.Yang, Z.B.Hu, Y.F.Lu, C.C.Han, " Polyaniline-silica composite conductive capsules and hollowspheres ", and Adv.Funct.Mater.2003,13,949-954).
Utilizing the hollow ball of template preparation at present all is to be template with the colloidal particle, reacts or successively alternately adsorb by surface deposition to make the nucleocapsid structure compound particle, obtains hollow ball after the stoning.
Summary of the invention
It is the method for the hollow ball of template for preparing inorganic matter, metal and/or organic matter composite construction that one of purpose of the present invention provides with the polymer hollow ball.
A further object of the present invention provides the method for preparing the hollow ball of inorganic matter, metal and/or organic matter composite construction by complex method.
An also purpose of the present invention provides the purposes of hollow ball and composite construction hollow ball.
The present invention utilizes the polymer hollow ball to be template, utilizes its housing for forcing the interface, and cavity is as a reaction component raw material silo, and ball is thrown in another reaction component outward, prepares hollow ball or its composite construction by reaction.
The present invention is by being the colloidal particle that template has prepared a series of hollow structures with the polymer hollow ball.By sol-gel, sedimentation reaction, redox chemistry or polymerisation, prepared the compound hollow ball of variform.Control reaction speed by the choice reaction thing,, can control the morphosis of compound hollow ball by regulating feed way, concentration of reactants, reaction condition.After removing template polymer, high temperature sintering or solvent selectivity extracting obtain inorganic matter, metal or organic matter hollow ball.
The present invention uses the polymer hollow ball to be template, can be used to prepare inorganic matter, metal and organic hollow ball or compound hollow ball.The hollow ball of inorganic matter or compound hollow ball comprise: the hollow ball of metal oxide or hydroxide or compound hollow ball, and as TiO
2, SiO
2, SnO
2, ZrO
2, Al
2O
3, V
2O
5, ZnO, WO
3, MoO
3, Al (OH)
3Or Mg (OH)
2The hollow ball of biomineralization material or compound hollow ball are as CaCO
3, Ca
10(PO
4)
6(OH)
2, BaSO
4Or CaSO
4The hollow ball of semi-conducting material or compound hollow ball are as CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; The hollow ball of magnetic compound or compound hollow ball are as Fe
3O
4, Fe
2O
3Or contain the ferrite of zinc, manganese, cobalt.The hollow ball of metal or compound hollow ball are as hollow ball or the compound hollow ball of Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe.Organic hollow ball or compound hollow ball comprise: the hollow ball of conducting polymer or compound hollow ball, as polyaniline, polypyrrole, polythiophene or p-phenylene vinylene and derivative thereof; The hollow ball of sensitiveness gel or compound hollow ball are as poly-N-isopropyl acrylamide, polyacrylic acid or polymethylacrylic acid.The swollen-state polymerization method can be used to prepare the hollow ball or the compound hollow ball of high-performance polymer, as crosslinked polystyrene, polyurethane, polyacrylate, phenolic resins, unsaturated polyester (UP), epoxy resin, polyimides, polyether-ketone or polyether sulfone.
The present invention prepares the method for hollow ball and compound hollow ball with template, adopting commercially available or homemade polymer hollow ball is that (diameter is 0.02 μ m～10 μ m to template, cavity volume be whole microballoon 10～95%), this polymer hollow ball housing is made up of inside and outside two-layer material, internal layer is a hydrophilic polymer, skin is the lipophile polymer backbone, and has hydrophilic pathway to connect cavity and particle external environment.By control feed way and reaction speed, can control the growth of material, thereby make the hollow structure material of variform at polymer hollow ball housing outer surface, internal layer and/or hydrophilic channel.
One. in preparation method's step of polymer hollow ball template housing internal layer growth material:
(1). with the polymer hollow ball is template, reactant is divided into two reaction components, reactionless between the raw material in the each component, utilize polymer hollow ball housing for forcing the interface, its cavity is as a reaction component raw material silo, outside ball, throw in another reaction component again, can prepare the compound hollow ball of polymer hollow ball internal layer growth material by reaction.
(1.1) polymer hollow ball template particles is immersed in the inorganic matter precursor solution of 0.01wt%～60.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make the inorganic matter precursor solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.The polymer hollow ball that contains the inorganic matter precursor solution that will obtain then under agitation joins in the reaction component aqueous solution.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning promptly obtains the compound hollow ball of layer growth inorganic matter in the polymer hollow ball housing.Or
To react the component aqueous solution earlier and infiltrate polymer hollow ball template particles cavity, the polymer hollow ball that contains the reaction component aqueous solution that will obtain then under agitation joins in the inorganic matter precursor solution that concentration is 10.0wt%～60.0wt%.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning obtains the compound hollow ball of layer growth inorganic matter in the polymer hollow ball housing equally.By the control reactant concentration, the internal layer product of the compound hollow ball of prepared inorganic matter can be by the nano particle of single dispersion to network of nanoparticles, up to the closely knit shell of formation different-thickness.Or
(1.2) polymer hollow ball template particles is immersed in the metal ion salt solution of 0.01wt%～60.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make metal ion salt solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.Polymer hollow ball with the metal ion salting liquid that obtains under agitation joins in the reductant solution of 0.01wt%～60.0wt% then.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and about 0.5～24 hour reaction time, reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball of polymer hollow ball housing internal layer growing metal.Or
Reductant solution with 0.01wt%～60.0wt% infiltrates in the polymer hollow ball template particles cavity earlier, and the polymer hollow ball that contains reductant solution that will obtain then under agitation joins in the metal ion salt solution that concentration is 10.0wt%～60.0wt%.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning obtains the compound hollow ball of polymer hollow ball housing internal layer growing metal equally.By the control reaction condition, the internal layer product of prepared metal composite hollow ball can be by the nano particle of single dispersion to network of nanoparticles, up to the closely knit shell of formation different-thickness.Or
(1.3) polymer hollow ball template particles is immersed in the polymer monomer solution that concentration is 0.01wt%～40.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make polymer monomer solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.The polymer hollow ball that contains polymer monomer solution that will obtain then under agitation joins in 0.01wt%～30.0wt% initiator solution.In reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning promptly obtains the organic compound hollow ball of layer growth in the polymer hollow ball housing.Or
Earlier 0.01wt%～30.0wt% initiator solution is infiltrated polymer hollow ball template particles cavity, the polymer hollow ball that contains initiator solution that will obtain then under agitation joins in the polymer monomer solution that concentration is 5wt%～40wt%.In reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning obtains the organic compound hollow ball of layer growth in the polymer hollow ball equally.By the control reaction condition, the internal layer product of the compound hollow ball of prepared organic thing can be by the nano particle of single dispersion to network of nanoparticles, up to the closely knit shell of formation different-thickness.
(2). the polymer template that step (1.1), step (1.2) are obtained and the hollow ball of inorganic matter or metal composite place in the sintering furnace respectively, and blowing air, be warming up to 300～700 ℃ of (preferred 450 ℃) calcinations with 0.1～10 ℃/minute speed and obtain inorganic matter or metal hollow ball respectively about 0.2～3 hour;
Perhaps the compound hollow ball of the polymer template that step (1.1), step (1.2), step (1.3) are obtained and inorganic matter, metal or organic matter uses selective solvent to carry out extracting respectively, remove template polymer, obtain inorganic matter, metal or organic matter hollow ball respectively.
(3). carrying out step (2) before, can be further repeatedly repeating step (1.1), step (1.2), step (1.3).The compound hollow ball that obtains respectively with step (1.1), step (1.2), step (1.3) is a template, difference further repeating step (1.1), step (1.2) and step (1.3), carry out circular response, when the above circular response of twice or twice generates same substance, the product shell that can increase compound hollow ball is thick, promptly can control the thickness of hollow spherical shell by control reactant concentration and circular response number of times; Or
The compound hollow ball that step (1.2) or step (1.3) are obtained is carried out circular response as the template particles of step (1.1); Or
The compound hollow ball that step (1.1) or step (1.3) are obtained is carried out circular response as the template particles of step (1.2); Or
The compound hollow ball that step (1.1) or step (1.2) are obtained is carried out circular response as the template particles of step (1.3).
When the above circular response of twice or twice generates not material of the same race, can obtain the compound hollow ball of multiple material, generate titanium dioxide at the housing internal layer earlier as polymer template, generate the compound hollow ball that silica promptly obtains polymer template and titanium dioxide and silica at the housing internal layer again; Perhaps polymer template generates tri-iron tetroxide at the housing internal layer earlier, generates the compound hollow ball that polyaniline promptly obtains polymer template and tri-iron tetroxide and polyaniline at the housing internal layer again.
Two. in preparation method's step of polymer hollow ball template housing internal layer and hydrophilic channel growth material:
(1). utilize the reactivity or the catalytic performance of polymer hollow ball template hydrophilic channel and housing internal layer, select suitable reactant and charging sequence, can obtain the compound hollow ball of surface band burr shape material, polymer hollow ball template housing internal layer generates continuous material, its hydrophilic channel by replica, expand even stretch out spheroid.
Polymer hollow ball template particles is immersed in the reaction component aqueous solution, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make the reaction component aqueous solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.The polymer hollow ball that contains the reaction component aqueous solution that will obtain then under agitation joins in the alcoholic solution of inorganic matter precursor, and inorganic matter precursor alcohols solution is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning, obtain polymer template and the compound hollow ball of inorganic matter of surface band burr shape material, its hydrophilic channel by replica, expand even stretch out spheroid, the material that the generation of housing internal layer is continuous; Or
Polymer hollow ball template particles is immersed in the reductant solution of 0.01wt%～60.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make reductant solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.The polymer hollow ball that contains reductant solution that will obtain then under agitation joins in the metal ion salt solution, and metal cation salt is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%; The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning, promptly obtain the polymer template and the hollow ball of metal composite of surface band burr shape material, its hydrophilic channel by replica, expand even stretch out spheroid, the material that the generation of housing internal layer is continuous; Or
It is in 0.01wt%～30.0wt% initiator solution that polymer hollow ball template particles is immersed in reaction component concentration, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make initiator solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.The polymer hollow ball that contains initiator solution that will obtain then under agitation joins in the polymer monomer solution, and polymer monomer is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%; In reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, and eccentric cleaning promptly obtains polymer template and the compound hollow ball of organic matter that burr shape material is with on the surface, its hydrophilic channel by replica, expand even stretch out spheroid, the housing internal layer generates continuous material.
(2). the hollow ball of polymer template that step (1) is obtained and inorganic matter, metal composite places in the sintering furnace, and blowing air, be warming up to 300～700 ℃ of (preferred 450 ℃) calcinations 0.2～3 hour with 0.1～10 ℃/minute speed, obtain the inorganic or metal hollow ball of surface band burr; Or
Polymer template that step (1) is obtained and inorganic matter, metal, the compound hollow ball of organic matter use selective solvent to carry out extracting, remove template polymer, obtain inorganic matter, metal or the organic matter hollow ball of surface band burr.The hollow sphere of this burr type hollow ball is formed by material layer growth replica in housing, and burr is formed in hydrophilic channel growth expansion by material.
Three. in preparation method's step of polymer hollow ball template housing outer surface growth material:
With the polymer hollow ball is template, it is dispersed in the solution, in solution, adds inorganic matter, metal or organic two reaction components simultaneously, the control finite concentration, can make product at polymer hollow ball housing outer surface deposition growing, and reactionless product particle generate in solution.
Polymer hollow ball template particles is dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, control reactant liquor in the inorganic matter precursor at ultimate density 0.01wt%～30wt%, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth inorganic matter; Remove polymer template, obtain the inorganic matter hollow ball; Or
Polymer hollow ball template particles is dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growing metal; Remove polymer template, obtain the metal hollow ball; Or
Polymer hollow ball template particles is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time made product be deposited on polymer hollow ball housing outer surface, formed continuous shell; Reaction finishes, and eccentric cleaning promptly obtains polymer and organic compound hollow ball in the growth of polymer hollow ball housing outer surface; Remove template polymer, obtain the organic matter hollow ball.
Four. preparation method's step of the double-decker hollow ball of eccentric structure:
(1). with the polymer hollow ball is template, reactant is divided into two reaction components, reactionless between the raw material in the each component, utilize polymer hollow ball housing for forcing the interface, its cavity is as a reaction component raw material silo, outside ball, throw in another reaction component again, by the compound hollow ball of prepared in reaction polymer hollow ball housing internal layer growth material.
(1.1) polymer hollow ball template particles is immersed in the inorganic matter precursor solution of 0.01wt%～60.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make the inorganic matter precursor solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.The polymer hollow ball that contains the inorganic matter precursor solution that will obtain then under agitation joins in the reaction component aqueous solution.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning promptly obtains the compound hollow ball of layer growth inorganic matter in the polymer hollow ball housing.Or
To react the component aqueous solution earlier and infiltrate polymer hollow ball template particles cavity, the polymer hollow ball that contains the reaction component aqueous solution that will obtain then under agitation joins in the inorganic matter precursor solution that concentration is 10.0wt%～60.0wt%.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning obtains the compound hollow ball of layer growth inorganic matter in the polymer hollow ball housing equally.Or
(1.2) polymer hollow ball template particles is immersed in the metal ion salt solution of 0.01wt%～60.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make metal ion salt solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.Polymer hollow ball with the metal ion salting liquid that obtains under agitation joins in the reductant solution of 0.01wt%～60.0wt% then.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and about 0.5～24 hour reaction time, reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball of polymer hollow ball housing internal layer growing metal.Or
Reductant solution with 0.01wt%～60.0wt% infiltrates in the polymer hollow ball template particles cavity earlier, and the polymer hollow ball that contains reductant solution that will obtain then under agitation joins in the metal ion salt solution that concentration is 10.0wt%～60.0wt%.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning obtains the compound hollow ball of polymer hollow ball housing internal layer growing metal equally.Or
(1.3) polymer hollow ball template particles is immersed in the polymer monomer solution that concentration is 0.01wt%～40.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make polymer monomer solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.The polymer hollow ball that contains polymer monomer solution that will obtain then under agitation joins in 0.01wt%～30.0wt% initiator solution.In reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning promptly obtains the organic compound hollow ball of layer growth in the polymer hollow ball housing.Or
Earlier 0.01wt%～30.0wt% initiator solution is infiltrated polymer hollow ball template particles cavity, the polymer hollow ball that contains initiator solution that will obtain then under agitation joins in the polymer monomer solution that concentration is 5wt%～40wt%.In reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning obtains the organic compound hollow ball of layer growth in the polymer hollow ball equally.
(2). the compound hollow ball of the internal layer growth material that step (1) is obtained is dispersed in the solution, add inorganic matter, metal or organic two reaction components simultaneously, the control reactant concentration, product is deposited on polymer hollow ball housing outer surface, can obtain removing polymer template, obtain the double-decker hollow ball in polymer hollow ball housing outer surface and internal layer MULTILAYER COMPOSITE hollow ball of growth material all, be to contain hollow ball in the hollow ball, hollow ball is moved in the hollow ball outside in it.
The compound hollow ball of the interior layer growth inorganic matter that step (1.1) is obtained is dispersed in the alcoholic solution, add the inorganic matter precursor and the reaction component aqueous solution, ultimate density 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface and interior layer growth inorganic matter.Remove polymer template, obtain double-decker inorganic hollow ball, promptly contain hollow ball in the hollow ball, hollow ball is moved in the hollow ball outside in the double-decker that obtains; Or
The compound hollow ball of the interior layer growth inorganic matter that step (1.1) is obtained is dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growing metal and interior layer growth inorganic matter.Remove polymer template, obtain double-decker metal-inorganic matter hollow ball, promptly contain an inorganic matter hollow ball in the metal hollow ball, the inorganic matter hollow ball that obtains can be moved in the metal hollow ball; Or
The compound hollow ball of the interior layer growth inorganic matter that step (1.1) is obtained is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth organic matter and interior layer growth inorganic matter.Remove polymer template, obtain double-decker organic matter-inorganic matter hollow ball, promptly contain an inorganic matter hollow ball in the organic matter hollow ball, the inorganic matter hollow ball that obtains can be moved in the organic matter hollow ball; Or
The compound hollow ball of the internal layer growing metal that step (1.2) is obtained is dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth inorganic matter and internal layer growing metal.Remove polymer template, obtain double-decker inorganic matter-metal hollow ball, promptly contain a metal hollow ball in the inorganic matter hollow ball, the metal hollow ball that obtains can be moved in the inorganic matter ball; Or
The compound hollow ball of the internal layer growing metal that step (1.2) is obtained is dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface and internal layer growing metal.Remove polymer template, obtain double-decker metal hollow ball, promptly contain a metal hollow ball in the metal hollow ball, the interior metal hollow ball that obtains is moved in the Metal Ball outside; Or
The compound hollow ball of the internal layer growing metal that step (1.2) is obtained is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time made product be deposited on polymer hollow ball housing outer surface, formed continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth organic matter and internal layer growing metal.Remove polymer template, obtain double-decker organic matter-metal hollow ball, promptly contain a metal hollow ball in the organic matter hollow ball, the metal hollow ball that obtains can be moved in the organic matter hollow ball; Or
The organic compound hollow ball of interior layer growth that step (1.3) is obtained is dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains in polymer hollow ball housing outer surface growth inorganic matter and the organic compound hollow ball of interior layer growth.Remove polymer template, obtain double-decker inorganic matter-organic matter hollow ball, promptly contain an organic matter hollow ball in the inorganic matter hollow ball, the organic matter hollow ball that obtains can be moved in the inorganic matter ball; Or
The organic compound hollow ball of interior layer growth that step (1.3) is obtained is dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains in polymer hollow ball housing outer surface growing metal and the organic compound hollow ball of interior layer growth.Remove polymer template, obtain double-decker metal-organic hollow ball, promptly contain an organic matter hollow ball in the metal hollow ball, the organic matter hollow ball that obtains can be moved in the metal hollow ball; Or
The organic compound hollow ball of interior layer growth that step (1.3) is obtained is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains in polymer hollow ball housing outer surface and the organic compound hollow ball of interior layer growth.Remove polymer template, obtain double-decker organic matter hollow ball, promptly contain an organic matter hollow ball in the organic matter hollow ball, the interior organic matter hollow ball that obtains is moved in the organic matter ball outside.
Five. preparation method's step of the double-decker hollow ball of concentric structure:
(1). utilize the reactivity or the catalytic performance of polymer hollow ball hydrophilic channel and housing internal layer, select suitable reactant and charging sequence, can obtain the compound hollow ball of surface band burr shape material, polymer hollow ball housing internal layer generates continuous material, its hydrophilic channel by replica, expand even stretch out spheroid.
(1.1) polymer hollow ball template particles is immersed in the reaction component aqueous solution, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make the reaction component aqueous solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.The polymer hollow ball that contains the reaction component aqueous solution that will obtain then under agitation joins in the alcoholic solution of inorganic matter precursor, and the inorganic matter precursor is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning, obtain polymer template and the compound hollow ball of inorganic matter of surface band burr shape material, its hydrophilic channel by replica, expand even stretch out spheroid, the material that the generation of housing internal layer is continuous; Or
(1.2) polymer hollow ball template particles is immersed in the reductant solution of 0.01wt%～60.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make reductant solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.The polymer hollow ball that contains reductant solution that will obtain then under agitation joins in the metal ion salt solution, and metal cation salt is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%; The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, eccentric cleaning, promptly obtain the polymer template and the hollow ball of metal composite of surface band burr shape material, its hydrophilic channel by replica, expand even stretch out spheroid, the material that the generation of housing internal layer is continuous; Or
(1.3) polymer hollow ball template particles being immersed in reaction component concentration is in 0.01wt%～30.0wt% initiator solution, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make initiator solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity.The polymer hollow ball that contains initiator solution that will obtain then under agitation joins in the polymer monomer solution, and polymer monomer is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%; In reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, about 0.5～24 hour reaction time, reaction finishes, and eccentric cleaning promptly obtains polymer template and the compound hollow ball of organic matter that burr shape material is with on the surface, its hydrophilic channel by replica, expand even stretch out spheroid, the housing internal layer generates continuous material.
(2). the internal layer that step (1) is obtained and the compound hollow ball of passage growth material are dispersed in the alcohol or the aqueous solution, add inorganic matter, metal or organic matter two reaction components simultaneously, the control reactant concentration, product is deposited on polymer hollow ball housing outer surface, obtains in polymer hollow ball housing outer surface, internal layer and passage compound hollow ball of growth material all.Remove polymer template, obtain the double-decker hollow ball, promptly contain hollow ball in the hollow ball, but have column to link to each other between two hollow ball, interior hollow ball is moved in the hollow ball outside, and two hollow ball are concentric.
The compound hollow ball of internal layer that step (1.1) is obtained and passage growth inorganic matter is dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface, internal layer and passage growth inorganic matter.Remove polymer template, obtain double-decker inorganic matter hollow ball, promptly contain hollow ball in the hollow ball, in the inorganic matter hollow ball that obtains between two hollow ball the organic/inorganic substance post link to each other, the motion in the hollow ball outside of interior hollow ball, two hollow ball are concentric; Or
The compound hollow ball of internal layer that step (1.1) is obtained and passage growth inorganic matter is dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growing metal and internal layer, passage growth inorganic matter.Remove polymer template, obtain double-decker metal-inorganic matter hollow ball, promptly contain an inorganic matter hollow ball in the metal hollow ball, in the double-decker hollow ball that obtains between two hollow ball the organic/inorganic substance post link to each other, the inorganic matter hollow ball can not be moved in the metal hollow ball, and two hollow ball are concentric; Or
The compound hollow ball of internal layer that step (1.1) is obtained and passage growth inorganic matter is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth organic matter and internal layer, passage growth inorganic matter.Remove polymer template, obtain double-decker organic matter-inorganic matter hollow ball, be to contain an inorganic matter hollow ball in the organic matter hollow ball, in the double-decker hollow ball that obtains between two hollow ball the organic/inorganic substance post link to each other, the inorganic matter hollow ball can not be moved in the organic matter hollow ball, and two hollow ball are concentric; Or
The internal layer that step (1.2) is obtained and the compound hollow ball of passage growing metal are dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth inorganic matter and internal layer, passage growing metal.Remove polymer template, obtain double-decker inorganic matter-metal hollow ball, promptly contain a metal hollow ball in the inorganic matter hollow ball, have metal column to link to each other in the double-decker hollow ball that obtains between two hollow ball, the metal hollow ball can not be moved in the inorganic matter ball, and two hollow ball are concentric; Or
The internal layer that step (1.2) is obtained and the compound hollow ball of passage growing metal are dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growing metal and internal layer, passage growing metal.Remove polymer template, obtain double-decker metal hollow ball, promptly contain a metal hollow ball in the metal hollow ball, have metal column to link to each other in the double-decker hollow ball that obtains between two hollow ball, interior metal hollow ball is moved in the hollow ball outside, and two hollow ball are concentric; Or
The internal layer that step (1.2) is obtained and the compound hollow ball of passage growing metal are dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth organic matter and internal layer, passage growing metal.Remove polymer template, obtain double-decker organic matter-metal hollow ball, promptly contain a metal hollow ball in the organic matter hollow ball, have metal column to link to each other in the double-decker hollow ball that obtains between two hollow ball, the metal hollow ball can not be moved in the organic matter hollow ball, and two hollow ball are concentric; Or
Internal layer that step (1.3) is obtained and the passage organic compound hollow ball of growing is dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains in polymer hollow ball outer surface growth inorganic matter, internal layer and the passage organic compound hollow ball of growing.Remove polymer template, obtain double-decker inorganic matter-organic matter hollow ball, promptly contain an organic matter hollow ball in the inorganic matter hollow ball, have the organic matter post to link to each other in the double-decker hollow ball that obtains between two hollow ball, the organic matter hollow ball can not be moved in the inorganic matter ball, and two hollow ball are concentric; Or
The internal layer that step (1.3) is obtained and the compound hollow ball of organic matter of passage growth substance are dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains the organic compound hollow ball in polymer hollow ball housing outer surface growing metal and internal layer, passage growth.Remove polymer template, obtain double-decker metal-organic hollow ball, promptly contain an organic matter hollow ball in the metal hollow ball, have the organic matter post to link to each other in the double-decker hollow ball that obtains between two hollow ball, the organic matter hollow ball can not be moved in the metal hollow ball, and two hollow ball are concentric; Or
Internal layer that step (1.3) is obtained and the passage organic compound hollow ball of growing is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, 0.5～24 hour reaction time, make product be deposited on polymer hollow ball housing outer surface, form continuous shell.Reaction finishes, and eccentric cleaning promptly obtains in polymer hollow ball housing outer surface and internal layer, the passage organic compound hollow ball of growing.Remove polymer template, obtain double-decker organic matter hollow ball, promptly contain an organic matter hollow ball in the organic matter hollow ball, have the organic matter post to link to each other in the double-decker hollow ball that obtains between two hollow ball, interior hollow ball is moved in the hollow ball outside, and two hollow ball are concentric.
Six. preparation method's step of double-decker hollow ball:
Pass through surface hydrophilic modification, make polymer hollow ball outer surface also become hydrophilic surface, promptly obtain the intermediate layer oleophylic, and three layers of housing of internal layer, surface and hydrophilic outer, replace polymer hollow ball template with this kind surface modification polymer hollow ball, react, but one-step method makes the compound hollow ball of sandwich construction.Remove template polymer with selective solvent, can make the double-decker hollow ball.
Polymer-modified hollow ball is immersed in the inorganic matter precursor solution that concentration is 0.01wt%～60.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make the inorganic matter precursor solution infiltrate the cavity and the hydrophilic layer of polymer-modified hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the cavity.The polymer-modified hollow ball that contains the inorganic matter precursor solution that will obtain then under agitation joins in the reaction component aqueous solution.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and about 0.5～24 hour reaction time, reaction finishes, and eccentric cleaning promptly obtains the MULTILAYER COMPOSITE hollow ball of polymer and inorganic matter.Remove template polymer with selective solvent, can make double-decker inorganic hollow ball; Or
To react the component aqueous solution earlier and infiltrate the cavity and the hydrophilic layer of polymer-modified hollow ball, the polymer-modified hollow ball that will obtain containing the reaction component aqueous solution then under agitation joins in the inorganic matter precursor solution that concentration is 0.01wt%～60.0wt%.The concentration of polymer-modified hollow ball remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and about 0.5～24 hour reaction time, reaction finishes, and eccentric cleaning obtains the MULTILAYER COMPOSITE hollow ball of polymer and inorganic matter equally.Remove template polymer with selective solvent, can make double-decker inorganic hollow ball.Or
Polymer-modified hollow ball is immersed in the metal ion salt solution of 0.01wt%～60.0wt%, polymer-modified hollow ball keeps concentration in these solution be 0.1wt%～40.0wt%, make metal ion salt solution infiltrate the cavity and the hydrophilic layer of polymer-modified hollow ball, reach the solution centrifugal flush away that not to infiltrate after the balance.Then the polymer-modified hollow ball of the metal ion salting liquid that obtains is under agitation joined the reductant solution of 0.01wt%～60.0wt%.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and about 0.5～24 hour reaction time, reaction finishes, and eccentric cleaning promptly obtains the MULTILAYER COMPOSITE hollow ball of polymer and metal.Remove template polymer with selective solvent, can make the double-decker metal hollow ball; Or
Reductant solution with 0.01wt%～60.0wt% infiltrates in polymer-modified hollow ball particle cavity and the hydrophilic layer earlier, and the polymer-modified hollow ball that contains reductant solution that will obtain then under agitation joins in the metal ion salt solution that concentration is 0.01wt%～60.0wt%.The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and about 0.5～24 hour reaction time, reaction finishes, and eccentric cleaning obtains the MULTILAYER COMPOSITE hollow ball of polymer and metal equally.Remove template polymer with selective solvent, can make the double-decker metal hollow ball.Or
Polymer-modified hollow ball is immersed in the polymer monomer solution that concentration is 0.01wt%～40.0wt%, polymer-modified hollow ball keeps concentration in these solution be 0.1wt%～40.0wt%, make polymer monomer solution infiltrate the cavity and the hydrophilic layer of polymer-modified hollow ball, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer-modified hollow ball cavity.The polymer-modified hollow ball that contains polymer monomer solution that will obtain then under agitation joins in 0.01wt%～30.0wt% initiator solution.Feed inert gas in reaction vessel, the concentration of template particles remains on 0.1wt%～40.0wt%, 0 ℃～100 ℃ of reaction temperatures in the control reactant liquor, about 0.5～24 hour reaction time, reaction finishes, and eccentric cleaning promptly obtains polymer and organic MULTILAYER COMPOSITE hollow ball.Remove template polymer with selective solvent, can make the organic hollow ball of double-decker.Or
Earlier 0.01wt%～30.0wt% initiator solution is infiltrated the cavity and the hydrophilic layer of polymer-modified hollow ball, the polymer-modified hollow ball that contains initiator solution that will obtain then under agitation joins in the polymer monomer solution that concentration is 0.01wt%～40wt%.Feed inert gas in reaction vessel, the concentration of template particles remains on 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures in the control reactant liquor, about 0.5～24 hour reaction time, reaction finishes, and eccentric cleaning obtains polymer and organic MULTILAYER COMPOSITE hollow ball equally.Remove template polymer with selective solvent, can make the organic hollow ball of double-decker.
Seven. the swollen-state polymerization legal system is equipped with preparation method's step of the compound hollow ball of polymer:
Polymer hollow ball template particles is dispersed in the water, add monomer and crosslinking agent, or monomer and crosslinking agent and organic solvent, by monomer or organic solvent polymer hollow ball template housing is carried out swelling, and with monomer and initator introduction polymer hollow ball shell, carry out addition polymerization then, polycondensation or ring-opening polymerisation, in reaction vessel, feed inert gas, the concentration of template particles is 0.1wt%～20wt% in the control reactant liquor, reactant monomer concentration is 0.1wt%～20wt%, initiator concentration is 0.01wt%～10wt%, organic solvent concentration is 0wt%～20wt%, swelling time is 0.5～24 hour, 20 ℃～250 ℃ of reaction temperatures, 0.5～48 hour reaction time.Reaction finishes, and eccentric cleaning can make polymer hollow ball and organic compound hollow ball.
The external diameter of described polymer hollow ball template particles is 0.02 μ m～10 μ m, cavity volume is 10～95% of a whole microballoon, and the synthetic method that is adopted has spray drying process, block copolymer self-assembly method, soda acid swelling method, dynamic swelling method, complex phase emulsion polymerization.
The internal layer hydrophilic polymer of described polymer hollow ball template comprises polystyrolsulfon acid, polymethylacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide-based, polyvinyl pyrroles, poly-(2-vinylpyridine), poly-(4-vinylpridine), poly hydroxy ethyl acrylate, polyvinylesters, polyoxyethylene or polyvinyl ammonium chloride.
The outer lipophile polymer of described polymer hollow ball template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl tert-butyl acrylate, polymethylacrylic acid cinnamic acid ethyl ester, PMA, polyethyl acrylate, butyl polyacrylate, the polyacrylic acid tert-butyl ester, polyoxypropylene, poly dimethyl silane, polyvinyl butyl ester or polyisobutene.
The selective solvent that described usefulness removes polymer template is chloroform, toluene, oxolane or N, dinethylformamide etc.
Described polymer hollow ball hydrophilic modifying is that (diameter is 0.02 μ m～10 μ m to commercially available or homemade polymer hollow ball, cavity size be whole microballoon size 10～95%) outer surface carries out hydrophilic modifying, method of modifying has Electrostatic Absorption, sulfonation processing, hydrolysis, surface grafting etc.
At preparation SiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4, Si (OCH
2CH
2CH
2CH
3)
4, Na
2SiO
3Alcoholic solution; The reaction component aqueous solution is that (0.1wt%～100wt%), regulating its pH value with 35wt% concentrated hydrochloric acid or 25wt% concentrated ammonia liquor is 1～13 for the alcoholic solution of water.
At preparation TiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is TiCl
4, Ti (OCH
3)
4, Ti (OCH
2CH
3)
4, Ti{OCH (CH
3)
2}
4, Ti (OCH
2CH
2CH
2CH
3)
4, TiOSO
4Alcoholic solution; The reaction component aqueous solution is that (0.1wt%～100wt%), regulating its pH value with 35wt% concentrated hydrochloric acid or 25wt% concentrated ammonia liquor is 1～13 for the alcoholic solution of water.
At preparation SnO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is SnCl
4, Sn (OCH
3)
4, Sn (OCH
2CH
3)
4, Sn{OCH (CH
3)
2}
4, Sn (OCH
2CH
2CH
2CH
3)
4Alcoholic solution; The reaction component aqueous solution is that (0.1wt%～100wt%), regulating its pH value with 35wt% concentrated hydrochloric acid or 25wt% concentrated ammonia liquor is 1～13 for the alcoholic solution of water.
At preparation ZrO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is ZrCl
4, Zr (OCH
3)
4, Zr (OCH
2CH
3)
4, Zr{OCH (CH
3)
2}
4, Zr (OCH
2CH
2CH
2CH
3)
4, Zr (SO
4)
2Alcoholic solution; The reaction component aqueous solution is that (0.1wt%～100wt%), regulating its pH value with 35wt% concentrated hydrochloric acid or 25wt% concentrated ammonia liquor is 1～13 for the alcoholic solution of water.
At preparation Al
2O
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is AlCl
3, Al (OCH
3)
3, Al (OCH
2CH
3)
3, Al{OCH (CH
3)
2}
3, Al (OCH
2CH
2CH
2CH
3)
3, Al
2(SO
4)
3Alcoholic solution; The reaction component aqueous solution is that (0.1wt%～100wt%), regulating its pH value with 35wt% concentrated hydrochloric acid or 25wt% concentrated ammonia liquor is 1～13 for the alcoholic solution of water.
At preparation V
2O
5When hollow ball or compound hollow ball, described inorganic matter precursor solution is VO (OCH
3)
3, VO (OCH
2CH
3)
3, VO{OCH (CH
3)
2}
3, VO (OCH
2CH
2CH
2CH
3)
3Alcoholic solution; The reaction component aqueous solution is that (0.1wt%～100wt%), regulating its pH value with 35wt% concentrated hydrochloric acid or 25wt% concentrated ammonia liquor is 1～13 for the alcoholic solution of water.
When preparation ZnO hollow ball or compound hollow ball, described inorganic matter precursor solution is Zn (NO
3)
2, Zn (OOCCH
3)
2, ZnCl
2, Zn (ClO
4)
2Alcoholic solution; The reaction component aqueous solution is that (0.01wt%～30wt%) is as NaOH, potassium hydroxide or ammoniacal liquor for the water of alkali or alcoholic solution.
At preparation WO
3When hollow ball or compound hollow ball, described inorganic precursor solution is (NH
4)
6H
2W
12O
41, NaWO
3The aqueous solution; The reaction component aqueous solution is that (0.1wt～100wt%), regulating its pH value with 35wt% concentrated hydrochloric acid or 25wt% concentrated ammonia liquor is 1～13 for the alcoholic solution of water.
At preparation MoO
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is MoO
32H
2The O aqueous solution; The reaction component aqueous solution is that (0.1wt%～100wt%), regulating its pH value with 35wt% concentrated hydrochloric acid or 25wt% concentrated ammonia liquor is 1～13 for the alcoholic solution of water.
At preparation Al (OH)
3Or Mg (OH)
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is the chloride of soluble aluminum, magnesium or the aqueous solution of sulfate; The reaction component aqueous solution is that (0.01wt%～30wt%) is as NaOH, potassium hydroxide or ammoniacal liquor for the aqueous solution of alkali.
At preparation biomineralization material C aCO
3, Ca
10(PO
4)
6(OH)
2, CaSO
4, or BaSO
4When hollow ball or compound hollow ball, described inorganic matter precursor solution is Ca (OH)
2, CaCl
2, Ba (OH)
2, or BaCl
2The aqueous solution; The reaction component aqueous solution is for containing CO
3 2-, PO
4 3-, SO
4 2-Na
+, or K
+Salt or H
2CO
3, H
3PO
4, H
2SO
4The aqueous solution (0.01wt%～30wt%).
When preparation semiconductor sulfuration thing hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble-salt of respective metal, as chloride, nitrate, sulfate; The reaction component aqueous solution is the aqueous solution (0.01wt%～30wt%) of vulcanized sodium, thiocarbamide.
When preparation semiconductor selenide or tellurides hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the soluble-salt of metal cation, as chloride, nitrate, sulfate; The reaction component aqueous solution is the aqueous solution (0.01wt%～30wt%) of sodium selenide or tellurium sodium.
At preparation magnetic compound such as Fe
3O
4, Fe
2O
3During with ferrite hollow ball that contains zinc, manganese, cobalt, nickel, copper, magnesium or compound hollow ball, described inorganic matter precursor solution is Fe
2+, Fe
3+, Zn
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+, Mg
2+The aqueous solution (as chloride, nitrate, sulfate) of soluble salt; The reaction component aqueous solution is that (0.01wt%～30wt%) as NaOH, potassium hydroxide or ammoniacal liquor, or is hydrazine hydrate solution (1wt%～60wt%) for the aqueous solution of alkali.
When preparation metal such as Au, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow ball or compound hollow ball, described metal ion salt solution is the aqueous solution of respective metal ionically-soluble salt, as perchlorate, chloride, nitrate, sulfate; Reductant solution is the aqueous solution of reducing agent, as NaBH
4, LiB (C
2H
5)
3H, N
2H
4The aqueous solution.
When preparation conducting polymer such as polyaniline, polypyrrole, polythiophene, p-phenylene vinylene and derivative hollow ball or compound hollow ball, water or alcoholic solution that described polymer monomer solution is corresponding monomer; Initiator solution is the aqueous solution of potassium peroxydisulfate, ammonium persulfate, ferric trichloride.
When preparation sensitiveness gel such as poly-N-isopropyl acrylamide, polyacrylic acid, polymethylacrylic acid hollow ball or compound hollow ball, described polymer monomer solution is monomer N-N-isopropylacrylamide, acrylic acid, methacrylic acid or its water or alcoholic solution; Initiator solution is the aqueous solution of potassium peroxydisulfate, ammonium persulfate.
When preparation many materials compound hollow ball, described compound compound in inorganic matter, metal, the organic matter of comprising as TiO
2And SiO
2, TiO
2And SnO
2, TiO
2With ZnO, Jin Heyin, palladium and nickel etc., also comprise compound between inorganic matter, metal and the organic matter as titanium dioxide and tri-iron tetroxide, polyaniline and di-iron trioxide, polyacrylic acid and silver.
Described inert gas is nitrogen or argon gas etc.
Described alcoholic solution is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols etc.
Described housing swollen-state polymerization method can be used to prepare the hollow ball or the compound hollow ball of high-performance polymer, as crosslinked polystyrene, polyacrylate, polyurethane, phenolic resins, unsaturated polyester (UP), epoxy resin, polyimides, polyether-ketone or polyether sulfone hollow ball or compound hollow ball.
The crosslinking agent of described preparation crosslinked polystyrene, polyacrylate hollow ball or compound hollow ball is azodiisobutyronitrile, ABVN, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, potassium peroxydisulfate or ammonium persulfate; Monomer is styrene, divinylbenzene, methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate;
The crosslinking agent of described preparation polyurethane hollow ball or compound hollow ball is PTMEG, polyester-diol or 1, the 4-butanediol; Monomer is hexamethylene diisocyanate or toluene di-isocyanate(TDI);
The crosslinking agent of described preparation phenolic resins hollow ball or compound hollow ball is phenol, orthoresol, paracresol, resorcinol or bisphenol-A; Monomer is formaldehyde, metaformaldehyde, acetaldehyde, para-acetaldehyde or furfural;
The crosslinking agent of described preparation unsaturated polyester (UP) hollow ball or compound hollow ball is ethylene glycol, propane diols, 1,3-butanediol, PTMEG or polyester-diol; Monomer is a maleic anhydride;
The crosslinking agent of described preparation epoxy resin hollow ball or compound hollow ball is hexamethylene diisocyanate, toluene di-isocyanate(TDI), phthalic anhydride, phthalic anhydride, maleic anhydride, ethylenediamine, hexamethylene diamine or trimethyl tetramine; Monomer is bisphenol-A epoxy or phenolic aldehyde epoxy;
The crosslinking agent of described preparation polyimides hollow ball or compound hollow ball is p-phenylenediamine (PPD) or hexamethylene diamine; Monomer is that span comes acid anhydrides or pyromellitic dianhydride;
The crosslinking agent of described preparation polyether-ketone or polyether sulfone hollow ball or compound hollow ball is 4,4-difluoro benzophenone or 4,4-dichloro diphenyl sulfone; Monomer is hydroquinones or tetramethyl biphenyl diphenol.
The described organic solvent that is used for polymer hollow ball housing is carried out swelling is chloroform, benzene,toluene,xylene, oxolane, N, dinethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO), acetone, cyclohexane.
The compound hollow ball and the hollow ball of the present invention's preparation have purposes widely:
(1). utilize the catalytic performance of silver, platinum, palladium, nickel etc., the preparation high performance catalyst can be made into the catalyst material hollow ball.The catalyst hollow ball is made up of nano particle, has big specific area also to guarantee the circulation of liquefied gas.
(2). utilize its cavity to can be used as capsule material, be applied to the mass transfer and the slow release control of every field, utilize magnetic material and sensitiveness gel, can obtain intelligent capsule; Can be used as microreactor, the limited reaction of research material or control its conditioned response and prepare the response material.
(3). since the shell material between and and air between higher difference in refractive index, can be used as brightening agent; Utilize the pigment and the ultraviolet-absorbing of oxides such as titanium dioxide, iron oxide, can be used as antiultraviolet additive and Masterbatch; Utilize its low density characteristics to can be used as light filler, be widely used in plastics, coating, printing ink, printed material, papermaking and cosmetic industry.
(4). semiconductors such as zinc oxide, cadmium sulfide utilize its ultraviolet light intensity absorbability and light transfer characteristic, can be used as solar cell material, also can be used as catalysis material, extensively be used in aspects such as antibacterial and deodouring, sewage disposal, purifying exhaust air, photodissociation water, also can be used as gas sensor, dielectric ceramic.
(5). can be used to prepare the controllable polymerization composite capsule.By Electrostatic Absorption and polymerisation, can as hydrogel, photoactive substance, phospholipid molecule and protein molecule, thereby realize the intelligent switch process at polymer template hole path composite sensing sexual function material.
(6). utilize the electric conductivity and the redox reversible of conduction high polymer, can prepare electrode active material, electrochemical catalysis active material, anti-corrosion of metal material, chemistry or electrochemistry adjustable gas diffusion barrier, electric driven color-changing part, biology sensor etc.
(7). functional material also can be used as insulating materials, heat-insulating material, sound-absorbing material, conductive material, orderly magnetic material, photoelectric functional material etc.
Preparation method of the present invention and products characteristics are as follows:
(1). preparation method of the present invention has adaptability widely, can prepare the hollow ball and the compound hollow ball of a series of unlike materials and form;
(2). hollow ball of the present invention and compound hollow ball not only have good dispersiveness, also have good intensity and dimensional stability;
(3). the made hollow ball and the size of compound hollow ball can be 10
1～10
4Regulate in the nm scope;
(4). the form of hollow ball and compound hollow ball is adjustable, and composition and thickness of shell are controlled;
(5). preparation technology is simple, the feed stock conversion height.
Below in conjunction with embodiment and accompanying drawing in detail the present invention is described in detail:
Description of drawings
Fig. 1. the polymer hollow ball template schematic diagram that the embodiment of the invention is used.
Fig. 2. the transmission electron microscope photo of the polystyrene-poly propylene of the embodiment of the invention 1/compound hollow ball of titanium dioxide metatitanic acid.
Fig. 3. the transmission electron microscope photo of the titanium dioxide hollow ball of the embodiment of the invention 1.
Fig. 4. the stereoscan photograph of the compound hollow ball of titanium dioxide tri-iron tetroxide of the embodiment of the invention 8.
Fig. 5. the stereoscan photograph of the burr type titanium dioxide of the embodiment of the invention 10/compound hollow ball of polystyrene-poly acrylic acid.
Fig. 6. the transmission electron microscope photo of the earth silicon/titanic oxide double-decker hollow ball of the embodiment of the invention 19.
The specific embodiment
The preparation of embodiment compound hollow ball of 1 polystyrene-poly acrylic acid/titanium dioxide and titanium dioxide hollow ball
Polystyrene-poly acrylic acid hollow ball template, hollow ball housing skin is a polystyrene, and internal layer is a polyacrylic acid, and its external diameter is 500nm, and the thickness of shell is 100nm.Getting the 0.1g template particles is distributed in the 1g butyl titanate, saturated absorption 4 hours, the hollow ball of having adsorbed butyl titanate is settled down with supercentrifuge, the ethanolic solution (40wt%) that adds 10g water, hydrolysis 4 hours, obtaining with polystyrene-poly acrylic acid hollow ball is template, and titanium dioxide is grown in the compound hollow ball of housing internal layer.After the hollow ball of this composite construction removed polystyrene and polyacrylic acid with chloroform, obtain the hollow ball of titanium dioxide, the result of transmission electron microscope shows that the titanium dioxide ball of this hollow is made up of 30～50nm particle, and shell is thick to be 60nm, and the size of cavity is 250nm.
The compound hollow ball that maybe will make obtains the hollow ball of crystalline titania 450 ℃ of sintering 2 hours, and the result of XRD shows that its crystal formation is a Detitanium-ore-type; Compound hollow ball 600 ℃ of sintering 2 hours, is obtained the hollow ball of crystalline titania, and the result of XRD shows that its crystal formation is that anatase and rutile are compound.
The preparation of embodiment compound hollow ball of 2 polystyrene-poly methacrylic acid/magnetic ferroferric oxides and tri-iron tetroxide hollow ball
0.1g the emulsion particle of polystyrene-poly methacrylic acid hollow structure, its external diameter is 1000nm, the thickness of shell is 150nm, be distributed in the 25wt% iron chloride and 19wt% frerrous chloride mixed solution of 1g, saturated absorption 4 hours, the polymer hollow ball supercentrifuge centrifugal sedimentation of solution will have been adsorbed, be scattered in the 15wt% ammoniacal liquor of 10g again, hydrolysis 4 hours, obtaining with polystyrene-poly methacrylic acid hollow ball is template, and tri-iron tetroxide is grown in the compound hollow ball of housing internal layer.After the hollow ball of this composite construction removed polystyrene and polymethylacrylic acid with chloroform, obtain the hollow ball of tri-iron tetroxide.The result of transmission electron microscope shows that the tri-iron tetroxide ball of this hollow is made up of 50～100nm particle, and shell is thick to be 200nm, and the size of cavity is 400nm.
The preparation of compound hollow ball of embodiment 3 polymethyl methacrylates-polyacrylic acid/calcium carbonate and calcium carbonate hollow ball
0.1g the emulsion particle of polymethyl methacrylate-polyacrylic acid hollow structure, its external diameter is 100nm, the thickness of shell is 20nm, be distributed in the calcium chloride solution of 15wt%, saturated absorption 4 hours, with the hollow ball of having adsorbed calcium chloride solution supercentrifuge centrifugal sedimentation, be distributed in the aqueous sodium carbonate of 10g 15wt%, ammoniacal liquor with 25wt% is regulated pH value to 9, reacted 4 hours, obtaining with polymethyl methacrylate-polyacrylic acid hollow ball is the compound hollow ball that template calcium carbonate is grown in the housing internal layer.After this compound hollow ball removed polymethyl methacrylate and polyacrylic acid with chloroform, obtain the hollow ball of calcium carbonate.The result of transmission electron microscope shows that the carbonic acid calcisphere of this hollow is made up of the 20nm particle, and shell is thick to be 20nm, and the size of cavity is 20nm.
The preparation of embodiment compound hollow ball of 4 polystyrene-poly acrylic acid/cadmium sulfides and cadmium sulfide hollow ball
0.1g the emulsion particle of polystyrene-poly acrylic acid hollow structure, its external diameter is 300nm, the thickness of shell is 60nm, be distributed in the cadmium nitrate aqueous solution of 20wt%, saturated absorption 24 hours with the hollow ball of having adsorbed solution supercentrifuge centrifugal sedimentation, is distributed in the sodium sulfide solution of 10g 20wt%, reacted 4 hours, obtaining with polystyrene-poly acrylic acid hollow ball is the compound hollow ball that the template cadmium sulfide is grown in the housing internal layer.After this compound hollow ball removed polystyrene and polyacrylic acid with oxolane, obtain the hollow ball of cadmium sulfide.The result of transmission electron microscope shows that the carbonic acid calcisphere of this hollow is made up of the 30nm particle, and shell is thick to be 40nm, and the size of cavity is 120nm.
The preparation of embodiment 5 polystyrene-poly 2-vinylpyridine/silver-colored compound hollow ball and silver-colored hollow ball
0.1g the emulsion particle of polystyrene-poly 2-vinylpyridine hollow structure, its external diameter is 100nm, the thickness of shell is 20nm, be distributed in the liquor argenti nitratis ophthalmicus of 15wt%, saturated absorption 4 hours will have been adsorbed the polymer hollow ball supercentrifuge centrifugal sedimentation of liquor argenti nitratis ophthalmicus, be scattered in the hydrazine hydrate of 10g 20wt% again, hydrolysis 4 hours, obtaining with polystyrene-poly 2-vinylpyridine hollow ball is template, silver-colored germination is in the compound hollow ball of shell inner surface.After the hollow ball of this composite construction removed polystyrene and poly 2 vinyl pyridine with oxolane, obtain the silver-colored particle of 10nm.Increase the concentration of liquor argenti nitratis ophthalmicus, can make silver-colored particle form continuous shell, remove and to obtain the hollow ball formed by silver-colored particle after the template at internal layer.This silver-colored hollow ball is made up of the 10nm particle, and shell is thick to be 20nm, and the size of cavity is 40nm.
The preparation of embodiment 6 polymethyl methacrylates-compound hollow ball of poly propenoic acid N-N-isopropylacrylamide and poly-N-isopropyl acrylamide hollow ball
0.1g the emulsion particle of polymethyl methacrylate-polyacrylic acid hollow structure, its external diameter are 5000nm, the thickness of shell is 500nm, is distributed in the 10g water, adds the N-N-isopropylacrylamide of 0.5g, 0.05gN, N-dimethyl bisacrylamide.After charging into nitrogen 30min, add 0.1% ammonium persulfate aqueous solution 0.01g.Be warming up to 70 ℃, stir reaction 8h down, obtain the compound hollow ball of polymethyl methacrylate-polyacrylic acid and poly-N-propyl group acrylamide.After this compound hollow ball removed polymethyl methacrylate and polyacrylic acid with chloroform, obtain the poly-N-isopropyl acrylamide hollow ball of the temperature sensitive property of hollow.
The preparation of embodiment compound hollow ball of 7 polystyrene-poly acrylic acid/polyanilines and polyaniline hollow ball
0.1g the emulsion particle of polystyrene-poly acrylic acid hollow structure, its external diameter are 400nm, the thickness of shell is 80nm, adds the ammonium persulfate aqueous solution of 1g 22.8%, stirs 4 hours, and eccentric cleaning is distributed in the 10g water again, adds 0.8g aniline.Reaction is 24 hours under the room temperature, obtains the compound hollow ball of polystyrene-poly acrylic acid/polyaniline.After the hollow ball of this composite construction removed polystyrene and polyacrylic acid with chloroform, obtain the polyaniline hollow ball.
The preparation of embodiment 8 polystyrene-polies acrylic acid/compound hollow ball of titanium dioxide magnetic ferroferric oxide and the compound hollow ball of titanium dioxide tri-iron tetroxide
Press the compound hollow ball of embodiment 1 preparation polystyrene-poly acrylic acid/titanium dioxide, this compound particle 0.1g is distributed in the 25wt% iron chloride and 19wt% frerrous chloride mixed solution of 1g, saturated absorption 4 hours, the polymer hollow ball supercentrifuge centrifugal sedimentation of solution will have been adsorbed, be scattered in again in the ammoniacal liquor of 10g15wt%, hydrolysis 4 hours obtains polystyrene-poly acrylic acid/compound hollow ball of titanium dioxide magnetic ferroferric oxide.After the hollow ball of this composite construction removed polystyrene and polyacrylic acid with chloroform, obtain the compound hollow ball of titanium dioxide and tri-iron tetroxide.
The preparation of embodiment 9 polystyrene-polies acrylic acid/compound hollow ball of titanium dioxide polyaniline and polyaniline silicon dioxide hollow sphere
Press the compound hollow ball of embodiment 1 preparation polystyrene-poly acrylic acid/titanium dioxide, this compound particle 0.1g is distributed in the ammonium persulfate aqueous solution of 5g 22.8%, saturated absorption 24 hours, with the supercentrifuge centrifugal sedimentation of the compound hollow ball of the polymer that has adsorbed solution, be scattered in again in the 10g water, stir adding 0.5g aniline down.Reaction is 24 hours in ice-water bath, obtains polystyrene-poly acrylic acid/compound hollow ball of titanium dioxide polyaniline.After the hollow ball of this composite construction removed polystyrene and polyacrylic acid with chloroform, obtain the compound hollow ball of titanium dioxide and polyaniline.
The preparation of embodiment 10 burr type titanium dioxide/compound hollow ball of polystyrene-poly methacrylic acid and burr type titanium dioxide hollow ball
Get the emulsion that contains 0.1g polystyrene-poly methacrylate polymer hollow ball, its external diameter is 1000nm, the thickness of shell is 150nm, be distributed in the 10g ethanol, added the 1g butyl titanate at twice 1 hour at interval, reinforced finishing continued hydrolysis 4 hours, and obtaining with polystyrene-poly methacrylate polymer hollow ball is template, and titanium dioxide is grown in housing internal layer and passage and stretches out the surface and forms burr.After the hollow ball of this composite construction removed polystyrene and polymethylacrylic acid with chloroform, obtain the titanium dioxide hollow ball with burr, the result of transmission electron microscope shows that the titanium dioxide ball of this hollow is made up of 50～100nm particle, shell is thick to be 100nm, and the size of cavity is 600nm.Long 50～the 200nm of titanium dioxide burr, wide 20～100nm, high 10～150nm.
The preparation of embodiment 11 burr type silver/compound hollow ball of polystyrene-poly 4-vinylpridine and burr type silver hollow ball
Get the emulsion that contains 0.1g polystyrene-poly 4-vinylpridine polymer hollow ball, its external diameter is 300nm, the thickness of shell is 60nm, be distributed in the hydrazine hydrate solution of 10g 20wt%, soaked 24 hours, the polymer hollow ball supercentrifuge centrifugal sedimentation of hydrazine hydrate solution will have been adsorbed, be distributed to again in the liquor argenti nitratis ophthalmicus of 20g 1wt%, reacted 4 hours, obtaining with polystyrene-poly 4-vinylpridine polymer hollow ball is template, and silver is grown in housing internal layer and passage and stretches out the surface and forms burr.After the hollow ball of this composite construction removed polystyrene and poly 4 vinyl pyridine with oxolane, obtain silver-colored hollow ball with burr.
The preparation of embodiment 12 compound hollow ball of burr type polyaniline/polystyrene-polyacrylic acid and burr type polyaniline hollow ball
Get the emulsion that contains 0.1g polystyrene-poly acrylate copolymer hollow ball, its external diameter is 400nm, the thickness of shell is 80nm, be distributed in the ferric chloride in aqueous solution of 5g 20%, saturated absorption 24 hours, with the supercentrifuge centrifugal sedimentation of the compound hollow ball of the polymer that has adsorbed solution, be scattered in again in the 10g water, stir following minute 4 times and add 0.8g aniline, each 1 hour at interval, 25 ℃ of reaction temperatures, 24 hours reaction time, obtaining with polystyrene-poly acrylate copolymer hollow ball is template, and polyaniline grows is at housing internal layer and passage and stretch out surface formation burr.After the hollow ball of this composite construction removed polystyrene and polyacrylic acid with chloroform, obtain polyaniline hollow ball with burr.
Embodiment 13 housing outer surface growth shell, preparation silica/compound hollow ball of polystyrene-poly acrylic acid and silicon dioxide hollow sphere
Get 0.1g polystyrene-poly acrylate copolymer hollow ball, its external diameter is 8000nm, the thickness of shell is 200nm, be distributed in the 10g ethanol, add 1g15% ammoniacal liquor and 2g tetraethyl orthosilicate, hydrolysis 4 hours, obtaining with polystyrene-poly acrylic acid hollow ball is template, silicon dioxide growth is in the compound hollow ball of housing outer surface.After this compound hollow ball removed polystyrene and polyacrylic acid with chloroform, obtain silicon dioxide hollow sphere, the result of transmission electron microscope shows that the silica spheres of this hollow is made up of the 30nm particle, and shell is thick to be 200nm, and the size of cavity is 8000nm.
Embodiment 14 housing outer surface growth shell, preparation gold/compound hollow ball of polystyrene-poly oxygen ethene and golden hollow ball
Get 0.1g polystyrene-poly oxygen ethene polymers hollow ball, its external diameter is 40nm, the thickness of shell is 10nm, be distributed in the 10g water, add 1g15% hydrazine hydrate and 0.5g gold chloride, reacted 2 hours, obtaining with polystyrene-poly oxygen ethene hollow ball is template, and gold is grown in the compound hollow ball of housing outer surface.After this compound hollow ball removed polystyrene and polyoxyethylene with chloroform, obtain golden hollow ball, the result of transmission electron microscope shows that the gold goal of this hollow is made up of 5～10nm particle, and shell is thick to be 20nm, and the size of cavity is 40nm.
Embodiment 15 housing outer surface growth shell, the preparation of preparation compound hollow ball of polyaniline/polystyrene-polymethylacrylic acid and polyaniline hollow ball
0.1g the emulsion particle of polystyrene-poly methacrylic acid hollow structure, its external diameter are 400nm, the thickness of shell is 80nm, is distributed in the 10g water.Logical people's nitrogen in reaction vessel, the ammonium persulfate aqueous solution of adding 2g22.8% is behind the stirring 30min, add 0.5g aniline again, reaction is 24 hours in the ice-water bath, and obtaining with polystyrene-poly methacrylic acid hollow ball is template, and polyaniline grows is in the compound hollow ball of housing outer surface.After the hollow ball of this composite construction removed polystyrene and polymethylacrylic acid with oxolane, obtain the polyaniline hollow ball, the size of cavity is 400nm.
The preparation of embodiment 16 earth silicon/titanic oxide MULTILAYER COMPOSITE hollow ball and double-decker hollow ball thereof
Press the compound hollow ball of embodiment 1 preparation polystyrene-poly acrylic acid/titanium dioxide, this compound particle 0.1g is distributed in the 10g ethanol, add 1g silester and 1g25% ammoniacal liquor, 40 ℃ of reaction temperatures, reaction time 4h, promptly make silica/compound hollow ball of polystyrene-poly acrylic acid/titanium dioxide, this titanium dioxide is grown in polymer hollow ball housing internal layer, and silicon dioxide growth is in housing outer surface.After removing polystyrene and polyacrylic acid with chloroform, obtain silicon dioxide and titanium dioxide double-decker hollow ball, promptly contain the hollow ball of a titanium dioxide in the silicon dioxide hollow sphere.
The preparation of embodiment 17 gold medals/silica MULTILAYER COMPOSITE hollow ball and double-decker hollow ball thereof
0.1g the emulsion particle of polystyrene-poly methacrylic acid hollow structure, its external diameter is 100nm, the thickness of shell is 20nm, be distributed in the ethanolic solution of 50wt% tetraethyl orthosilicate of 1g, saturated absorption 24 hours will have been adsorbed the polymer hollow ball supercentrifuge centrifugal sedimentation of solution, be scattered in the 15wt% ammoniacal liquor of 10g again, hydrolysis 4 hours, obtaining with polystyrene-poly methacrylic acid hollow ball is template, silicon dioxide growth is in the compound hollow ball of housing internal layer.This compound particle is distributed in the 10g aqueous solution again, the chlorauric acid solution and the 4g50wt% hydrazine hydrate solution that add 6g30wt%, 40 ℃ of reaction temperatures, reaction time 4h, promptly make gold/compound hollow ball of polystyrene-poly acrylic acid/silica, this silicon dioxide growth is at polymer hollow ball housing internal layer, and gold is grown in housing outer surface.After removing polystyrene and polymethylacrylic acid with oxolane, obtain gold/silica double-decker hollow ball, contain the hollow ball of a silica in the promptly golden hollow ball.
The preparation of embodiment 18 polyaniline/argentum MULTILAYER COMPOSITE hollow ball and double-decker hollow ball thereof
0.1g the emulsion particle of polymethyl methacrylate-polyacrylic acid hollow structure, its external diameter is 300nm, the thickness of shell is 60nm, be distributed in the aqueous solution of 20wt% silver nitrate of 1g, saturated absorption 24 hours will have been adsorbed the polymer hollow ball supercentrifuge centrifugal sedimentation of solution, be scattered in again in the 15wt% hydrazine hydrate solution of 10g, reacted 4 hours, obtaining with polymethyl methacrylate-polyacrylic acid hollow ball is template, and silver is grown in the compound hollow ball of housing internal layer.This compound particle is distributed in the 10g aqueous solution again, feed nitrogen, add the 0.5g aniline and the 3g30wt% ammonium persulfate aqueous solution, be placed on and react 24h in the ice-water bath, promptly make polyaniline/polymethyl methacrylate-polyacrylic acid/silver-colored compound hollow ball, this silver is grown in polymer hollow ball housing internal layer, and polyaniline grows is in housing outer surface.After removing polystyrene and polymethylacrylic acid with chloroform, obtain polyaniline/argentum double-decker hollow ball, promptly contain the hollow ball of a silver in the polyaniline hollow ball.
The preparation of embodiment 19 earth silicon/titanic oxide MULTILAYER COMPOSITE hollow ball and concentric bilayer structure hollow ball
0.1g the emulsion particle of polystyrene-poly methacrylic acid hollow structure, its external diameter is 400nm, the thickness of shell is 80nm, and centrifugal the cleaning with ethanol removed outer surface water, is scattered in the 10g ethanol again, divide 4 times and add the 0.5g butyl titanate, each one hour at interval, reinforced finishing continued reaction 4 hours, 40 ℃ of reaction temperatures, obtaining with polystyrene-poly methacrylic acid hollow ball is template, and titanium dioxide is grown in the compound burr shape hollow ball of housing internal layer and passage.This compound particle is distributed in the 10g ethanol, add 2g silester and 1g15% ammoniacal liquor, 40 ℃ of reaction temperatures, reaction time 4h, promptly make silica/compound hollow ball of polystyrene-poly methacrylic acid/titanium dioxide, this titanium dioxide is grown in polymer hollow ball housing internal layer and passage, and silicon dioxide growth is in housing outer surface.After removing polystyrene and polymethylacrylic acid with oxolane, obtain silicon dioxide and titanium dioxide double-decker hollow ball, it is the hollow ball that contains a titanium dioxide in the silicon dioxide hollow sphere, there is the titanium dioxide post to link to each other between the two empty balls, interior hollow ball is moved in the hollow ball outside, and two hollow ball are concentric.
The preparation of embodiment 20 titanium dioxide/platinum MULTILAYER COMPOSITE hollow ball and concentric bilayer structure hollow ball
0.1g the emulsion particle of polystyrene-poly methacrylic acid hollow structure, its external diameter is 200nm, the thickness of shell is 50nm, it is dispersed in the sodium borohydride aqueous solution of 1g20wt%, soaked 24 hours, eccentric cleaning is removed outer surface solution, be scattered in again in the 10g water, divide 4 times and add the 4mL20wt% chloroplatinic acid, each one hour at interval, reinforced finishing continued reaction 8 hours, 20 ℃ of reaction temperatures, obtaining with polystyrene-poly methacrylic acid hollow ball is template, and platinum is grown in the compound burr shape hollow ball of housing internal layer and passage.This compound particle is distributed in the 10g ethanol, add 2g butyl titanate and 1g water, 40 ℃ of reaction temperatures, reaction time 4h, promptly make titanium dioxide/compound hollow ball of polystyrene-poly methacrylic acid/platinum, this platinum is grown in polymer hollow ball housing internal layer and passage, and titanium dioxide is grown in housing outer surface.After removing polystyrene and polymethylacrylic acid with oxolane, obtain titanium dioxide platinum double-decker hollow ball, promptly contain the hollow ball of a platinum in the titanium dioxide hollow ball, have the platinum post to link to each other between the two empty balls, interior hollow ball is moved in the hollow ball outside, and two hollow ball are concentric.
The preparation of embodiment 21 titanium dioxide/polyaniline MULTILAYER COMPOSITE hollow ball and concentric bilayer structure hollow ball
Press the compound hollow ball of embodiment 12 preparation burr shape polyaniline/polystyrene-polyacrylic acid, this compound particle 0.1g is distributed in the 10g ethanol, add 1g butyl titanate and 1g water, 60 ℃ of reaction temperatures, reaction time 4h, promptly make titanium dioxide/compound hollow ball of polystyrene-poly acrylic acid/polyaniline, this polyaniline grows is at polymer hollow ball housing internal layer and passage, and titanium dioxide is grown in housing outer surface.After removing polystyrene and polyacrylic acid with oxolane, obtain titanium dioxide polyaniline double-decker hollow ball, promptly contain the hollow ball of a polyaniline in the titanium dioxide hollow ball, have the polyaniline post to link to each other between the two empty balls, interior hollow ball is moved in the hollow ball outside, and two hollow ball are concentric.
The preparation of embodiment 22 titanium dioxide MULTILAYER COMPOSITE hollow ball and concentric bilayer structure hollow ball
Get the dried powder of 0.1g polystyrene-poly acrylic acid hollow structure, its external diameter is 400nm, the thickness of shell is 100nm, being distributed in the 5g concentrated sulfuric acid sulfonation handled 2 hours, eccentric cleaning obtains sulfonation modifying polymer hollow ball, its housing is outer for sulfonated polystyrene, intermediate layer are that polystyrene, internal layer are polyacrylic three-decker, so housing internal layer and outer hydrophilic, the centre also has hydrophilic channel.Polymer-modified hollow ball is immersed in the butyl titanate butanol solution of 1g 50%, soaked 24 hours, eccentric cleaning, then it is joined in the butanol solution of 10g 40% water, 40 ℃ were reacted 6 hours, obtain titanium dioxide/polystyrene-poly acrylic acid MULTILAYER COMPOSITE hollow ball, titanium dioxide is grown in polymer hollow ball housing internal layer, passage and skin.With the hollow ball of this composite construction 450 ℃ of sintering 2 hours, remove polystyrene and polyacrylic acid after, obtain titanium dioxide double-decker hollow ball.
The preparation of embodiment 23 silver medal MULTILAYER COMPOSITE hollow ball and concentric bilayer structure hollow ball
Get the dried powder of 0.1g polystyrene-poly methacrylic acid hollow structure, its external diameter is 400nm, the thickness of shell is 100nm, being distributed in the 5g concentrated sulfuric acid sulfonation handled 2 hours, eccentric cleaning obtains sulfonation modifying polymer hollow ball, its housing is outer for sulfonated polystyrene, intermediate layer are that polystyrene, internal layer are the three-decker of polymethylacrylic acid, so housing internal layer and outer hydrophilic, the centre also has hydrophilic channel.Polymer-modified hollow ball is immersed in the silver nitrate aqueous solution of 1g 20%, soaked 24 hours, eccentric cleaning, then it is joined in 10g 30% hydrazine hydrate solution, 20 ℃ were reacted 6 hours, obtain silver/polystyrene-poly methacrylic acid MULTILAYER COMPOSITE hollow ball, silver is grown in polymer hollow ball housing internal layer, passage and skin.With the hollow ball N of this composite construction, after the N dimethyl formamide is removed polystyrene and polymethylacrylic acid, obtain silver-colored double-decker hollow ball.
The preparation of embodiment 24 polyaniline MULTILAYER COMPOSITE hollow ball and concentric bilayer structure hollow ball
Get the dried powder of 0.1g polystyrene-poly acrylic acid hollow structure, its external diameter is 400nm, the thickness of shell is 100nm, being distributed in the 5g concentrated sulfuric acid sulfonation handled 2 hours, eccentric cleaning obtains sulfonation modifying polymer hollow ball, its housing is outer for sulfonated polystyrene, intermediate layer are that polystyrene, internal layer are polyacrylic three-decker, so housing internal layer and outer hydrophilic, the centre also has hydrophilic channel.Polymer-modified hollow ball is immersed in the liquor ferri trichloridi of 1g 30%, soaked 24 hours, eccentric cleaning, it is joined in the 10g water then, add 0.5g aniline, criticize pH value 1-2 with concentrated hydrochloric acid conditioned reaction solution, reaction is 24 hours in the ice-water bath, obtain polyaniline/polystyrene-polyacrylic acid MULTILAYER COMPOSITE hollow ball, polyaniline grows is at polymer hollow ball housing internal layer, passage and skin.With the hollow ball N of this composite construction, after the N dimethyl formamide is removed polystyrene and polyacrylic acid, obtain polyaniline double-decker hollow ball.
Embodiment 25 butyl polyacrylates prepare the compound hollow ball of polymer at the shell swollen-state polymerization
Get 0.1g polystyrene-poly methacrylate polymer hollow ball, its external diameter is 400nm, the thickness of shell is 80nm, is distributed in the 10g water, charges into nitrogen, contain 0.2% dodecyl sodium sulfate in the water, add 0.2g butyl acrylate and 2mg azodiisobutyronitrile, the room temperature lower magnetic force stirred swelling 8 hours, and 80 ℃ of polymerizations 18 hours heat up, obtaining with polystyrene-poly methacrylic acid hollow ball is template, and butyl polyacrylate is grown in the compound hollow ball of polymer in the housing.
Claims (14)
1. one kind prepares the method for hollow ball and compound hollow ball with template, it is characterized in that, in preparation method's step of polymer hollow ball template housing internal layer growth material:
(1.1) polymer hollow ball template particles is immersed in the inorganic matter precursor solution of 0.01wt%～60.0wt%, template particles keeps concentration in solution be 0.1wt%～40.0wt%, make the inorganic matter precursor solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity; The polymer hollow ball that contains the inorganic matter precursor solution that will obtain then under agitation joins in the reaction component aqueous solution; The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball of layer growth inorganic matter in the polymer hollow ball housing; Or
To react the component aqueous solution earlier and infiltrate polymer hollow ball template particles cavity, the polymer hollow ball that contains the reaction component aqueous solution that will obtain then under agitation joins in the inorganic matter precursor solution that concentration is 10.0wt%～60.0wt%, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning obtains the compound hollow ball of layer growth inorganic matter in the polymer hollow ball housing; Or
(1.2) polymer hollow ball template particles is immersed in the metal ion salt solution of 0.01wt%～60.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make metal ion salt solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity; Polymer hollow ball with the metal ion salting liquid that obtains under agitation joins in the reductant solution of 0.01wt%～60.0wt% then, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning promptly obtains the compound hollow ball of polymer hollow ball housing internal layer growing metal; Or
Reductant solution with 0.01wt%～60.0wt% infiltrates in the polymer hollow ball template particles cavity earlier, the polymer hollow ball that contains reductant solution that will obtain then under agitation joins in the metal ion salt solution that concentration is 10.0wt%～60.0wt%, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning obtains the compound hollow ball of polymer hollow ball housing internal layer growing metal; Or
(1.3) polymer hollow ball template particles is immersed in the polymer monomer solution that concentration is 0.01wt%～40.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make polymer monomer solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity; The polymer hollow ball that contains polymer monomer solution that will obtain then under agitation joins in 0.01wt%～30.0wt% initiator solution, in reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning promptly obtains the organic compound hollow ball of layer growth in the polymer hollow ball housing; Or
Earlier 0.01wt%～30.0wt% initiator solution is infiltrated polymer hollow ball template particles cavity, the polymer hollow ball that contains initiator solution that will obtain then under agitation joins in the polymer monomer solution that concentration is 5wt%～40wt%, in reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning obtains the organic compound hollow ball of layer growth in the polymer hollow ball;
(2). the polymer template that step (1.1), step (1.2) are obtained and the hollow ball of inorganic matter or metal composite place in the sintering furnace respectively, and blowing air, be warming up to 300～700 ℃ of calcinations with 0.1～10 ℃/minute speed, obtain inorganic matter or metal hollow ball respectively;
Perhaps the compound hollow ball of the polymer template that step (1.1), step (1.2), step (1.3) are obtained and inorganic matter, metal or organic matter uses selective solvent to carry out extracting respectively, remove template polymer, obtain inorganic matter, metal or organic matter hollow ball respectively;
The external diameter of described polymer hollow ball template particles is 0.02 μ m～10 μ m, and cavity volume is 10～95% of a whole microballoon;
The internal layer hydrophilic polymer of described polymer hollow ball template comprises polystyrolsulfon acid, polymethylacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide-based, polyvinyl pyrroles, poly-(2-vinylpyridine), poly-(4-vinylpridine), poly hydroxy ethyl acrylate, polyvinylesters, polyoxyethylene or polyvinyl ammonium chloride;
The outer lipophile polymer of described polymer hollow ball template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl tert-butyl acrylate, polymethylacrylic acid cinnamic acid ethyl ester, PMA, polyethyl acrylate, butyl polyacrylate, the polyacrylic acid tert-butyl ester, polyoxypropylene, poly dimethyl silane, polyvinyl butyl ester or polyisobutene;
The selective solvent that described usefulness removes polymer template is chloroform, toluene, oxolane, N, dinethylformamide;
At preparation SiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4, Si (OCH
2CH
2CH
2CH
3)
4, Na
2SiO
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation TiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is TiCl
4, Ti (OCH
3)
4, Ti (OCH
2CH
3)
4, Ti{OCH (CH
3)
2}
4, Ti (OCH
2CH
2CH
2CH
3)
4, TiOSO
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation SnO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is SnCl
4, Sn (OCH
3)
4, Sn (OCH
2CH
3)
4, Sn{OCH (CH
3)
2}
4, Sn (OCH
2CH
2CH
2CH
3)
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation ZrO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is ZrCl
4, Zr (OCH
3)
4, Zr (OCH
2CH
3)
4, Zr{OCH (CH
3)
2)
4, Zr (OCH
2CH
2CH
2CH
3)
4, Zr (SO
4)
2Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al
2O
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is AlCl
3, Al (OCH
3)
3, Al (OCH
2CH
3)
3, Al{OCH (CH
3)
2}
3, Al (OCH
2CH
2CH
2CH
3)
3, Al
2(SO
4)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation V
2O
5When hollow ball or compound hollow ball, described inorganic matter precursor solution is VO (OCH
3)
3, VO (OCH
2CH
3)
3, VO{OCH (CH
3)
2}
3, VO (OCH
2CH
2CH
2CH
3)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
When preparation ZnO hollow ball or compound hollow ball, described inorganic matter precursor solution is Zn (NO
3)
2, Zn (OOCCH
3)
2, ZnCl
2, Zn (ClO
4)
2Alcoholic solution; The reaction component aqueous solution is the water or the alcoholic solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation WO
3When hollow ball or compound hollow ball, described inorganic precursor solution is (NH
4)
6H
2W
12O
41, NaWO
3The aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt～100wt% water, and regulating its pH value with the concentrated ammonia liquor of concentration 35wt% concentrated hydrochloric acid or concentration 25wt% is 1～13;
At preparation MoO
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is MoO
32H
2The O aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al (OH)
3Or Mg (OH)
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is the chloride of soluble aluminum, magnesium or the aqueous solution of sulfate; The reaction component aqueous solution is NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation biomineralization material C aCO
3, Ca
10(PO
4)
6(OH)
2, CaSO
4, or BaSO
4When hollow ball or compound hollow ball, described inorganic matter precursor solution is Ca (OH)
2, CaCl
2, Ba (OH)
2Or BaCl
2The aqueous solution; The reaction component aqueous solution is for containing CO
3 2-, PO
4 3-, SO
4 2-Na
+Or K
+Salt, perhaps concentration is 0.01wt%～30wt%H
2CO
3, H
3PO
4, H
2SO
4The aqueous solution;
When preparation semiconductor sulfuration thing hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble chloride of respective metal, nitrate, sulfate; The reaction component aqueous solution is that concentration is the aqueous solution of 0.01wt%～30wt% vulcanized sodium or thiocarbamide;
When preparation semiconductor selenide or tellurides hollow ball or compound hollow ball, the aqueous solution of the soluble chloride that described inorganic matter precursor solution is a metal cation, nitrate, sulfate; The reaction component aqueous solution is the aqueous solution of concentration 0.01wt%～30wt% sodium selenide or tellurium sodium;
At preparation magnetic compound Fe
3O
4, Fe
2O
3Or when containing the ferrite hollow ball of zinc, manganese, cobalt, nickel, copper, magnesium or compound hollow ball, described inorganic matter precursor solution is Fe
2+, Fe
3+, Zn
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+, Mg
2+Soluble chloride, nitrate, the aqueous solution of sulfate; The reaction component aqueous solution is that concentration is the aqueous solution of NaOH, potassium hydroxide or the ammoniacal liquor of 0.01wt%～30wt%, or concentration is 1wt%～60wt% hydrazine hydrate solution;
When preparation metal A u, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow ball or compound hollow ball, described metal ion salt solution is the aqueous solution of respective metal ionically-soluble perchlorate, chloride, nitrate, sulfate; Reductant solution is NaBH
4, LiB (C
2H
5)
3H or N
2H
4The aqueous solution;
When preparation conducting polymer polyaniline, polypyrrole, polythiophene, p-phenylene vinylene and derivative hollow ball or compound hollow ball, water or alcoholic solution that described polymer monomer solution is corresponding monomer; Initiator solution is the aqueous solution of potassium peroxydisulfate, ammonium persulfate or ferric trichloride;
When preparation sensitiveness gel poly-N-isopropyl acrylamide, polyacrylic acid, polymethylacrylic acid hollow ball or compound hollow ball, described polymer monomer solution is N-N-isopropylacrylamide, acrylic acid, methacrylic acid or its water or alcoholic solution; Initiator solution is the aqueous solution of potassium peroxydisulfate or ammonium persulfate;
Described inert gas is nitrogen or argon gas;
Described alcoholic solution is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols.
2. method according to claim 1 is characterized in that: the hollow ball of described inorganic matter or compound hollow ball comprise: TiO
2, SiO
2, SnO
2, ZrO
2, Al
2O
3, V
2O
5, ZnO, WO
3, MoO
3, Al (OH)
3Or Mg (OH)
2The hollow ball of biomineralization material or compound hollow ball comprise: CaCO
3, Ca
10(PO
4)
6(OH)
2, BaSO
4Or CaSO
4The hollow ball of semi-conducting material or compound hollow ball comprise: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; The hollow ball of magnetic compound or compound hollow ball comprise: Fe
3O
4, Fe
2O
3Or contain the ferrite of zinc, manganese, cobalt; The hollow ball of metal or compound hollow ball comprise: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe; Organic hollow ball or compound hollow ball comprise: polyaniline, polypyrrole, polythiophene or p-phenylene vinylene and derivative thereof, poly-N-isopropyl acrylamide, polyacrylic acid or polymethylacrylic acid.
3. method according to claim 1, it is characterized in that: describedly carrying out step (2) before, the compound hollow ball that obtains respectively with step (1.1), step (1.2), step (1.3) is a template, difference further repeating step (1.1), step (1.2) and step (1.3), carry out circular response, when the above circular response of twice or twice generated same substance, the product shell that increases compound hollow ball was thick; Or
The compound hollow ball that step (1.2) or step (1.3) are obtained is carried out circular response as the template particles of step (1.1); Or
The compound hollow ball that step (1.1) or step (1.3) are obtained is carried out circular response as the template particles of step (1.2); Or
The compound hollow ball that step (1.1) or step (1.2) are obtained is carried out circular response as the template particles of step (1.3);
When the above circular response of twice or twice generates not material of the same race, obtain the compound hollow ball of multiple material.
4. one kind prepares the method for hollow ball and compound hollow ball with template, it is characterized in that, in preparation method's step of polymer hollow ball template housing internal layer and hydrophilic channel growth material:
(1). polymer hollow ball template particles is immersed in the reaction component aqueous solution, template particles keeps concentration in the reaction component aqueous solution be 0.1wt%～40.0wt%, make the reaction component aqueous solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity, the polymer hollow ball that contains the reaction component aqueous solution that will obtain then under agitation joins in the alcoholic solution of inorganic matter precursor, and the inorganic matter precursor is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%; The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning, obtain the polymer template and the compound hollow ball of inorganic matter of surface band burr shape material, its hydrophilic channel by replica, expand even stretch out spheroid, the housing internal layer generates continuous material; Or
Polymer hollow ball template particles is immersed in the reductant solution of 0.01wt%～60.0wt%, template particles keeps concentration in solution be 0.1wt%～40.0wt%, make reductant solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity; The polymer hollow ball that contains reductant solution that will obtain then under agitation joins in the metal ion salt solution, and metal cation salt is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%; The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning, promptly obtain the polymer template of surface band burr shape material and the hollow ball of metal composite, its hydrophilic channel by replica, expand even stretch out spheroid, the housing internal layer generates continuous material; Or
It is in 0.01wt%～30.0wt% initiator solution that polymer hollow ball template particles is immersed in reaction component concentration, template particles keeps concentration in solution be 0.1wt%～40.0wt%, make initiator solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity; The polymer hollow ball that contains initiator solution that will obtain then under agitation joins in the polymer monomer solution, and polymer monomer is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%; In reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning, promptly obtain polymer template and the compound hollow ball of organic matter of surface band burr shape material, its hydrophilic channel by replica, expand even stretch out spheroid, the material that the generation of housing internal layer is continuous;
(2). the hollow ball of polymer template that step (1) is obtained and inorganic matter, metal composite places in the sintering furnace, and blowing air, is warming up to 300～700 ℃ of calcinations with 0.1～10 ℃/minute speed, obtains the inorganic or metal hollow ball of surface band burr; Or
Polymer template that step (1) is obtained and inorganic matter, metal, the compound hollow ball of organic matter use selective solvent to carry out extracting, remove template polymer, obtain inorganic matter, metal or the organic matter hollow ball of surface band burr;
The external diameter of described polymer hollow ball template particles is 0.02 μ m～10 μ m, and cavity volume is 10～95% of a whole microballoon;
The internal layer hydrophilic polymer of described polymer hollow ball template comprises polystyrolsulfon acid, polymethylacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide-based, polyvinyl pyrroles, poly-(2-vinylpyridine), poly-(4-vinylpridine), poly hydroxy ethyl acrylate, polyvinylesters, polyoxyethylene or polyvinyl ammonium chloride;
The outer lipophile polymer of described polymer hollow ball template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl tert-butyl acrylate, polymethylacrylic acid cinnamic acid ethyl ester, PMA, polyethyl acrylate, butyl polyacrylate, the polyacrylic acid tert-butyl ester, polyoxypropylene, poly dimethyl silane, polyvinyl butyl ester or polyisobutene;
The selective solvent that described usefulness removes polymer template is chloroform, toluene, oxolane or N, dinethylformamide;
At preparation SiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4, Si (OCH
2CH
2CH
2CH
3)
4Or Na
2SiO
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation TiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is TiCl
4, Ti (OCH
3)
4, Ti (OCH
2CH
3)
4, Ti{OCH (CH
3)
2}
4, Ti (OCH
2CH
2CH
2CH
3)
4Or TiOSO
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation SnO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is SnCl
4, Sn (OCH
3)
4, Sn (OCH
2CH
3)
4, Sn{OCH (CH
3)
2}
4, Sn (OCH
2CH
2CH
2CH
3)
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation ZrO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is ZrCl
4, Zr (OCH
3)
4, Zr (OCH
2CH
3)
4, Zr{OCH (CH
3)
2}
4, Zr (OCH
2CH
2CH
2CH
3)
4, Zr (SO
4)
2Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al
2O
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is AlCl
3, Al (OCH
3)
3, Al (OCH
2CH
3)
3, Al{OCH (CH
3)
2}
3, Al (OCH
2CH
2CH
2CH
3)
3, Al
2(SO
4)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation V
2O
5When hollow ball or compound hollow ball, described inorganic matter precursor solution is VO (OCH
3)
3, VO (OCH
2CH
3)
3, VO{OCH (CH
3)
2}
3, VO (OCH
2CH
2CH
2CH
3)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
When preparation ZnO hollow ball or compound hollow ball, described inorganic matter precursor solution is Zn (NO
3)
2, Zn (OOCCH
3)
2, ZnCl
2, Zn (ClO
4)
2Alcoholic solution; The reaction component aqueous solution is the water or the alcoholic solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation WO
3When hollow ball or compound hollow ball, described inorganic precursor solution is (NH
4)
6H
2W
12O
41Or NaWO
3The aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation MoO
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is MoO
32H
2The O aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al (OH)
3Or Mg (OH)
2When hollow ball or compound hollow ball, chloride or sulfate solution that described inorganic matter precursor solution is soluble aluminum, magnesium; The reaction component aqueous solution is the aqueous solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation biomineralization material C aCO
3, Ca
10(PO
4)
6(OH)
2, CaSO
4Or BaSO
4When hollow ball or compound hollow ball, described inorganic matter precursor solution is Ca (OH)
2, CaCl
2, Ba (OH)
2Or BaCl
2The aqueous solution; The reaction component aqueous solution is that concentration 0.01wt%～30wt% contains CO
3 2-, PO
4 3-, SO
4 2-Na
+Or K
+Salt, perhaps H
2CO
3, H
3PO
4, H
2SO
4The aqueous solution;
When preparation semiconductor sulfuration thing hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble chloride of respective metal, nitrate or sulfate; The reaction component aqueous solution is the aqueous solution of concentration 0.01wt%～30wt% vulcanized sodium or thiocarbamide;
When preparation semiconductor selenide or tellurides hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble chloride of respective metal, nitrate or sulfate; The reaction component aqueous solution is the aqueous solution of concentration 0.01wt%～30wt% sodium selenide or tellurium sodium;
At preparation magnetic compound Fe
3O
4, Fe
2O
3Or when containing the ferrite hollow ball of zinc, manganese, cobalt, nickel, copper, magnesium or compound hollow ball, described inorganic matter precursor solution is Fe
2+, Fe
3+, Zn
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+, Mg
2+The aqueous solution of soluble chloride, nitrate or sulfate; The reaction component aqueous solution is the aqueous solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%, or concentration is the hydrazine hydrate solution of 1wt%～60wt%;
When preparation metal A u, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow ball or compound hollow ball, described metal ion salt solution is the aqueous solution of respective metal ionically-soluble perchlorate, chloride, nitrate, sulfate; Reductant solution is NaBH
4, LiB (C
2H
5)
3H or N
2H
4The aqueous solution;
When preparation conducting polymer polyaniline, polypyrrole, polythiophene, p-phenylene vinylene and derivative hollow ball or compound hollow ball, water or alcoholic solution that described polymer monomer solution is corresponding monomer; Initiator solution is the aqueous solution of potassium peroxydisulfate, ammonium persulfate or ferric trichloride;
When preparation sensitiveness gel poly-N-isopropyl acrylamide, polyacrylic acid, polymethylacrylic acid hollow ball or compound hollow ball, described polymer monomer solution is N-N-isopropylacrylamide, acrylic acid, methacrylic acid or its water or alcoholic solution; Initiator solution is the aqueous solution of potassium peroxydisulfate or ammonium persulfate;
Described inert gas is nitrogen or argon gas;
Described alcoholic solution is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols.
5. method according to claim 4 is characterized in that: the hollow ball of described inorganic matter or compound hollow ball comprise: TiO
2, SiO
2, SnO
2, ZrO
2, Al
2O
3, V
2O
5, ZnO, WO
3, MoO
3, Al (OH)
3Or Mg (OH)
2The hollow ball of biomineralization material or compound hollow ball comprise: CaCO
3, Ca
10(PO
4)
6(OH)
2, BaSO
4Or CaSO
4The hollow ball of semi-conducting material or compound hollow ball comprise: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; The hollow ball of magnetic compound or compound hollow ball comprise: Fe
3O
4, Fe
2O
3Or contain the ferrite of zinc, manganese, cobalt; The hollow ball of metal or compound hollow ball comprise: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe; Organic hollow ball or compound hollow ball comprise: polyaniline, polypyrrole, polythiophene or p-phenylene vinylene and derivative thereof, poly-N-isopropyl acrylamide, polyacrylic acid or polymethylacrylic acid.
6. one kind prepares the method for hollow ball and compound hollow ball with template, it is characterized in that, in preparation method's step of polymer hollow ball template housing outer surface growth material:
Polymer hollow ball template particles is dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth inorganic matter; Remove polymer template, obtain the inorganic matter hollow ball; Or
Polymer hollow ball template particles is dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growing metal; Remove polymer template, obtain the metal hollow ball; Or
Polymer hollow ball template particles is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains polymer and organic compound hollow ball in the growth of polymer hollow ball housing outer surface; Remove template polymer, obtain the organic matter hollow ball;
The external diameter of described polymer hollow ball template particles is 0.02 μ m～10 μ m, and cavity volume is 10～95% of a whole microballoon;
The internal layer hydrophilic polymer of described polymer hollow ball template comprises polystyrolsulfon acid, polymethylacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide-based, polyvinyl pyrroles, poly-(2-vinylpyridine), poly-(4-vinylpridine), poly hydroxy ethyl acrylate, polyvinylesters, polyoxyethylene or polyvinyl ammonium chloride.
The outer lipophile polymer of described polymer hollow ball template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl tert-butyl acrylate, polymethylacrylic acid cinnamic acid ethyl ester, PMA, polyethyl acrylate, butyl polyacrylate, the polyacrylic acid tert-butyl ester, polyoxypropylene, poly dimethyl silane, polyvinyl butyl ester or polyisobutene;
The selective solvent that described usefulness removes polymer template is chloroform, toluene, oxolane or N, dinethylformamide;
At preparation SiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4, Si (OCH
2CH
2CH
2CH
3)
4Or Na
2SiO
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation TiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is TiCl
4, Ti (OCH
3)
4, Ti (OCH
2CH
3)
4, Ti{OCH (CH
3)
2}
4, Ti (OCH
2CH
2CH
2CH
3)
4Or TiOSO
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation SnO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is SnCl
4, Sn (OCH
3)
4, Sn (OCH
2CH
3)
4, Sn{OCH (CH
3)
2}
4Or Sn (OCH
2CH
2CH
2CH
3)
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation ZrO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is ZrCl
4, Zr (OCH
3)
4, Zr (OCH
2CH
3)
4, Zr{OCH (CH
3)
2}
4, Zr (OCH
2CH
2CH
2CH
3)
4Or Zr (SO
4)
2Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al
2O
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is AlCl
3, Al (OCH
3)
3, Al (OCH
2CH
3)
3, Al{OCH (CH
3)
2}
3, Al (OCH
2CH
2CH
2CH
3)
3Or Al
2(SO
4)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation V
2O
5When hollow ball or compound hollow ball, described inorganic matter precursor solution is VO (OCH
3)
3, VO (OCH
2CH
3)
3, VO{OCH (CH
3)
2}
3Or VO (OCH
2CH
2CH
2CH
3)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
When preparation ZnO hollow ball or compound hollow ball, described inorganic matter precursor solution is Zn (NO
3)
2, Zn (OOCCH
3)
2, ZnCl
2Or Zn (ClO
4)
2Alcoholic solution; The reaction component aqueous solution be concentration O.01wt%～water or the alcoholic solution of NaOH, potassium hydroxide or the ammoniacal liquor of 30wt%;
At preparation WO
3When hollow ball or compound hollow ball, described inorganic precursor solution is (NH
4)
6H
2W
12O
41Or NaWO
3The aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation MoO
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is MoO
32H
2The O aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al (OH)
3Or Mg (OH)
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is the chloride of soluble aluminum, magnesium, the aqueous solution of sulfate; The reaction component aqueous solution is the aqueous solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation biomineralization material C aCO
3, Ca
10(PO
4)
6(OH)
2, CaSO
4, or BaSO
4When hollow ball or compound hollow ball, described inorganic matter precursor solution is Ca (OH)
2, CaCl
2, Ba (OH)
2Or BaCl
2The aqueous solution; The reaction component aqueous solution is for containing CO
3 2-, PO
4 3-, SO
4 2-Na
+Or K
+Salt, the perhaps H of concentration 0.01wt%～30wt%
2CO
3, H
3PO
4Or H
2SO
4The aqueous solution;
When preparation semiconductor sulfuration thing hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble chloride of respective metal, nitrate or sulfate; The reaction component aqueous solution is the vulcanized sodium of concentration 0.01wt%～30wt% or the aqueous solution of thiocarbamide;
When preparation semiconductor selenide or tellurides hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble chloride of respective metal, nitrate, sulfate; The reaction component aqueous solution is the aqueous solution of concentration 0.01wt%～30wt% sodium selenide or tellurium sodium;
At preparation magnetic compound Fe
3O
4Or Fe
2O
3Or when containing the ferrite hollow ball of zinc, manganese, cobalt, nickel, copper, magnesium or compound hollow ball, described inorganic matter precursor solution is Fe
2+, Fe
3+, Zn
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+Or Mg
2+The aqueous solution of soluble chloride, nitrate or sulfate; The reaction component aqueous solution is the aqueous solution of concentration 0.01wt%～30wt% NaOH, potassium hydroxide or ammoniacal liquor, or the hydrazine hydrate solution of concentration 1wt%～60wt%;
When preparation metal A u, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow ball or compound hollow ball, described metal ion salt solution is the aqueous solution of respective metal ionically-soluble perchlorate, chloride, nitrate or sulfate; Reductant solution is NaBH
4, LiB (C
2H
5)
3H or N
2H
4The aqueous solution;
When preparation conducting polymer polyaniline, polypyrrole, polythiophene, p-phenylene vinylene and derivative hollow ball or compound hollow ball, water or alcoholic solution that described polymer monomer solution is corresponding monomer; Initiator solution is the aqueous solution of potassium peroxydisulfate, ammonium persulfate or ferric trichloride;
When preparation sensitiveness gel poly-N-isopropyl acrylamide, polyacrylic acid, polymethylacrylic acid hollow ball or compound hollow ball, described polymer monomer solution is monomer N-N-isopropylacrylamide, acrylic acid, methacrylic acid or its water or alcoholic solution; Initiator solution is the aqueous solution of potassium peroxydisulfate or ammonium persulfate;
Described inert gas is nitrogen or argon gas.
Described alcoholic solution is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols.
7. method according to claim 6 is characterized in that: the hollow ball of described inorganic matter or compound hollow ball comprise: TiO
2, SiO
2, SnO
2, ZrO
2, Al
2O
3, V
2O
5, ZnO, WO
3, MoO
3, Al (OH)
3Or Mg (OH)
2The hollow ball of biomineralization material or compound hollow ball comprise: CaCO
3, Ca
10(PO
4)
6(OH)
2, BaSO
4Or CaSO
4The hollow ball of semi-conducting material or compound hollow ball comprise: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; The hollow ball of magnetic compound or compound hollow ball comprise: Fe
3O
4, Fe
2O
3Or contain the ferrite of zinc, manganese, cobalt; The hollow ball of metal or compound hollow ball comprise: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe; Organic hollow ball or compound hollow ball comprise: polyaniline, polypyrrole, polythiophene or p-phenylene vinylene and derivative thereof, poly-N-isopropyl acrylamide, polyacrylic acid or polymethylacrylic acid.
8. one kind prepares the method for hollow ball and compound hollow ball with template, it is characterized in that preparation method's step of the double-decker hollow ball of eccentric structure:
(1.1) polymer hollow ball template particles is immersed in the inorganic matter precursor solution of 0.01wt%～60.0wt%, template particles keeps concentration in solution be 0.1wt%～40.0wt%, make the inorganic matter precursor solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity; The polymer hollow ball that contains the inorganic matter precursor solution that will obtain then under agitation joins in the reaction component aqueous solution, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning promptly obtains the compound hollow ball of layer growth inorganic matter in the polymer hollow ball housing; Or
To react the component aqueous solution earlier and infiltrate polymer hollow ball template particles cavity, the polymer hollow ball that contains the reaction component aqueous solution that will obtain then under agitation joins in the inorganic matter precursor solution that concentration is 10.0wt%～60.0wt%, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning obtains the compound hollow ball of layer growth inorganic matter in the polymer hollow ball housing; Or
(1.2) polymer hollow ball template particles is immersed in the metal ion salt solution of 0.01wt%～60.0wt%, template particles keeps concentration in solution be 0.1wt%～40.0wt%, make metal ion salt solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity; Polymer hollow ball with the metal ion salting liquid that obtains under agitation joins in the reductant solution of 0.01wt%～60.0wt% then, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning promptly obtains the compound hollow ball of polymer hollow ball housing internal layer growing metal; Or
Reductant solution with 0.01wt%～60.0wt% infiltrates in the polymer hollow ball template particles cavity earlier, the polymer hollow ball that contains reductant solution that will obtain then under agitation joins in the metal ion salt solution that concentration is 10.0wt%～60.0wt%, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning obtains the compound hollow ball of polymer hollow ball housing internal layer growing metal; Or
(1.3) polymer hollow ball template particles is immersed in the polymer monomer solution that concentration is 0.01wt%～40.0wt%, template particles keeps concentration in these solution be 0.1wt%～40.0wt%, make polymer monomer solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity; The polymer hollow ball that contains polymer monomer solution that will obtain then under agitation joins in 0.01wt%～30.0wt% initiator solution, in reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning promptly obtains the organic compound hollow ball of layer growth in the polymer hollow ball housing; Or
Earlier 0.01wt%～30.0wt% initiator solution is infiltrated polymer hollow ball template particles cavity, the polymer hollow ball that contains initiator solution that will obtain then under agitation joins in the polymer monomer solution that concentration is 5wt%～40wt%; Feed inert gas in reaction vessel, the concentration of template particles remains on 0.1wt%～40wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and reaction finishes, and eccentric cleaning obtains the organic compound hollow ball of layer growth in the polymer hollow ball;
(2). the compound hollow ball of the interior layer growth inorganic matter that step (1.1) is obtained is dispersed in the alcoholic solution, add the inorganic matter precursor and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface and interior layer growth inorganic matter; Or
The compound hollow ball of the interior layer growth inorganic matter that step (1.1) is obtained is dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growing metal and interior layer growth inorganic matter; Or
The compound hollow ball of the interior layer growth inorganic matter that step (1.1) is obtained is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth organic matter and interior layer growth inorganic matter; Or
The compound hollow ball of the internal layer growing metal that step (1.2) is obtained is dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth inorganic matter and internal layer growing metal; Or
The compound hollow ball of the internal layer growing metal that step (1.2) is obtained is dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface and internal layer growing metal; Or
The compound hollow ball of the internal layer growing metal that step (1.2) is obtained is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth organic matter and internal layer growing metal; Or
The organic compound hollow ball of interior layer growth that step (1.3) is obtained is dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains in polymer hollow ball housing outer surface growth inorganic matter and the organic compound hollow ball of interior layer growth; Or
The organic compound hollow ball of interior layer growth that step (1.3) is obtained is dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains in polymer hollow ball housing outer surface growing metal and the organic compound hollow ball of interior layer growth; Or
The organic compound hollow ball of interior layer growth that step (1.3) is obtained is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains in polymer hollow ball housing outer surface and the organic compound hollow ball of interior layer growth;
The external diameter of described polymer hollow ball template particles is 0.02 μ m～10 μ m, and cavity volume is 10～95% of a whole microballoon;
The internal layer hydrophilic polymer of described polymer hollow ball template comprises polystyrolsulfon acid, polymethylacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide-based, polyvinyl pyrroles, poly-(2-vinylpyridine), poly-(4-vinylpridine), poly hydroxy ethyl acrylate, polyvinylesters, polyoxyethylene or polyvinyl ammonium chloride;
The outer lipophile polymer of described polymer hollow ball template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl tert-butyl acrylate, polymethylacrylic acid cinnamic acid ethyl ester, PMA, polyethyl acrylate, butyl polyacrylate, the polyacrylic acid tert-butyl ester, polyoxypropylene, poly dimethyl silane, polyvinyl butyl ester or polyisobutene;
The selective solvent that described usefulness removes polymer template is chloroform, toluene, oxolane or N, dinethylformamide;
At preparation SiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4, Si (OCH
2CH
2CH
2CH
3)
4, Na
2SiO
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation TiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is TiCl
4, Ti (OCH
3)
4, Ti (OCH
2CH
3)
4, Ti{OCH (CH
3)
2}
4, Ti (OCH
2CH
2CH
2CH
3)
4, TiOSO
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation SnO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is SnCl
4, Sn (OCH
3)
4, Sn (OCH
2CH
3)
4, Sn{OCH (CH
3)
2}
4, Sn (OCH
2CH
2CH
2CH
3)
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation ZrO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is ZrCl
4, Zr (OCH
3)
4, Zr (OCH
2CH
3)
4, Zr{OCH (CH
3)
2}
4, Zr (OCH
2CH
2CH
2CH
3)
4, Zr (SO
4)
2Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al
2O
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is AlCl
3, Al (OCH
3)
3, Al (OCH
2CH
3)
3, Al{OCH (CH
3)
2}
3, Al (OCH
2CH
2CH
2CH
3)
3, Al
2(SO
4)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation V
2O
5When hollow ball or compound hollow ball, described inorganic matter precursor solution is VO (OCH
3)
3, VO (OCH
2CH
3)
3, VO{OCH (CH
3)
2}
3, VO (OCH
2CH
2CH
2CH
3)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
When preparation ZnO hollow ball or compound hollow ball, described inorganic matter precursor solution is Zn (NO
3)
2, Zn (OOCCH
3)
2, ZnCl
2, Zn (ClO
4)
2Alcoholic solution; The reaction component aqueous solution is the water or the alcoholic solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation WO
3When hollow ball or compound hollow ball, described inorganic precursor solution is (NH
4)
6H
2W
12O
41, NaWO
3The aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt～100wt% water, and regulating its pH value with the concentrated ammonia liquor of concentration 35wt% concentrated hydrochloric acid or concentration 25wt% is 1～13;
At preparation MoO
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is MoO
32H
2The O aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al (OH)
3Or Mg (OH)
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is the chloride of soluble aluminum, magnesium or the aqueous solution of sulfate; The reaction component aqueous solution is NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation biomineralization material C aCO
3, Ca
10(PO
4)
6(OH)
2, CaSO
4, or BaSO
4When hollow ball or compound hollow ball, described inorganic matter precursor solution is Ca (OH)
2, CaCl
2, Ba (OH)
2Or BaCl
2The aqueous solution; The reaction component aqueous solution is for containing CO
3 2-, PO
4 3-, SO
4 2-Na
+Or K
+Salt, perhaps concentration is 0.01wt%～30wt%H
2CO
3, H
3PO
4, H
2SO
4The aqueous solution;
When preparation semiconductor sulfuration thing hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble chloride of respective metal, nitrate, sulfate; The reaction component aqueous solution is that concentration is the aqueous solution of 0.01wt%～30wt% vulcanized sodium or thiocarbamide;
When preparation semiconductor selenide or tellurides hollow ball or compound hollow ball, the aqueous solution of the soluble chloride that described inorganic matter precursor solution is a metal cation, nitrate, sulfate; The reaction component aqueous solution is the aqueous solution of concentration 0.01wt%～30wt% sodium selenide or tellurium sodium;
At preparation magnetic compound Fe
3O
4, Fe
2O
3Or when containing the ferrite hollow ball of zinc, manganese, cobalt, nickel, copper, magnesium or compound hollow ball, described inorganic matter precursor solution is Fe
2+, Fe
3+, Zn
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+, Mg
2+Soluble chloride, nitrate, the aqueous solution of sulfate; The reaction component aqueous solution is the aqueous solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%, or concentration is 1wt%～60wt% hydrazine hydrate solution;
When preparation metal A u, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow ball or compound hollow ball, described metal ion salt solution is the aqueous solution of respective metal ionically-soluble perchlorate, chloride, nitrate, sulfate; Reductant solution is NaBH
4, LiB (C
2H
5)
3H or N
2H
4The aqueous solution;
When preparation conducting polymer polyaniline, polypyrrole, polythiophene, p-phenylene vinylene and derivative hollow ball or compound hollow ball, water or alcoholic solution that described polymer monomer solution is corresponding monomer; Initiator solution is the aqueous solution of potassium peroxydisulfate, ammonium persulfate or ferric trichloride;
When preparation sensitiveness gel poly-N-isopropyl acrylamide, polyacrylic acid, polymethylacrylic acid hollow ball or compound hollow ball, described polymer monomer solution is N-N-isopropylacrylamide, acrylic acid, methacrylic acid or its water or alcoholic solution; Initiator solution is the aqueous solution of potassium peroxydisulfate or ammonium persulfate;
Described inert gas is nitrogen or argon gas;
Described alcoholic solution is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or butanols.
9. method according to claim 8 is characterized in that: the hollow ball of described inorganic matter or compound hollow ball comprise: TiO
2, SiO
2, SnO
2, ZrO
2, Al
2O
3, V
2O
5, ZnO, WO
3, MoO
3, Al (OH)
3Or Mg (OH)
2The hollow ball of biomineralization material or compound hollow ball comprise: CaCO
3, Ca
10(PO
4)
6(OH)
2, BaSO
4Or CaSO
4The hollow ball of semi-conducting material or compound hollow ball comprise: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; The hollow ball of magnetic compound or compound hollow ball comprise: Fe
3O
4, Fe
2O
3Or contain the ferrite of zinc, manganese, cobalt; The hollow ball of metal or compound hollow ball comprise: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe; Organic hollow ball or compound hollow ball comprise: polyaniline, polypyrrole, polythiophene or p-phenylene vinylene and derivative thereof, poly-N-isopropyl acrylamide, polyacrylic acid or polymethylacrylic acid.
10. one kind prepares the method for hollow ball and compound hollow ball with template, it is characterized in that preparation method's step of the double-decker hollow ball of concentric structure:
(1.1) polymer hollow ball template particles is immersed in the reaction component aqueous solution, template particles keeps concentration in solution be 0.1wt%～40.0wt%, make the reaction component aqueous solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity; The polymer hollow ball that contains the reaction component aqueous solution that will obtain then under agitation joins in the alcoholic solution of inorganic matter precursor, and the inorganic matter precursor is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%; The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and reaction finishes, and eccentric cleaning obtains polymer template and the compound hollow ball of inorganic matter that burr shape material is with on the surface; Or
(1.2) polymer hollow ball template particles is immersed in the reductant solution of 0.01wt%～60.0wt%, template particles keeps concentration in solution be 0.1wt%～40.0wt%, make reductant solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity, the polymer hollow ball that contains reductant solution that will obtain then under agitation joins in the metal ion salt solution, and metal cation salt is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%; The concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and reaction finishes, and eccentric cleaning promptly obtains the polymer template of surface band burr shape material and the hollow ball of metal composite; Or
(1.3) polymer hollow ball template particles being immersed in reaction component concentration is in 0.01wt%～30.0wt% initiator solution, template particles keeps concentration in solution be 0.1wt%～40.0wt%, make initiator solution infiltrate the cavity of polymer hollow ball template, reach the solution centrifugal flush away that not to infiltrate after the balance in the polymer hollow ball template cavity, the polymer hollow ball that contains initiator solution that will obtain then under agitation joins in the polymer monomer solution, and polymer monomer is by constantly replenishing a constant density that maintains 0.01wt%～10.0wt%; In reaction vessel, feed inert gas, the concentration of template particles remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, and reaction finishes, eccentric cleaning promptly obtains polymer template and the compound hollow ball of organic matter that burr shape material is with on the surface;
(2). the compound hollow ball of internal layer that step (1.1) is obtained and passage growth inorganic matter is dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface, internal layer and passage growth inorganic matter; Remove polymer template, obtain double-decker inorganic matter hollow ball, promptly contain hollow ball in the hollow ball, in the inorganic matter hollow ball that obtains between two hollow ball the organic/inorganic substance post link to each other, the motion in the hollow ball outside of interior hollow ball, two hollow ball are concentric; Or
The compound hollow ball of internal layer that step (1.1) is obtained and passage growth inorganic matter is dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growing metal and internal layer, passage growth inorganic matter; Remove polymer template, obtain double-decker metal-inorganic matter hollow ball, promptly contain an inorganic matter hollow ball in the metal hollow ball, in the double-decker hollow ball that obtains between two hollow ball the organic/inorganic substance post link to each other, the inorganic matter hollow ball can not be moved in the metal hollow ball, and two hollow ball are concentric; Or
The compound hollow ball of internal layer that step (1.1) is obtained and passage growth inorganic matter is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth organic matter and internal layer, passage growth inorganic matter; Remove polymer template, obtain double-decker organic matter-inorganic matter hollow ball, be to contain an inorganic matter hollow ball in the organic matter hollow ball, in the double-decker hollow ball that obtains between two hollow ball the organic/inorganic substance post link to each other, the inorganic matter hollow ball can not be moved in the organic matter hollow ball, and two hollow ball are concentric; Or
The internal layer that step (1.2) is obtained and the compound hollow ball of passage growing metal are dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth inorganic matter and internal layer, passage growing metal; Remove polymer template, obtain double-decker inorganic matter-metal hollow ball, promptly contain a metal hollow ball in the inorganic matter hollow ball, have metal column to link to each other in the double-decker hollow ball that obtains between two hollow ball, the metal hollow ball can not be moved in the inorganic matter ball, and two hollow ball are concentric; Or
The internal layer that step (1.2) is obtained and the compound hollow ball of passage growing metal are dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growing metal and internal layer, passage growing metal; Remove polymer template, obtain double-decker metal hollow ball, promptly contain a metal hollow ball in the metal hollow ball, have metal column to link to each other in the double-decker hollow ball that obtains between two hollow ball, interior metal hollow ball is moved in the hollow ball outside, and two hollow ball are concentric; Or
The internal layer that step (1.2) is obtained and the compound hollow ball of passage growing metal are dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the compound hollow ball at polymer hollow ball housing outer surface growth organic matter and internal layer, passage growing metal; Remove polymer template, obtain double-decker organic matter-metal hollow ball, promptly contain a metal hollow ball in the organic matter hollow ball, have metal column to link to each other in the double-decker hollow ball that obtains between two hollow ball, the metal hollow ball can not be moved in the organic matter hollow ball, and two hollow ball are concentric; Or
Internal layer that step (1.3) is obtained and the passage organic compound hollow ball of growing is dispersed in the alcoholic solution, add the inorganic matter precursor solution and the reaction component aqueous solution, concentration 0.01wt%～the 30wt% of inorganic matter precursor in the control reactant liquor, the ultimate density of the reaction component aqueous solution is 0.1wt%～50wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains in polymer hollow ball outer surface growth inorganic matter, internal layer and the passage organic compound hollow ball of growing; Remove polymer template, obtain double-decker inorganic matter-organic matter hollow ball, promptly contain an organic matter hollow ball in the inorganic matter hollow ball, have the organic matter post to link to each other in the double-decker hollow ball that obtains between two hollow ball, the organic matter hollow ball can not be moved in the inorganic matter ball, and two hollow ball are concentric; Or
The internal layer that step (1.3) is obtained and the compound hollow ball of organic matter of passage growth substance are dispersed in the water, add metal ion salt solution and reductant solution, metal ion salinity 0.01wt%～30wt% in the control reactant liquor, reductant concentration 0.01wt%～30wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains the organic compound hollow ball in polymer hollow ball housing outer surface growing metal and internal layer, passage growth; Remove polymer template, obtain double-decker metal-organic hollow ball, promptly contain an organic matter hollow ball in the metal hollow ball, have the organic matter post to link to each other in the double-decker hollow ball that obtains between two hollow ball, the organic matter hollow ball can not be moved in the metal hollow ball, and two hollow ball are concentric; Or
Internal layer that step (1.3) is obtained and the passage organic compound hollow ball of growing is dispersed in the water, in reaction vessel, feed inert gas, add polymer monomer and initiator solution, polymer monomer concentration 0.01wt%～20wt% in the control reactant liquor, initiator concentration 0.01wt%～20wt%, the concentration of template particles is 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, make product be deposited on polymer hollow ball housing outer surface, form continuous shell; Reaction finishes, and eccentric cleaning promptly obtains in polymer hollow ball housing outer surface and internal layer, the passage organic compound hollow ball of growing; Remove polymer template, obtain double-decker organic matter hollow ball, promptly contain an organic matter hollow ball in the organic matter hollow ball, have the organic matter post to link to each other in the double-decker hollow ball that obtains between two hollow ball, interior hollow ball is moved in the hollow ball outside, and two hollow ball are concentric.
The external diameter of described polymer hollow ball template particles is 0.02 μ m～10 μ m, and cavity volume is 10～95% of a whole microballoon;
The internal layer hydrophilic polymer of described polymer hollow ball template comprises polystyrolsulfon acid, polymethylacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide-based, polyvinyl pyrroles, poly-(2-vinylpyridine), poly-(4-vinylpridine), poly hydroxy ethyl acrylate, polyvinylesters, polyoxyethylene or polyvinyl ammonium chloride;
The outer lipophile polymer of described polymer hollow ball template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl tert-butyl acrylate, polymethylacrylic acid cinnamic acid ethyl ester, PMA, polyethyl acrylate, butyl polyacrylate, the polyacrylic acid tert-butyl ester, polyoxypropylene, poly dimethyl silane, polyvinyl butyl ester or polyisobutene;
The selective solvent that described usefulness removes polymer template is chloroform, toluene, oxolane or N, dinethylformamide;
At preparation SiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4, Si (OCH
2CH
2CH
2CH
3)
4Or Na
2SiO
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation TiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is TiCl
4, Ti (OCH
3)
4, Ti (OCH
2CH
3)
4, Ti{OCH (CH
3)
2}
4, Ti (OCH
2CH
2CH
2CH
3)
4Or TiOSO
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation SnO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is SnCl
4, Sn (OCH
3)
4, Sn (OCH
2CH
3)
4, Sn{OCH (CH
3)
2}
4Or Sn (OCH
2CH
2CH
2CH
3)
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation ZrO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is ZrCl
4, Zr (OCH
3)
4, Zr (OCH
2CH
3)
4, Zr{OCH (CH
3)
2}
4, Zr (OCH
2CH
2CH
2CH
3)
4Or Zr (SO
4)
2Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al
2O
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is AlCl
3, Al (OCH
3)
3, Al (OCH
2CH
3)
3, Al{OCH (CH
3)
2}
3, Al (OCH
2CH
2CH
2CH
3)
3Or Al
2(SO
4)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation V
2O
5When hollow ball or compound hollow ball, described inorganic matter precursor solution is VO (OCH
3)
3, VO (OCH
2CH
3)
3, VO{OCH (CH
3)
2}
3Or VO (OCH
2CH
2CH
2CH
3)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～1O0wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
When preparation ZnO hollow ball or compound hollow ball, described inorganic matter precursor solution is Zn (NO
3)
2, Zn (OOCCH
3)
2, ZnCl
2Or Zn (ClO
4)
2Alcoholic solution; The reaction component aqueous solution is the water or the alcoholic solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation WO
3When hollow ball or compound hollow ball, described inorganic precursor solution is (NH
4)
6H
2W
12O
41Or NaWO
3The aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation MoO
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is MoO
32H
2The O aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al (OH)
3Or Mg (OH)
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is the chloride of soluble aluminum, magnesium, the aqueous solution of sulfate; The reaction component aqueous solution is the aqueous solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation biomineralization material C aCO
3, Ca
10(PO
4)
6(OH)
2, CaSO
4, or BaSO
4When hollow ball or compound hollow ball, described inorganic matter precursor solution is Ca (OH)
2, CaCl
2, Ba (OH)
2Or BaCl
2The aqueous solution; The reaction component aqueous solution is for containing CO
3 2-, PO
4 3-, SO
4 2-Na
+Or K
+Salt, perhaps concentration O.01wt%～H of 30wt%
2CO
3, H
3PO
4Or H
2SO
4The aqueous solution;
When preparation semiconductor sulfuration thing hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble chloride of respective metal, nitrate or sulfate; The reaction component aqueous solution is the vulcanized sodium of concentration 0.01wt%～30wt% or the aqueous solution of thiocarbamide;
When preparation semiconductor selenide or tellurides hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble chloride of respective metal, nitrate, sulfate; The reaction component aqueous solution is the aqueous solution of concentration 0.01wt%～30wt% sodium selenide or tellurium sodium;
At preparation magnetic compound Fe
3O
4Or Fe
2O
3Or when containing the ferrite hollow ball of zinc, manganese, cobalt, nickel, copper, magnesium or compound hollow ball, described inorganic matter precursor solution is Fe
2+, Fe
3+, Zn
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+Or Mg
2+The aqueous solution of soluble chloride, nitrate or sulfate; The reaction component aqueous solution is the aqueous solution of concentration 0.01wt%～30wt% NaOH, potassium hydroxide or ammoniacal liquor, or the hydrazine hydrate solution of concentration 1wt%～60wt%;
When preparation metal A u, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow ball or compound hollow ball, described metal ion salt solution is the aqueous solution of respective metal ionically-soluble perchlorate, chloride, nitrate or sulfate; Reductant solution is NaBH
4, LiB (C
2H
5)
3H or N
2H
4The aqueous solution;
When preparation conducting polymer polyaniline, polypyrrole, polythiophene, p-phenylene vinylene and derivative hollow ball or compound hollow ball, water or alcoholic solution that described polymer monomer solution is corresponding monomer; Initiator solution is the aqueous solution of potassium peroxydisulfate, ammonium persulfate or ferric trichloride;
When preparation sensitiveness gel poly-N-isopropyl acrylamide, polyacrylic acid, polymethylacrylic acid hollow ball or compound hollow ball, described polymer monomer solution is monomer N-N-isopropylacrylamide, acrylic acid, methacrylic acid or its water or alcoholic solution; Initiator solution is the aqueous solution of potassium peroxydisulfate or ammonium persulfate;
Described inert gas is nitrogen or argon gas;
Described alcoholic solution is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols.
11. method according to claim 10 is characterized in that: the hollow ball of described inorganic matter or compound hollow ball comprise: TiO
2, SiO
2, SnO
2, ZrO
2, Al
2O
3, V
2O
5, ZnO, WO
3, MoO
3, Al (OH)
3Or Mg (OH)
2The hollow ball of biomineralization material or compound hollow ball comprise: CaCO
3, Ca
10(PO
4)
6(OH)
2, BaSO
4Or CaSO
4The hollow ball of semi-conducting material or compound hollow ball comprise: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; The hollow ball of magnetic compound or compound hollow ball comprise: Fe
3O
4, Fe
2O
3Or contain the ferrite of zinc, manganese, cobalt; The hollow ball of metal or compound hollow ball comprise: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe; Organic hollow ball or compound hollow ball comprise: polyaniline, polypyrrole, polythiophene or p-phenylene vinylene and derivative thereof, poly-N-isopropyl acrylamide, polyacrylic acid or polymethylacrylic acid.
12. one kind prepares the method for hollow ball and compound hollow ball with template, it is characterized in that preparation method's step of double-decker hollow ball:
Polymer-modified hollow ball is immersed in the inorganic matter precursor solution that concentration is 0.01wt%～60.0wt%, polymer-modified hollow ball keeps concentration in solution be 0.1wt%～40.0wt%, make the inorganic matter precursor solution infiltrate the cavity and the hydrophilic layer of polymer-modified hollow ball, reach the solution centrifugal flush away that not to infiltrate after the balance in the cavity, the polymer-modified hollow ball that contains the inorganic matter precursor solution that will obtain then under agitation joins in the reaction component aqueous solution, the concentration that contains the polymer-modified hollow ball of inorganic matter precursor solution in the control reactant liquor remains on 0.1wt%～40.0wt%, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning promptly obtains the MULTILAYER COMPOSITE hollow ball of polymer and inorganic matter; Remove template polymer with selective solvent, can make double-decker inorganic hollow ball; Or
The component aqueous solution be will react earlier and the cavity and the hydrophilic layer of polymer-modified hollow ball template particles infiltrated, to obtain containing the polymer-modified hollow ball of reacting the component aqueous solution then under agitation joins in the inorganic matter precursor solution that concentration is 0.01wt%～60.0wt%, the concentration that contains the polymer-modified hollow ball of the reaction component aqueous solution in the control reactant liquor remains on 0.1wt%～40.0wt%, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning obtains the MULTILAYER COMPOSITE hollow ball of polymer and inorganic matter; Remove template polymer with selective solvent, can make double-decker inorganic hollow ball; Or
Polymer-modified hollow ball is immersed in the metal ion salt solution of 0.01wt%～60.0wt%, polymer-modified hollow ball keeps concentration in solution be 0.1wt%～40.0wt%, make metal ion salt solution infiltrate the cavity and the hydrophilic layer of polymer-modified hollow ball, reach the solution centrifugal flush away that not to infiltrate after the balance; Polymer-modified hollow ball with the metal ion salting liquid that obtains under agitation joins in the reductant solution of 0.01wt%～60.0wt% then, the concentration of the polymer-modified hollow ball of metal ion salting liquid remains on 0.1wt%～40.0wt% in the control reactant liquor, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning promptly obtains the MULTILAYER COMPOSITE hollow ball of polymer and metal; Remove template polymer with selective solvent, can make the double-decker metal hollow ball; Or
Reductant solution with 0.01wt%～60.0wt% infiltrates in polymer-modified hollow ball particle cavity and the hydrophilic layer earlier, the polymer-modified hollow ball that contains reductant solution that will obtain then under agitation joins in the metal ion salt solution that concentration is 0.01wt%～60.0wt%, the concentration that contains the polymer-modified hollow ball of reductant solution in the control reactant liquor remains on 0.1wt%～40.0wt%, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning obtains the MULTILAYER COMPOSITE hollow ball of polymer and metal; Remove template polymer with selective solvent, can make the double-decker metal hollow ball; Or
Polymer-modified hollow ball is immersed in the polymer monomer solution that concentration is 0.01wt%～40.0wt%, polymer-modified hollow ball keeps concentration in these solution be 0.1wt%～40.0wt%, make polymer monomer solution infiltrate the cavity and the hydrophilic layer of polymer-modified hollow ball, reach the solution centrifugal flush away that will not infiltrate after the balance in the polymer-modified hollow ball cavity, the polymer-modified hollow ball that contains polymer monomer solution that will obtain then under agitation joins in 0.01wt%～30.0wt% initiator solution; In reaction vessel, feed inert gas, the concentration that contains the polymer-modified hollow ball of polymer monomer solution in the control reactant liquor remains on 0.1wt%～40.0wt%, 0 ℃～100 ℃ of reaction temperatures, and reaction finishes, eccentric cleaning promptly obtains polymer and organic MULTILAYER COMPOSITE hollow ball; Remove template polymer with selective solvent, can make the organic hollow ball of double-decker; Or
Earlier 0.01wt%～30.0wt% initiator solution is infiltrated the cavity and the hydrophilic layer of polymer-modified hollow ball, the polymer-modified hollow ball that contains initiator solution that will obtain then under agitation joins in the polymer monomer solution that concentration is 0.01wt%～40wt%, in reaction vessel, feed inert gas, the concentration that contains the polymer-modified hollow ball of initiator solution in the control reactant liquor remains on 0.1wt%～40wt%, 0 ℃～100 ℃ of reaction temperatures, reaction finishes, eccentric cleaning obtains polymer and organic MULTILAYER COMPOSITE hollow ball; Remove template polymer with selective solvent, can make the organic hollow ball of double-decker;
The external diameter of described polymer-modified hollow ball template particles is 0.02 μ m～10 μ m, and cavity volume is 10～95% of a whole microballoon, and inside and outside surface is a hydrophilic polymer;
The hydrophilic polymer of described polymer-modified hollow ball template comprises polystyrolsulfon acid, polymethylacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide-based, polyvinyl pyrroles, poly-(2-vinylpyridine), poly-(4-vinylpridine), poly hydroxy ethyl acrylate, polyvinylesters, polyoxyethylene or polyvinyl ammonium chloride;
The selective solvent that described usefulness removes polymer template is chloroform, toluene, oxolane, N, dinethylformamide etc.
At preparation SiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4, Si (OCH
2CH
2CH
2CH
3)
4Or Na
2SiO
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation TiO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is TiCl
4, Ti (OCH
3)
4, Ti (OCH
2CH
3)
4, Ti{OCH (CH
3)
2}
4, Ti (OCH
2CH
2CH
2CH
3)
4Or TiOSO
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation SnO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is SnCl
4, Sn (OCH
3)
4, Sn (OCH
2CH
3)
4, Sn{OCH (CH
3)
2}
4Or Sn (OCH
2CH
2CH
2CH
3)
4Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation ZrO
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is ZrCl
4, Zr (OCH
3)
4, Zr (OCH
2CH
3)
4, Zr{OCH (CH
3)
2}
4, Zr (OCH
2CH
2CH
2CH
3)
4Or Zr (SO
4)
2Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al
2O
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is AlCl
3, Al (OCH
3)
3, Al (OCH
2CH
3)
3, Al{OCH (CH
3)
2}
3, Al (OCH
2CH
2CH
2CH
3)
3Or Al
2(SO
4)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation V
2O
5When hollow ball or compound hollow ball, described inorganic matter precursor solution is VO (OCH
3)
3, VO (OCH
2CH
3)
3, VO{OCH (CH
3)
2}
3Or VO (OCH
2CH
2CH
2CH
3)
3Alcoholic solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
When preparation ZnO hollow ball or compound hollow ball, described inorganic matter precursor solution is Zn (NO
3)
2, Zn (OOCCH
3)
2, ZnCl
2Or Zn (ClO
4)
2Alcoholic solution; The reaction component aqueous solution is the water or the alcoholic solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation WO
3When hollow ball or compound hollow ball, described inorganic precursor solution is (NH
4)
6H
2Wt
2O
41Or NaWO
3The aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation MoO
3When hollow ball or compound hollow ball, described inorganic matter precursor solution is MoO
32H
2The O aqueous solution; The reaction component aqueous solution is the alcoholic solution of concentration 0.1wt%～100wt% water, and regulating its pH value with concentration 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia liquor is 1～13;
At preparation Al (OH)
3Or Mg (OH)
2When hollow ball or compound hollow ball, described inorganic matter precursor solution is the chloride of soluble aluminum, magnesium, the aqueous solution of sulfate; The reaction component aqueous solution is the aqueous solution of NaOH, potassium hydroxide or the ammoniacal liquor of concentration 0.01wt%～30wt%;
At preparation biomineralization material C aCO
3, Ca
10(PO
4)
6(OH)
2, CaSO
4, or BaSO
4When hollow ball or compound hollow ball, described inorganic matter precursor solution is Ca (OH)
2, CaCl
2, Ba (OH)
2Or BaCl
2The aqueous solution; The reaction component aqueous solution is for containing CO
3 2-, PO
4 3-, SO
4 2-Na
+Or K
+Salt, the perhaps H of concentration 0.01wt%～30wt%
2CO
3, H
3PO
4Or H
2SO
4The aqueous solution;
When preparation semiconductor sulfuration thing hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble chloride of respective metal, nitrate or sulfate; The reaction component aqueous solution is the vulcanized sodium of concentration 0.01wt%～30wt% or the aqueous solution of thiocarbamide;
When preparation semiconductor selenide or tellurides hollow ball or compound hollow ball, described inorganic matter precursor solution is the aqueous solution of the cationic soluble chloride of respective metal, nitrate, sulfate; The reaction component aqueous solution is the aqueous solution of concentration 0.01wt%～30wt% sodium selenide or tellurium sodium;
At preparation magnetic compound Fe
3O
4Or Fe
2O
3Or when containing the ferrite hollow ball of zinc, manganese, cobalt, nickel, copper, magnesium or compound hollow ball, described inorganic matter precursor solution is Fe
2+, Fe
3+, Zn
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+Or Mg
2+The aqueous solution of soluble chloride, nitrate or sulfate; The reaction component aqueous solution is the aqueous solution of concentration 0.01wt%～30wt% NaOH, potassium hydroxide or ammoniacal liquor, or the hydrazine hydrate solution of concentration 1wt%～60wt%;
When preparation metal A u, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow ball or compound hollow ball, described metal ion salt solution is the aqueous solution of respective metal ionically-soluble perchlorate, chloride, nitrate or sulfate; Reductant solution is NaBH
4, LiB (C
2H
5)
3H or N
2H
4The aqueous solution;
When preparation conducting polymer polyaniline, polypyrrole, polythiophene, p-phenylene vinylene and derivative hollow ball or compound hollow ball, water or alcoholic solution that described polymer monomer solution is corresponding monomer; Initiator solution is the aqueous solution of potassium peroxydisulfate, ammonium persulfate or ferric trichloride;
When preparation sensitiveness gel poly-N-isopropyl acrylamide, polyacrylic acid, polymethylacrylic acid hollow ball or compound hollow ball, described polymer monomer solution is monomer N-N-isopropylacrylamide, acrylic acid, methacrylic acid or its water or alcoholic solution; Initiator solution is the aqueous solution of potassium peroxydisulfate or ammonium persulfate;
Described inert gas is nitrogen or argon gas;
Described alcoholic solution is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or butanols.
13. method according to claim 12 is characterized in that: the hollow ball of described inorganic matter or compound hollow ball comprise: TiO
2, SiO
2, SnO
2, ZrO
2, Al
2O
3, V
2O
5, ZnO, WO
3, MoO
3, Al (OH)
3Or Mg (OH)
2The hollow ball of biomineralization material or compound hollow ball comprise: CaCO
3, Ca
10(PO
4)
6(OH)
2, BaSO
4Or CaSO
4The hollow ball of semi-conducting material or compound hollow ball comprise: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; The hollow ball of magnetic compound or compound hollow ball comprise: Fe
3O
4, Fe
2O
3Or contain the ferrite of zinc, manganese, cobalt; The hollow ball of metal or compound hollow ball comprise: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe; Organic hollow ball or compound hollow ball comprise: polyaniline, polypyrrole, polythiophene or p-phenylene vinylene and derivative thereof, poly-N-isopropyl acrylamide, polyacrylic acid or polymethylacrylic acid.
14. method for preparing hollow ball and compound hollow ball with template, it is characterized in that: polymer hollow ball template particles is dispersed in the reaction component aqueous solution, add monomer and crosslinking agent, or monomer and crosslinking agent and organic solvent, by monomer or organic solvent polymer hollow ball template housing is carried out swelling, and with monomer and initator introduction polymer hollow ball shell, carry out addition polymerization then, polycondensation or ring-opening polymerisation, in reaction vessel, feed inert gas, the concentration of template particles is 0.1wt%～20wt% in the control reactant liquor, reactant monomer concentration is 0.1wt%～20wt%, crosslinker concentration is 0.01wt%～10wt%, organic solvent concentration is 0wt%～20wt%, 20 ℃～250 ℃ of reaction temperatures; Reaction finishes, and eccentric cleaning makes polymer hollow ball and organic compound hollow ball;
The external diameter of described polymer hollow ball template particles is 0.02 μ m～10 μ m, and cavity volume is 10～95% of a whole microballoon;
The internal layer hydrophilic polymer of described polymer hollow ball template comprises polystyrolsulfon acid, polymethylacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide-based, polyvinyl pyrroles, poly-(2-vinylpyridine), poly-(4-vinylpridine), poly hydroxy ethyl acrylate, polyvinylesters, polyoxyethylene or polyvinyl ammonium chloride;
The outer lipophile polymer of described polymer hollow ball template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl tert-butyl acrylate, polymethylacrylic acid cinnamic acid ethyl ester, PMA, polyethyl acrylate, butyl polyacrylate, the polyacrylic acid tert-butyl ester, polyoxypropylene, poly dimethyl silane, polyvinyl butyl ester or polyisobutene;
The described organic solvent that is used for polymer hollow ball housing is carried out swelling is chloroform, benzene,toluene,xylene, oxolane, N, dinethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO), acetone or cyclohexane;
Described inert gas is nitrogen or argon gas;
The crosslinking agent of described preparation crosslinked polystyrene, polyacrylate hollow ball or compound hollow ball is azodiisobutyronitrile, ABVN, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, potassium peroxydisulfate or ammonium persulfate; Monomer is styrene, divinylbenzene, methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate;
The crosslinking agent of described preparation polyurethane hollow ball or compound hollow ball is PTMEG, polyester-diol or 1, the 4-butanediol; Monomer is hexamethylene diisocyanate or toluene di-isocyanate(TDI);
The crosslinking agent of described preparation phenolic resins hollow ball or compound hollow ball is phenol, orthoresol, paracresol, resorcinol or bisphenol-A; Monomer is formaldehyde, metaformaldehyde, acetaldehyde, para-acetaldehyde or furfural;
The crosslinking agent of described preparation unsaturated polyester (UP) hollow ball or compound hollow ball is ethylene glycol, propane diols, 1,3-butanediol, PTMEG or polyester-diol; Monomer is a maleic anhydride;
The crosslinking agent of described preparation epoxy resin hollow ball or compound hollow ball is hexamethylene diisocyanate, toluene di-isocyanate(TDI), phthalic anhydride, phthalic anhydride, maleic anhydride, ethylenediamine, hexamethylene diamine or trimethyl tetramine; Monomer is bisphenol-A epoxy or phenolic aldehyde epoxy;
The crosslinking agent of described preparation polyimides hollow ball or compound hollow ball is p-phenylenediamine (PPD) or hexamethylene diamine; Monomer is that span comes acid anhydrides or pyromellitic dianhydride;
The crosslinking agent of described preparation polyether-ketone or polyether sulfone hollow ball or compound hollow ball is 4,4-difluoro benzophenone or 4,4-dichloro diphenyl sulfone; Monomer is hydroquinones or tetramethyl biphenyl diphenol.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100097747A CN100464833C (en) | 2004-11-11 | 2004-11-11 | Template process of preparing hollow ball and composite hollow ball |
| PCT/CN2004/001382 WO2006050638A1 (en) | 2004-11-11 | 2004-11-30 | The method for preparation of hollow spheres and composite hollow spheres with template |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100097747A CN100464833C (en) | 2004-11-11 | 2004-11-11 | Template process of preparing hollow ball and composite hollow ball |
Related Child Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007103021921A Division CN101259403B (en) | 2004-11-11 | 2004-11-11 | Method for preparing hollow ball with polymer complex structure by swelling polymerization |
| CN2007103021902A Division CN101259401B (en) | 2004-11-11 | 2004-11-11 | Method for preparing hollow ball and hollow ball with complex structure by template method |
| CN2007103021917A Division CN101259402B (en) | 2004-11-11 | 2004-11-11 | Method for preparing hollow ball with double-layer structure and hollow ball with multi-layer complex structure by template method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1772363A true CN1772363A (en) | 2006-05-17 |
| CN100464833C CN100464833C (en) | 2009-03-04 |
Family
ID=36336193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100097747A Expired - Fee Related CN100464833C (en) | 2004-11-11 | 2004-11-11 | Template process of preparing hollow ball and composite hollow ball |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100464833C (en) |
| WO (1) | WO2006050638A1 (en) |
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| ATE228883T1 (en) * | 1998-03-19 | 2002-12-15 | Max Planck Gesellschaft | PRODUCTION OF MULTI-LAYER PAINTED PARTICLES AND HOLLOW SHELLS BY ELECTROSTATIC SELF-ORGANIZATION OF NANOCOMPOSITE MULTI-LAYERS ON DECOMPOSIBLE STENCILS |
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- 2004-11-11 CN CNB2004100097747A patent/CN100464833C/en not_active Expired - Fee Related
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