WO2006050638A1 - The method for preparation of hollow spheres and composite hollow spheres with template - Google Patents

Abstract

The present invention relates to hollow structured materials, particularly, relates to the preparation of inorganic, metal, organic hollow spheres and composite hollow spheres with polymer hollow spheres as template, and to the method for preparing hollow spheres having photic, electric, magnetic, catalytic characteristics and composite structure thereof. With polymer hollow spheres as template, as well as sol-gel method, sedimentation, redox process, the composite hollow spheres were prepared by forced interface method or surface settling process, after the template polymer were eliminated by high temperature sintering or solvent selectively extraction, the inorganic, metal, organic hollow spheres were obtained. By controlling the reactivity of reactants, charging manner, the concentration of reactants and recycle reactive method, the control of the structure and size of the hollow spheres could be realized, and at the same time, the composition of numeral materials could also be realized. The hollow spheres of the invention not only have good dispersibility, but also have excellent strength and size stability. The present invention also relates to the applications of those hollow structured materials.

Description

 Method for preparing hollow sphere and composite hollow sphere by template method

Technical field

 The invention belongs to the field of hollow structural materials, and particularly relates to a method for preparing inorganic materials, metal, organic hollow spheres and composite structural hollow spheres by using polymer hollow spheres as a template. Background technique

 The hollow structure sphere is a functional material with special structure. The hollow sphere has great application prospects in the fields of catalysis, drug delivery, artificial cells, lightweight fillers, insulating materials, low dielectric materials, photonic crystals and the like. The preparation of such materials by core-shell structured colloidal particles is a common method. A shell of another (or several) substances is coated or reacted on the surface of one particle to impart new properties to the particle. For example, the shell material can change the surface charge of the colloidal particles, the surface reaction characteristics, and enhance its stability and dispersibility. Further, charged, magnetic, catalytic, optically active, and electrically conductive substances may be introduced on the surface of the colloidal particles as needed to impart functionality to the particles.

At present, the method for preparing the core-shell structure mainly includes the following two aspects: (1) surface reaction; (2) surface deposition. American Matijevi0 et al. prepared a core-shell colloidal particle of polydivinylbenzene coated inorganic material by adding a dicobenzene and a free radical initiator to the surface of the inorganic particle (HT Oyama, R. Sprycha, A. Zelenev, E. Mati jevic, "Coating of Uniform Inorganic Particles with Polymers", J. Colloid Polym. Sci. 1993, 160, 298-303; R. Sprycha, HT Oyama, A. Zelenev, E Mati jevic, "Characterization of Polymer-coated Silica Particles by Microelectrophoresis", Colloid Polym. Sci. 1995, 273, 693-670). The Arms research team in the United Kingdom prepared colloidal particles of conductive polypyrrole and conductive polyaniline coated polystyrene (C. Barthet, SP Armes, SF Lascelles, SY Luk, HME Stanley, "Synthesis and Characterization of Micrometer-Sized Polyani line- Coated Polystyrene Latexs " , Langmuir 1998, 14, 2032-2041). When the content of polypyrrole or polyaniline is about 8 wt%, the conductivity equivalent to that of the bulk can be achieved. Layer adsorption of polyelectrolytes is a very effective method for preparing core-shell structure colloidal particles. The polyelectrolyte-coated colloidal particles can be prepared by adsorbing the oppositely charged polyelectrolyte layer to the surface of the colloidal particles and repeating it a plurality of times. Germany Caruso et al. used monomeric polystyrene colloidal particles as a template to prepare colloidal particles coated with polyvinyl ammonium chloride and polystyrene b: sodium sulfonate by layer-by-layer electrostatic self-assembly. 5 nm。 The average diameter of the colloidal particles increased by about 1. 5 nm. They also assembled charged silica particles, titanium dioxide, triiron tetroxide, and metallic silver and gold nanoparticles onto the surface of polystyrene colloidal particles by electrostatic adsorption to prepare colloidal particles with core-shell structure (F. Caruso). , "Hollow Capsules Processing through Colloidal Tempi at ing and Self-Assembly", Chera. Eur. J. 2000, 6, 413-419; F. Caruso, M. Spasova, A. Susha, M. Giersig, RA Caruso, " Magnetic Nanocomposite Particles Hollow Titania Spheres From Layered Precursor Deposition on Sacrificial Colloidal Core Particles " , Adv. Mater. 2001, 13, 740-744). Advantages of layer self-assembly: The thickness of the polymer layer can be finely adjusted according to the number of adsorbed layers; colloidal particles of different sizes and shapes can be used as templates for polymerization The layer assembly of the electrolyte. The disadvantages are: the residual polyelectrolyte in the system must be removed by repeated centrifugation; the polymer layer of a certain thickness must undergo multiple self-assembly; the uncharged polymer cannot be assembled. Yang Zhenzhong et al. used partially sulfonated monodisperse polystyrene beads as templates to obtain core-shell microspheres by sol-gel, surface polymerization, and denuclearization to obtain inorganic, organic or composite hollow microspheres. The advantage of this method is to control sulfonation. The thickness of the layer can simultaneously adjust the size of the cavity and the thickness of the shell, and the sulfonated layer provides a hydrophilic layer. And positive charge, which facilitates the adsorption and reaction of inorganic precursors, charged monomers and polymers in the sulfonated layer, which facilitates the formation of a continuous smooth shell and improves the utilization of precursors (ZZ Yang, ZW Niu, YF Lu, ZB Hu , CC Han, "Templated sysnthesis of inorganic hollow spheres with a tunable cavity size onto core-shell gel particles", Angew. Chem. Int. Ed. Engl. 2003, 42, 1943-194; ZW Niu, ZZ Yang, ZB Hu , YF Lu, CC Han, "Polyani line-silica composite conductive capsules and hollow spheres", Adv. Funct. Mater. 2003, 13, 949-954).

 At present, the hollow spheres prepared by the template method are obtained by using colloidal particles as a template, and the core-shell composite particles are obtained by surface deposition reaction or layer-by-layer alternating adsorption, and hollow spheres are obtained after enucleation. Summary of the invention

 One of the objects of the present invention is to provide a method for preparing hollow spheres of inorganic, metal and/or organic composite structures using polymeric hollow spheres as a template.

 A further object of the present invention is to provide a method for preparing hollow spheres of inorganic, metal and/or organic composite structures by a composite process.

 Still another object of the present invention is to provide the use of hollow spheres and composite structural hollow spheres.

 The invention utilizes a polymer hollow sphere as a template, uses a shell as a forced interface, a cavity as a raw material warehouse of a reaction component, and another reaction component is placed outside the sphere, and a hollow sphere or a composite structure thereof is prepared by the reaction.

 The invention prepares a series of hollow structure colloidal particles by using a polymer hollow sphere as a template. Various forms of composite hollow spheres were prepared by sol-gel, sedimentation reaction, redox chemistry or polymerization. The reaction rate is controlled by selecting the reactants, and the morphology of the composite hollow sphere can be controlled by adjusting the feeding mode, the concentration of the reactants, and the reaction conditions. High temperature sintering or solvent selective extraction removes the template polymer to obtain inorganic, metal or organic hollow spheres.

The invention uses a polymer hollow sphere as a template to prepare hollow spheres or composites of inorganic substances, metals and organic substances. Hollow ball. Inorganic hollow sphere or hollow sphere composite comprising: a metal oxide or hydroxide composite hollow spheres or hollow spheres, such as _{Ti0 2, Si0 2, Sn0 2} , Zr0 2, A1 2 0 3, V 2 0 5, Zn0 , W0 ₃ , Mo0 ₃ , Al (0H) ₃ or M _g (0H) ₂ ; hollow spheres or composite hollow spheres of biomineralized materials, such as CaC0 ₃ , Ca _l0 (P0 ₄ ) _e (0H) ₂ , BaS0 ₄ Or CaS0 _4; hollow spheres or composite hollow spheres of semiconductor materials, such as CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; hollow spheres or composite hollow spheres of magnetic compounds, such as Fe ₃ 0 ₄ , Fe ₂ 0 ₃ or ferrite containing zinc, manganese and cobalt. A hollow sphere of a metal or a composite hollow sphere, such as a hollow sphere of a Au, Ag, yttrium, Pd, Pb, Ni, Co, Cu or Fe or a composite hollow sphere. Hollow spheres or composite hollow spheres of organic matter include: hollow spheres or composite hollow spheres of conductive polymers, such as polyaniline, polypyrrole, polythiophene or polyparaphenylene acetylene and derivatives thereof; hollow spheres or composite hollows of sensitive gels A ball such as poly-N-isopropylacrylamide, polyacrylic acid or polymethacrylic acid. Swelling polymerization can be used to prepare high performance polymer hollow spheres or composite hollow spheres, such as crosslinked polystyrene, polyurethane, polyacrylate, phenolic resin, unsaturated polyester, epoxy resin, polyimide, polyether Ketone or polyether sulfones.

 The method for preparing a hollow sphere and a composite hollow sphere by using a template adopts a commercially available or self-made polymer hollow sphere as a template (diameter is 0.02 ΐ·4ι!~10μω, and the cavity volume is 10 to 95% of the entire microsphere). The polymer hollow spherical shell is composed of two layers of inner and outer materials, the inner layer is a hydrophilic polymer, the outer layer is a lipophilic polymer skeleton, and a hydrophilic channel connects the cavity and the outer environment of the particle. By controlling the feeding mode and the reaction speed, it is possible to control the growth of the material on the outer surface, the inner layer and/or the hydrophilic channel of the hollow shell of the polymer, thereby producing a variety of hollow structural materials. 1. Steps for preparing the growth material in the inner layer of the polymer hollow sphere template shell:

 (1). Using the polymer hollow sphere as a template, the reactant is divided into two reaction components, and there is no reaction between the raw materials in each component. The polymer hollow sphere shell is used as a forced interface, and the cavity is used as a reaction group. In the raw material warehouse, another reaction component is placed outside the ball, and a composite hollow sphere of the polymer hollow sphere inner layer growth material can be prepared by the reaction.

 Lwt%〜40. Owt 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 %, the inorganic precursor solution is infiltrated into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution not infiltrated into the hollow cavity template cavity is centrifuged and washed away. The resulting polymer hollow sphere containing the inorganic precursor solution is then added to the aqueous solution of the reaction component with stirring. The concentration of the template particles in the reaction solution is maintained at 0. lwt% ~ 40. Owt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction time is 0. 5 ~ 24 hours or so, the reaction is completed, centrifugal cleaning, the polymer is obtained A composite hollow sphere in which an inorganic substance is grown in the inner layer of the hollow spherical shell. Or

0重量的质量物。 The chemical solution containing the aqueous solution of the reaction vessel is infiltrated into the polymer hollow sphere template particle cavity, and then the obtained polymer hollow sphere containing the reaction component aqueous solution is added to a concentration of 10. 0wt%~60. In the precursor solution, the concentration of the template particles in the reaction solution is maintained at 0. lwt%~40. 0wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction time is 0. 5 ~ 24 hours, the reaction is completed, centrifugal cleaning A composite hollow sphere in which an inorganic substance is grown in the inner layer of the polymer hollow spherical shell is also obtained. By controlling the concentration of the reactant, the inner layer product of the prepared inorganic composite hollow sphere can be from a single dispersed nanoparticle to a nanoparticle network until Forming a dense shell of different thicknesses. or Lwt%~40. Owt%, so that the polymer spheroidal slabs are immersed in a 0. lwt%~40. The metal ion salt solution penetrates into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution which has not penetrated into the cavity of the polymer hollow sphere template is centrifuged and washed away. 0重量%的还原剂溶液。 The polymer hollow ball containing the metal ion salt solution was then added to 0. 01wt% ~ 60. 0wt% of the reducing agent solution. Lwt°/. 0wt°/. The concentration of the template particles in the reaction solution is maintained at 0. lwt%~40. 0wt ° /. , reaction temperature (TC ~ 10 (TC, reaction time 0. 5 ~ 24 hours or so, the reaction is completed, centrifugal cleaning, that is, the composite hollow sphere of the metal inner layer of the polymer hollow spherical shell is obtained. or

 0wt 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 %~60. Owt% of metal ion salt solution. The concentration of the template particles in the reaction solution is maintained at 0. lwt%~40. 0wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction time is 0. 5~24 hours, the reaction is completed, centrifugal cleaning, the same polymer is obtained. A composite hollow sphere of metal is grown in the inner layer of the hollow spherical shell. By controlling the reaction conditions, the resulting inner layer product of the metal composite hollow sphere can be from a single dispersed nanoparticle to a nanoparticle network until a dense shell of different thickness is formed. Or

 01wt°/。 The polymer hollow sphere template particles were soaked at a concentration of 0. 01wt ° /. 〜0. 0wt% of the polymer monomer solution, the template particles in the solution to maintain a concentration of 0. lwt% ~ 40. 0wt ° /», the polymer monomer solution penetrates into the cavity of the polymer hollow sphere template, After the equilibrium is reached, the solution that has not penetrated into the cavity of the hollow polymer template is centrifuged and washed away. The polymer hollow cell containing the polymer monomer solution is then added to 0. 01wt%~30. 0% of the initiator solution in a stirred solution. The reaction time is 0. 5~24 hours or so, the reaction time is 0. 5~24 hours or so, the reaction time is 0. 5~24 hours, the reaction time is 0. After completion, centrifugal cleaning, that is, a composite hollow sphere in which organic matter is grown in the inner layer of the polymer hollow spherical shell. Or

 0. 01wt%~30. (kt% initiator solution is infiltrated into the hollow cavity template particle cavity of the polymer, and then the obtained polymer hollow sphere containing the initiator solution is added to the concentration of 5^%~40 under stirring. Lw«〜40wt%, reaction temperature 0°C~100°C, reaction time 0, the inert gas is introduced into the reaction vessel, and the concentration of the template particles in the reaction solution is controlled to be maintained at 0. lw «~40wt%, reaction temperature 0 ° C ~ 100 ° C, reaction time 0 5~24 hours, the reaction is completed, centrifugal cleaning, and the composite hollow sphere of the organic matter in the inner layer of the polymer hollow sphere is also obtained. By controlling the reaction conditions, the inner layer product of the prepared organic composite hollow sphere can be individually dispersed. Nanoparticles to the nanoparticle network until a dense shell of different thickness is formed.

 1〜10°。 The singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the present invention. The temperature of C/min is increased to 300~700 ° C (preferably 450 ° C) and the ignition is about 0.2 to 3 hours, respectively, to obtain inorganic or metal hollow spheres;

 Alternatively, the polymer template obtained by the step (1.1), the step (1.2), the step (1.3), and the hollow sphere compounded with the inorganic substance, the metal or the organic substance are respectively extracted by using a selective solvent to remove the template polymerization. Objects, respectively, get inorganic, metal or organic hollow spheres.

(3). Step (1. 1), step (1.2), and step (1. 3) may be repeated a plurality of times before proceeding to step (2). Take Step (1.1), step (1.2), and step (1.3) respectively, the composite hollow spheres are used as templates, and steps (1.1), steps (1.2), and steps (1. 3), performing a cyclic reaction, when two or more cycles of the reaction to form the same substance, the shell thickness of the composite hollow sphere can be increased, that is, the thickness of the hollow spherical shell can be controlled by controlling the concentration of the reactants and the number of cycles of the reaction; or

 The composite hollow sphere obtained in the step (1.2) or the step (1.3) is used as a template particle of the step (1.1) to carry out a cyclic reaction; or

 The composite hollow sphere obtained in the step (1.1) or the step (1.3) is used as a template particle of the step (1.2) to carry out a cyclic reaction; or

 The composite hollow sphere obtained in the step (1.1) or the step (1.2) is used as a template particle of the step (1.3) to carry out a cyclic reaction.

 When two or more cycles are reacted to form different kinds of substances, composite hollow spheres of various materials can be obtained. For example, the polymer template first forms titanium dioxide in the inner layer of the shell, and then forms silica in the inner layer of the shell to obtain a polymer. a composite hollow sphere of template and titanium dioxide and silicon dioxide; or a polymer template first generates ferroferric oxide in the inner layer of the shell, and then forms polyaniline in the inner layer of the shell to obtain a composite of the polymer template and triiron tetroxide and polyaniline. Hollow ball. 2. Preparation steps for the inner layer of the polymer hollow sphere template shell and the hydrophilic channel growth material:

 (1). Using the reactivity or catalytic performance of the hydrophilic channel of the polymer hollow sphere template and the inner layer of the shell, selecting the appropriate reactants and feeding sequence, the composite hollow sphere with the surface of the burr-like substance can be obtained, and the polymer hollow sphere template The inner layer of the shell creates a continuous material whose hydrophilic channels are reshaped, expanded, and even extended out of the sphere.

 Lwt%〜40. Owt%, the aqueous solution of the reaction component is infiltrated into the cavity of the hollow polymer template of the polymer to reach a concentration of the polymer hollow sphere template particles in the solution After the equilibration, the solution that has not penetrated into the cavity of the hollow polymer template is centrifuged and washed away. The weight of the aqueous solution of the inorganic precursor is maintained at 0. 01wt ° / by the continuous replenishment. The reaction time is 0. 5~24 hours, the reaction time is 0. 5~24 hours or so, the reaction time is 0. lwt%~40. 0wt%, reaction temperature 0O~100 ° C, reaction time 0. 5~24 hours or so, reaction After completion, centrifugal cleaning is performed to obtain a hollow sphere in which a polymer template having a ruthenium-like substance is combined with an inorganic substance, and the hydrophilic channel is multiplexed, expanded, and even protruded from the sphere, and the inner layer of the shell generates a continuous material;

Lwt%~40. 0wt%, the reducing agent solution is infiltrated into the polymer. The weight of the template is kept in the solution. The cavity of the hollow sphere template is centrifuged to remove the solution that has not penetrated into the cavity of the polymer hollow sphere template. 01wt°/。 The polymer ionic salt was added to the metal ion salt solution with agitation. 5〜24小时左右左右。 The reaction time is 0. lwt%~40. 0wt%, reaction temperature 0 ° C ~ 100 ° C, reaction time 0. 5~24 hours or so , the reaction is completed, and the centrifugal cleaning is performed to obtain the surface band. The polymer template of the ranunculus-like material and the hollow sphere of the metal composite, the hydrophilic channel of which is shaped, expanded or even protruded from the sphere, and the inner layer of the shell generates a continuous material; or

 01wt%~30. 0wt°/。 The polymer hollow sphere template particles were immersed in the reaction composition concentration of 0. 01wt%~30. 0wt ° /. In the initiator solution, the template particles are kept at a concentration of 0. lwt%~40. (kt%, the initiator solution is infiltrated into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the polymer hollow sphere template is not infiltrated. The weight of the polymer monomer is maintained at 0. 01wt%~10. The concentration of the template particles in the reaction solution is maintained at 0. lwt%~40. (kt%, reaction temperature 0°C~100°C, reaction time) 0. 5~24 hours, after the reaction is completed, centrifugal cleaning, the hollow template of the polymer template with the burr-like substance on the surface and the organic material is obtained, and the hydrophilic channel is duplicated, expanded or even protruded from the sphere, and the inner layer of the shell is formed. Continuous material.

 (3⁄4. The polymer template obtained in the step (1) and the inorganic material, metal composite hollow spheres are placed in a sintering furnace, and air is passed, and the temperature is raised to a temperature of 0.1 to 10 ° C / minute to 300 ~ 700 ° C (preferably 450 Ό) burning 0. 2~3 hours, obtaining an inorganic or metallic hollow sphere with a burr surface; or

 The hollow template obtained by mixing the polymer template obtained in the step (1) with an inorganic material, a metal or an organic substance is extracted with a selective solvent to remove the template polymer to obtain a surface-burred inorganic material, metal or organic hollow sphere. The hollow sphere of the burr-type hollow sphere is formed by growing a material in the inner layer of the casing, and the burr is formed by the growth and expansion of the material in the hydrophilic passage. 3. Preparation method of growing material on the outer surface of the polymer hollow sphere template shell:

 The polymer hollow sphere is used as a template, which is dispersed in a solution, and two reaction components of the inorganic substance, the metal or the organic substance are added to the solution to control a certain concentration, and the reaction product can be deposited and grown on the outer surface of the hollow shell of the polymer. And no reaction product particles are formed in the solution.

 01重量%〜30重量%的反应的水溶液的水溶液Lwt°/。 The final concentration is 0. lwt%~50wt%, the concentration of the template particles is 0. lwt ° /. 〜40wt%, reaction temperature 0 ° C ~ 100 ° C, reaction time 0. 5~ 24 hours, the reaction product is deposited on the outer surface of the polymer hollow spherical shell to form a continuous shell. After the reaction is completed, the mixture is centrifuged to obtain a composite hollow sphere which grows inorganic substances on the outer surface of the hollow shell of the polymer; the polymer template is removed to obtain an inorganic hollow sphere; or

 The weight of the metal ion salt is 0.11% by weight to 30% by weight, and the reducing agent concentration is 0.11% by weight to 30% by weight. The concentration of the template particles is 0. lwt% ~ 40wt%, the reaction temperature is 0 ° C ~: L00 ° C, the reaction time is 0. 5~24 hours, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell Floor. After the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere which grows metal on the outer surface of the hollow shell of the polymer; the polymer template is removed to obtain a hollow metal sphere; or

Dispersing the polymer hollow sphere template particles in water, introducing an inert gas into the reaction vessel, and adding the polymer monomer Lwt%〜40wt%, The reaction temperature is 0°. The concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0°, and the concentration of the initiator is 0. 01wt%~20wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0°. C~100 ° C, reaction time 0. 5~24 hours, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell; after the reaction is completed, centrifugal cleaning, the outer surface of the hollow shell of the polymer is obtained. The hollow sphere of the polymer and the organic compound; the template polymer is removed to obtain an organic hollow sphere. The preparation method of the double-layer hollow sphere with eccentric structure steps:

 (1). Using the polymer hollow sphere as a template, the reactant is divided into two reaction components, and there is no reaction between the raw materials in each component. The polymer hollow sphere shell is used as a forced interface, and the cavity is used as a reaction group. In the raw material warehouse, another reaction component is placed outside the ball, and a composite hollow sphere of the inner growth material of the polymer hollow spherical shell is prepared by the reaction.

 Lwt°〜40. 0rt° 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 /. The inorganic precursor solution is infiltrated into the cavity of the hollow polymer template of the polymer, and after reaching equilibrium, the solution which has not penetrated into the cavity of the hollow polymer template is centrifuged and washed away. The resulting polymer hollow sphere containing the inorganic precursor solution is then added to the aqueous solution of the reaction component with stirring. The concentration of the template particles in the reaction solution is maintained at 0. lwt% ~ 40. 0wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction time is 0. 5 ~ 24 hours or so, the reaction is completed, centrifugal cleaning, the polymer is obtained A composite hollow sphere in which an inorganic substance is grown in the inner layer of the hollow spherical shell. Or

 The inorganic material of the present invention is added to the inorganic material having a concentration of 10. 0 wt% to 60. 03⁄4^%. In the precursor solution. The concentration of the template particles in the reaction solution is maintained at 0. rt%~40. 0wt%, reaction temperature 0 ° C; ~ 100 ° C, reaction time 0. 5~ 24 hours, the reaction is completed, centrifugal cleaning, the same polymerization A composite hollow sphere in which an inorganic substance is grown in the inner layer of the hollow spherical shell. Or

Lwt ^e /. The template particles are kept at a concentration of 0. lwt ^e /, in the solution of the metal ion salt solution. 〜40. 0wt%, the metal ion salt solution is infiltrated into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution not penetrating into the cavity of the polymer hollow sphere template is centrifuged and washed away. 0重量%的还原剂溶液。 The polymer hollow sphere containing the metal ion salt solution was then added to 0. 01wt% ~ 60. 0 ^% of the reducing agent solution. The concentration of the template particles in the reaction solution is maintained at 0. lwt% ~ 40. 0wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction time is 0. 5 ~ 24 hours, the reaction is completed, centrifuged, clear, that is A composite hollow sphere of metal is grown in the inner layer of the polymer hollow spherical shell. or

0wt。 The weight of the polymer hollow ball containing the reducing agent solution was added to a concentration of 10. 0wt 5〜24。 The reaction time 0. lwt%~40. 0wt%, reaction temperature 0 ° C ~ 100 ° C, reaction time 0. 5~24 After about an hour, the reaction is completed, and the mixture is centrifuged to obtain a composite hollow sphere in which the inner layer of the polymer hollow spherical shell grows metal. Lwt%~40. (1wt%~40. ( Kt%, the polymer monomer solution is infiltrated into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution not penetrating into the cavity of the polymer hollow sphere template is centrifugally washed away. Then the obtained polymer-containing monomer solution is obtained. 1wt%〜 40. The concentration of the template particles in the reaction solution is maintained at 0. 1wt%~ 40. 0wt%, reaction temperature 0 ° C ~ 100 ° C, reaction time 0. 5 ~ 24 hours or so, the reaction is completed, centrifugal cleaning, that is, a composite hollow sphere of organic matter grown in the inner layer of the polymer hollow spherical shell.

 01重量%~30. 0wt% initiator solution is infiltrated into the hollow cavity template particle cavity of the polymer, and then the obtained polymer hollow sphere containing the initiator solution is added to the concentration of 5^%~4 under stirring. Lwt%~40wt%, reaction temperature 0°C~100°C, reaction time 0. 1⁄21% of the polymer monomer solution. The inert gas is introduced into the reaction vessel, and the concentration of the template particles in the reaction solution is kept at 0. lwt%~40wt%, the reaction temperature is 0°C~100°C, and the reaction time is 0. 5~24 hours, the reaction is completed, and the mixture is centrifuged to obtain a composite hollow sphere in which the organic layer of the polymer hollow sphere is grown.

 (2) Dispersing the composite hollow sphere of the inner layer growth material obtained in the step (1) in a solution, simultaneously adding two reaction components of an inorganic substance, a metal or an organic substance, controlling the concentration of the reactant, and depositing the reaction product in the hollow of the polymer The outer surface of the spherical shell can obtain a multi-layer composite hollow sphere which grows materials on both the outer surface and the inner layer of the polymer hollow spherical shell, and removes the polymer template to obtain a double-layer hollow sphere, that is, the hollow sphere contains a hollow sphere therein. The hollow sphere can move within the outer hollow sphere.

 01wt% The final concentration of the inorganic precursor in the reaction liquid is 0. 01wt%, the final concentration of the inorganic precursor in the reaction liquid is 0. 01wt% Lwt°/。 The final concentration of the aqueous solution of the reaction component is 0. lwt ° /. 〜50wt%, the concentration of the template particles is 0. lwt% ~ 40wt%, the reaction temperature is 0 ° C ~ 100 V, the reaction time is 0. 5~24 hours, the reaction product is deposited on the outer surface of the polymer hollow spherical shell, forming a continuous Shell layer. After the completion of the reaction and centrifugation, a composite hollow sphere in which inorganic substances are grown on the outer surface and the inner layer of the hollow shell of the polymer is obtained. The polymer template is removed to obtain a two-layer inorganic hollow sphere, that is, the hollow sphere contains a hollow sphere, and the hollow sphere obtained in the two-layer structure can move in the outer hollow sphere; or

 01wt%〜30vrt%, reducing agent, the concentration of the metal ion salt in the reaction solution is 0. 01wt%~30vrt%, reducing agent, the metal ion salt salt concentration in the reaction liquid is 0. 01wt%~30vrt%, reducing agent Lwt%〜40wt°/。 The concentration of the template particles is 0. lwt% ~ 40wt ° /. The reaction temperature is 0 ° C to 100 ° C, and the reaction time is 0.5 to 24 hours, and the reaction product is deposited on the outer surface of the hollow hollow spherical shell to form a continuous shell layer. After the completion of the reaction, the mixture is centrifuged to obtain a composite hollow sphere in which metal and inner layer growth inorganic substances are grown on the outer surface of the polymer hollow spherical shell. The polymer template is removed to obtain a double-layered metal-inorganic hollow sphere, that is, the hollow metal sphere contains an inorganic hollow sphere, and the obtained inorganic hollow sphere can move in the hollow metal sphere; or

Dissolving the inner hollow inorganic composite hollow sphere obtained in the step (1.1) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the concentration of the polymer monomer in the reaction liquid. 01重量%〜20wt%, The initiator concentration is 0. 01wt%~20wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0'C~100°C, The reaction time was 0.5 to 24 hours, and the reaction product was deposited on the outer surface of the hollow shell of the polymer to form a continuous shell layer. After the completion of the reaction, the mixture is centrifuged to obtain a composite hollow sphere in which an organic substance and an inner layer of inorganic substances are grown on the outer surface of the hollow shell of the polymer. Removing the polymer template to obtain a two-layer structure organic-inorganic hollow sphere, that is, the organic hollow sphere contains an inorganic hollow sphere, and the obtained inorganic hollow sphere can move in the organic hollow sphere; or

 01wt%~ The concentration of the inorganic precursor in the reaction solution is 0. 01wt%~ 5〜24小时。 The reaction time is 0. 5~24 hours, the reaction time is 0. 5~24 hours, the reaction time is 0. 5~24 hours, the reaction time is 0. 5~24 hours The reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell. After the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere in which an inorganic substance and an inner layer growing metal are grown on the outer surface of the polymer hollow spherical shell. The polymer template is removed to obtain a two-layer inorganic-metal hollow sphere, that is, the inorganic hollow sphere contains a hollow metal sphere, and the obtained hollow metal sphere can move in the inorganic sphere; or

 Rt%〜30wt%, reducing agent, the metal ion salt concentration in the reaction liquid is controlled to 0. 0 rt%~30wt%, reducing agent, the metal hollow salt solution and the reducing agent solution are added to the reaction liquid. The concentration of the template is 0. 01wt%~30wt%, the concentration of the template particles is 0. lwt% ~ 40wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction time is 0. 5~24 hours, the reaction product is deposited in the polymer hollow sphere The outer surface of the casing forms a continuous shell. After the completion of the reaction, centrifugal washing is carried out to obtain a composite hollow sphere in which metal is grown on the outer surface and the inner layer of the hollow shell of the polymer. Removing the polymer template to obtain a two-layer structure metal hollow sphere, that is, the metal hollow sphere contains a metal hollow sphere, and the obtained inner metal hollow sphere can move in the outer metal sphere; or

 Dissolving the inner hollow metal composite hollow sphere obtained in the step (1.2) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the concentration of the polymer monomer in the reaction liquid. 01wt%~20wt°/. The concentration of the initiator is 0. 01wt%~20wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction time is 0. 5~24 hours, the reaction product is deposited in the polymerization The outer surface of the hollow spherical shell forms a continuous shell. After the reaction is completed, the mixture is centrifuged to obtain a composite hollow sphere in which an organic substance and an inner layer of metal are grown on the outer surface of the hollow shell of the polymer. Removing the polymer template to obtain a two-layer structure organic-metal hollow sphere, that is, the organic hollow sphere contains a metal hollow sphere, and the obtained metal hollow sphere can move in the organic hollow sphere; or

 01wt%~ The concentration of the inorganic precursor in the reaction solution is 0. 01wt%~ 5〜24小时,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The reaction product is deposited on the outer surface of the polymeric hollow sphere shell to form a continuous shell. After completion of the reaction, centrifugal washing is carried out to obtain a composite hollow sphere in which an inorganic substance and an inner layer-grown organic substance are grown on the outer surface of the polymer hollow spherical shell. The polymer template is removed to obtain a two-layer structure inorganic-organic hollow sphere, that is, the inorganic hollow sphere contains an organic hollow sphere, and the obtained organic hollow sphere can move in the inorganic sphere; or

Dispersing the composite hollow sphere of the inner layer growing organic body obtained in the step (1.3) in water, adding the metal ion salt solution And the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0°C, and the concentration of the template is 0. 01wt%~ 30wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0°C. 〜10 (TC, reaction time 0. 5~24 hours, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell. After the reaction is completed, centrifugal cleaning is performed to obtain metal on the outer surface of the hollow shell of the polymer. And a composite hollow sphere with an inner layer of organic matter. The polymer template is removed to obtain a double-layered metal-organic hollow sphere, that is, the hollow sphere of the metal contains an organic hollow sphere, and the obtained hollow hollow sphere can move in the hollow sphere of the metal;

 Dissolving the composite hollow sphere of the inner layer growing organic body obtained in the step (1.3) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the concentration of the polymer monomer in the reaction liquid. 01重量%〜20wt°/。 01wt%〜20wt%, initiator concentration 0. 01wt%~20wt ° /. , the concentration of the template particles is 0. lwt% ~ 40wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction time is 0. 5~24 hours, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell . After the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere in which organic matter is grown on the outer surface and the inner layer of the polymer hollow spherical shell. The polymer template is removed to obtain a two-layer organic hollow sphere, that is, the organic hollow sphere contains an organic hollow sphere, and the obtained inner organic hollow sphere can move in the outer organic sphere. V. Preparation method of two-layer hollow spheres with concentric structure Steps:

 (1). Using the reactivity or catalytic performance of the hydrophilic channel of the polymer hollow sphere and the inner layer of the shell, selecting the appropriate reactants and feeding sequence, a composite hollow sphere with a burr-like substance on the surface can be obtained, and the polymer hollow sphere shell is The layer creates a continuous material whose hydrophilic channels are replicated, expanded, and even extended out of the sphere.

 (1) The aqueous solution of the reaction solution is immersed in the aqueous solution of the reaction solution. The template particles are kept at a concentration of 0. lwt%~40. 0wt%, the aqueous solution of the reaction component is infiltrated into the polymer hollow sphere template. The cavity is centrifuged and the solution that has not penetrated into the cavity of the hollow balloon template is centrifuged. 01重量%~10. (1⁄21%的一一 constant) The polymer hollow spheres containing the aqueous solution of the reaction component are added to the alcohol solution of the inorganic precursors, and the inorganic precursor is maintained at 0. 01wt%~10. The concentration of the template is maintained at 0. lwt%~40. 0wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction time is 0. 5~24 hours, the reaction is completed, centrifugal cleaning, the surface is obtained. a hollow sphere of a polymer template with a burr-like substance and an inorganic material, the hydrophilic channel of which is shaped, expanded, or even protruded from the sphere, and the inner layer of the shell generates a continuous material;

Lwt%~40. 0wt%, to restore the polymer hollow sphere template particles immersed in a 0. 01wt%~60. 0% reducing agent solution, the template particles in the solution to maintain a concentration of 0. lwt%~40. 0wt%, to restore The solution penetrates into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution that has not penetrated into the cavity of the hollow polymer template is centrifuged and washed away. 01重量%〜10. (1⁄2 % of a constant concentration; control of the reaction solution, the polymer hollow ball containing the reducing agent solution is added to the metal ion salt solution under stirring, the metal ion salt is continuously replenished at 0. 01wt%~10. The concentration of the template particles is maintained at 0. lwt%~40. 0wt%, the reaction temperature is 0°C~100°C, the reaction time is 0. 5~24 hours, the reaction is completed, and the centrifugal cleaning is performed to obtain the surface burr-like substance. The polymer template is a composite hollow sphere of metal, the hydrophilic channel of which is complexed, expanded, and even extended out of the sphere. The inner layer of the casing generates a continuous material; or

 Lwt%〜40. 0wt 0. lwt%~40. 0wt 0. lwt%~40. 0wt 0. lwt%~40. 0wt %, the initiator solution is infiltrated into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution that has not penetrated into the cavity of the polymer hollow sphere template is centrifuged and washed away. 01%〜10. 0%% of a constant concentration; in a constant concentration of 0. 01%~10. 0%%; The reaction is completed. The reaction temperature is 0. 5~24 hours, the reaction time is 0. 5~24 hours or so, the reaction is completed. The reaction temperature is 0. lwt%~40. 0wt%, the reaction temperature is 0°C~100°C, the reaction time is 0. 5~24 hours, the reaction is completed. Centrifugal cleaning, that is, a hollow sphere in which a polymer template having a burr-like substance on the surface is combined with an organic substance, the hydrophilic passage is reshaped, expanded, and even protruded from the sphere, and the inner layer of the casing generates a continuous material.

 (2) Dispersing the composite hollow spheres of the inner layer and the channel growth material obtained in the step (1) in an alcohol or an aqueous solution, and simultaneously adding two reaction components of an inorganic substance, a metal or an organic substance, controlling the concentration of the reactants, and depositing the reaction product in the reaction product. The outer surface of the hollow shell of the polymer obtains a composite hollow sphere in which the material is grown on the outer surface, the inner layer and the channel of the hollow shell of the polymer. In addition to the polymer template, a double-layer hollow sphere is obtained, that is, the hollow sphere contains a hollow sphere, but the two hollow spheres are connected by a column, and the inner hollow sphere cannot move in the outer hollow sphere, and the two hollow spheres are concentric.

 The inner hollow layer obtained by the step (1.1) and the composite hollow sphere of the channel growth inorganic substance are dispersed in the alcohol solution, and the inorganic precursor solution and the aqueous solution of the reaction component are added to control the concentration of the inorganic precursor in the reaction liquid. 01重量%〜40wt%, The concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0 °C~100 °C, the reaction time is 0. 5 ~24 hours, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell. After the reaction is completed, the mixture is centrifuged to obtain a composite hollow sphere in which the inorganic body is grown on the outer surface, the inner layer and the channel of the hollow shell of the polymer. The polymer template is removed to obtain a double-layered inorganic hollow sphere, that is, the hollow sphere contains a hollow sphere, and the obtained inorganic hollow sphere has an inorganic column connected between the two hollow spheres, and the inner hollow sphere cannot move in the outer hollow sphere, Hollow ball concentric; or

 01wt%〜30重量%, The concentration of the metal ion salt in the reaction solution is 0. 01wt%~30wt%, the concentration of the metal ion salt in the reaction solution is 0. 01wt%~30wt%, 5〜24小时, The reaction product is deposited on the polymer. The concentration of the template is 0. 01wt%~30wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0'C~100 °C, the reaction time is 0. 5~ 24 hours, the reaction product is deposited on the polymer. The outer surface of the hollow spherical shell forms a continuous shell. After the completion of the reaction, the mixture is centrifuged to obtain a composite hollow sphere in which a metal and an inner layer and a channel-grown inorganic substance are grown on the outer surface of the polymer hollow spherical shell. The polymer template is removed to obtain a double-layered metal-inorganic hollow sphere, that is, the hollow metal sphere contains an inorganic hollow sphere, and the obtained double-layer hollow sphere has an inorganic column connected between the two hollow spheres, and the inorganic hollow sphere Can't move in the hollow metal ball, the two hollow balls are concentric; or

Dispersing the inner layer and the channel-forming inorganic composite hollow sphere obtained in the step (1.1) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the polymer single in the reaction liquid. 01重量%〜20重量。 Body concentration 0. 01wt% ~ 20wt%, the initiator concentration of 0. 01wt% ~ 20wt. /. The concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0°C~ 100 ° C, reaction time 0. 5~24 hours, the reaction product is deposited on the outer surface of the polymer hollow spherical shell to form a continuous shell. After the reaction is completed, the mixture is centrifuged to obtain a composite hollow sphere in which an organic substance and an inner layer and a channel-grown inorganic substance are grown on the outer surface of the polymer hollow spherical shell. The polymer template is removed to obtain a two-layer organic-inorganic hollow sphere, that is, the organic hollow sphere contains an inorganic hollow sphere, and the obtained double-layer hollow sphere has an inorganic column connected between the two hollow spheres, and the inorganic hollow sphere Cannot move in the hollow sphere of organic matter, the two hollow spheres are concentric; or

 The weight of the inorganic precursor in the reaction solution is 0. 01wt. The weight of the inorganic precursor in the reaction solution is 0. 01wt %〜3( rt%, the final concentration of the aqueous solution of the reaction component is 0. lwt% ~ 50wt%, the concentration of the template particles is 0. lwt% ~ 40wt ° /., the reaction temperature 0 ° C ~ 100 ° C, reaction time 0. 5~24 hours, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell. After the reaction is completed, centrifugal cleaning is performed to obtain inorganic and inner layers and channel growth on the outer surface of the hollow shell of the polymer hollow shell. Metal composite hollow sphere. The polymer template is removed to obtain a two-layer structure inorganic-metal hollow sphere, that is, the inorganic hollow sphere contains a metal hollow sphere, and the obtained double-layer hollow sphere has two metal spheres connected by a hollow column. , the hollow metal sphere cannot move in the inorganic sphere, and the two hollow spheres are concentric; or

 The ionic salt concentration of the metal ionic salt in the reaction liquid is 0.11% by weight to 30% by weight. 5〜24小时, The reaction product is deposited in the polymerization. The concentration of the template is 0. 01wt%~ 30wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0°C~100°C, the reaction time is 0. 5~24 hours, the reaction product is deposited in the polymerization. The outer surface of the hollow spherical shell forms a continuous shell. After the reaction is completed, the mixture is centrifuged to obtain a composite hollow sphere in which metal and inner layer and channel growth metal are grown on the outer surface of the polymer hollow spherical shell. The polymer template is removed to obtain a double-layered metal hollow sphere, that is, the metal hollow sphere contains a metal hollow sphere, and the obtained double-layer hollow sphere has a metal column connected between the two hollow spheres, and the inner metal hollow sphere cannot be in the outer hollow sphere. Movement, two hollow balls concentric; or

 Dispersing the composite hollow sphere of the inner layer and the channel growth metal obtained in the step (1.2) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the polymer monomer in the reaction liquid. 5〜24小时, The reaction time is 0. 5~24 hours, the reaction time is 0. 5~24 hours, the reaction time is 0. 5~24 hours, the reaction time is 0. 5~24 hours, The reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell. After the completion of the reaction, the mixture is centrifuged to obtain a composite hollow sphere in which an organic substance and an inner layer and a channel are grown on the outer surface of the hollow shell of the polymer. The polymer template is removed to obtain a two-layer structure organic-metal hollow sphere, that is, the organic hollow sphere contains a metal hollow sphere, and the obtained double-layer hollow sphere has a metal column connected between the two hollow spheres, and the metal hollow sphere cannot be hollow in the organic matter. In-ball movement, two hollow balls concentric; or

0重量。 The concentration of the inorganic precursor in the reaction liquid is 0. 01wt /. 5〜24。 The reaction time is 0. 5~24, the reaction time is 0. 5~24 Hours, the reaction product is deposited on the outer surface of the polymer hollow sphere shell to form Continuous shell. After the reaction is completed, the mixture is centrifuged to obtain a composite hollow sphere in which an inorganic substance, an inner layer and a channel-growing organic substance are grown on the outer surface of the hollow sphere of the polymer. The polymer template is removed to obtain a two-layer structure inorganic-organic hollow sphere, that is, the inorganic hollow sphere contains an organic hollow sphere, and the obtained double-layer hollow sphere has an organic column connected between the two hollow spheres, and the organic hollow sphere cannot be Intra-spherical ball movement, two hollow balls concentric; or

 01wt%〜3(kt) The concentration of the metal ion salt in the reaction solution is 0. 01wt%~3(kt), the metal ion salt concentration in the reaction solution is 0. 01wt%~3(kt % 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约The outer surface of the hollow shell of the polymer forms a continuous shell. After the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere in which metal and inner layer and channel-grown organic matter are grown on the outer surface of the polymer hollow sphere shell. The double-layered metal-organic hollow sphere, that is, the hollow sphere of the metal contains an organic hollow sphere, and the obtained double-layer hollow sphere has an organic column connected between the two hollow spheres, and the organic hollow sphere cannot move in the hollow sphere of the metal, and the hollow Ball concentric; or

 Dispersing the composite hollow sphere of the inner layer and the channel growth organic material obtained in the step (1.3) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the polymer monomer in the reaction liquid. 5〜24。 The concentration of 0. 01wt%~ 20wt%, the concentration of the template is 0. lwt%~40wt%, the reaction temperature 0 ° C ~ 100 ° C, the reaction time 0. 5~24 In an hour, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell. After the reaction is completed, the mixture is centrifuged to obtain a composite hollow sphere in which organic matter is grown on the outer surface of the hollow shell of the polymer and the inner layer and the channel. The polymer template is removed to obtain a double-layered organic hollow sphere, that is, the organic hollow sphere contains an organic hollow sphere, and the obtained double-layer hollow sphere has an organic column connected between the two hollow spheres, and the inner hollow sphere cannot move in the outer hollow sphere. , the two hollow balls are concentric. 6. Preparation method of double-layer structure hollow sphere Steps:

 Through the surface hydrophilic modification, the outer surface of the hollow sphere of the polymer also becomes a hydrophilic surface, that is, the intermediate layer is oleophilic, and the inner layer and the outer surface are three-layer shell which is ice-friendly, and the surface modification polymerization is performed. The hollow sphere replaces the polymer hollow sphere template to carry out the reaction, and the composite hollow sphere of a multi-layer structure can be produced in one step. By removing the template polymer with a selective solvent, a two-layer hollow sphere can be obtained.

Lwt%~40. 0wt%, making inorganic substances, the inorganic polymer precursors are immersed in a concentration of 0. 01wt%~60. 0wt% of the inorganic precursor solution, the template particles in the solution to maintain a concentration of 0. lwt% ~ 40. 0wt%, make inorganic substances The precursor solution penetrates into the cavity and hydrophilic layer of the modified polymer hollow sphere template, and after reaching equilibrium, the solution that has not penetrated into the cavity is centrifuged and washed away. The obtained modified polymer hollow sphere containing the inorganic precursor solution is then added to the aqueous solution of the reaction component with stirring.约约约40. 0wt%, reaction temperature 0 ° C ~ 100 ° C, reaction time 0. 5~24 hours or so, the reaction is completed, centrifugal cleaning, the polymer is obtained Multi-layer composite hollow sphere with inorganic matter. The double-layered inorganic hollow sphere can be obtained by removing the template polymer with a selective solvent; or 01wt%〜60. The weight of the modified polymer hollow spheres containing the aqueous solution of the reaction mixture was added to a concentration of 0. 01wt%~60. Owt% in the inorganic precursor solution. The temperature of the modified polymer hollow sphere is controlled to be 0. lw «~40. 0wt%, the reaction temperature is 0 ° C ~ 100. C, The reaction time is about 0.5 to 24 hours, the reaction is completed, and the mixture is centrifuged to obtain a multilayer composite hollow sphere of a polymer and an inorganic material. By removing the template polymer with a selective solvent, a two-layer inorganic hollow sphere can be obtained. or

 Lwt%〜40. Owt%, so that the modified polymer hollow spheres in the solution of the metal ion salt solution, the modified polymer hollow spheres in the solution to maintain a concentration of 0. lwt% ~ 40. Owt%, so The metal ion salt solution penetrates into the cavity and the hydrophilic layer of the modified polymer hollow sphere, and after centrifugation, the uninfiltrated solution is centrifuged and washed away. Then, the obtained modified polymer hollow sphere containing the metal ion salt solution is stirred. 0wt%〜40. 0wt%, reaction temperature 0°C~100°C, reaction time 0. 0wt%~40. 0wt%, reaction temperature 0°C~100°C, reaction time 0. 01wt%~60. 0%% of the reducing agent solution. After 5~24 hours, the reaction is completed and centrifuged to obtain a multi-layer composite hollow sphere of polymer and metal. The double-structured metal hollow sphere can be obtained by removing the template polymer with a selective solvent;

 0. 01wt%~60. 0wt% of the reducing agent solution is infiltrated into the hollow cavity of the modified polymer hollow sphere particles and the hydrophilic layer, and then the obtained modified polymer hollow sphere containing the reducing agent solution is added under stirring. To a concentration of 0. 01wt% ~ 60. 0wt% of the metal ion salt solution. The concentration of the template particles in the reaction solution is maintained at 0. lwt% ~ 40. 0wt%, the reaction temperature is 0 ° C ~ 10 (TC, reaction time 0. 5 ~ 24 hours or so, the reaction is completed, centrifugal cleaning, the same polymer Multi-layer composite hollow sphere with metal. The double-structured metal hollow sphere can be obtained by removing the template polymer with a selective solvent.

 Lwt%~40. 0wt 0. lwt%~40. 0wt 0. lwt%~40. 0wt 0. lwt%~40. 0wt %, the polymer monomer solution is infiltrated into the cavity and hydrophilic layer of the modified polymer hollow sphere, and after reaching equilibrium, the solution not infiltrated into the hollow cavity of the modified polymer hollow is centrifuged and washed. The modified polymer hollow spheres of the monomer solution are added to 0. 01wt%~30. 0wt% in the initiator solution. The inert gas is introduced into the reaction vessel to control the concentration of the template particles in the reaction solution to be kept at 0. Lwt%~40. 0wt%, reaction temperature 0 °C ~ 100 ° C, reaction time 0. 5~24 hours or so, the reaction is completed, centrifugal cleaning, that is, a multi-layer composite hollow sphere of polymer and organic matter is obtained. The solvent removes the template polymer to produce a two-layer organic hollow sphere.

01wt%〜30. 0wt°/. 01^/。 The initiator solution is infiltrated into the cavity of the modified polymer hollow sphere and the hydrophilic layer, and then the modified polymer hollow sphere containing the initiator solution is added to a concentration of 0. 01 ^ /. 〜4 (1⁄2«) The polymer monomer solution. The inert gas is introduced into the reaction vessel, and the concentration of the template particles in the reaction solution is kept at 0. lwt ° / . ~ 40 wt%, the reaction temperature is 0 ° C ~ 100 ° C, The reaction time is about 0.5 to 24 hours, the reaction is completed, and the mixture is centrifuged to obtain a multilayer composite hollow sphere of polymer and organic matter. The template polymer can be removed by a selective solvent to obtain a two-layer organic hollow sphere. VII. Preparation method of polymer composite hollow sphere by swelling polymerization method Steps: Dispersing the polymer hollow sphere template particles in water, adding a monomer and a crosslinking agent, or a monomer and a crosslinking agent and an organic solvent, swelling the polymer hollow sphere template shell by a monomer or an organic solvent, and Lwt%〜20wt%的反应的反应。 The body and the initiator is introduced into the polymer hollow spherical shell layer, and then the polycondensation, polycondensation or ring-opening polymerization, the inert gas is introduced into the reaction vessel, the concentration of the template particles in the reaction solution is 0. lwt%~20wt%, the reaction The monomer concentration is 0. lwt%~20wt%, the initiator concentration is 0.01wt%~10wt%, the organic solvent concentration is 0wt%~20wt%, the swelling time is 0.5~24 hours, and the reaction temperature is 20 °C~250° C, reaction time 0.5 to 48 hours. After the reaction is completed and centrifuged, a composite hollow sphere of a polymer hollow sphere and an organic substance can be obtained. The outer diameter of the polymer hollow sphere template particles is 0.02Mm~10to, and the cavity volume is 10~95% of the whole microsphere. The synthetic methods used are spray drying method, block copolymer self-assembly method, acid Alkali swelling method, dynamic swelling method, multiphase emulsion polymerization method.

 The inner hydrophilic polymer of the polymer hollow sphere template comprises polystyrenesulfonic acid, polymethacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide, polyvinylpyrrole, poly(2-vinylpyrrolidone). Precipitate), poly(4-vinylpyridine), polyhydroxyethyl methacrylate, polyvinyl ester, polyoxyethylene or polyvinyl ammonium chloride.

 The outer lipophilic polymer of the polymeric hollow sphere template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, polymethyl Acrylic acid cinnamic acid ethyl ester, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polybutyl acrylate, polyoxypropylene, polydimethylsilyl, polyvinyl butyrate or polyisobutylene.

 The selective solvent for removing the polymer template is chloroform, toluene, tetrahydrofuran or N,N-dimethylformamide or the like.

 The hydrophilic modification of the polymer hollow sphere is carried out by hydrophilic modification of a commercially available or self-made polymer hollow sphere (having a diameter of 0.02 m to 10 Mm and a cavity size of 10 to 95% of the entire microsphere size). The modification methods include electrostatic adsorption, sulfonation treatment, hydrolysis reaction, surface grafting and the like. ,

In the preparation of the SiO ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is Si (0CH ₃ ) ₄ , Si (0CH ₂ C3⁄4), Si{0CH(C3⁄4) ₂ } ₄ , Si(0CH ₂ C CH ₂ CH ₃ ) ₄ , an alcohol solution of Na ₂ SiO ₃ ; the aqueous solution of the reaction component is an alcoholic solution of water (0. lwt ° / ~ 100 wt%), and its _P H is adjusted with 35 % concentrated hydrochloric acid or 25 w « concentrated ammonia water The value is 1~13.

In the preparation of the Ti0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is TiCl ₄ , Ti(0CH ₃ ) ₄ , Ti(0C C ) ₄ , Ti{0CH(CH ₃ ) ₂ } ₄ , Ti (0CH ₂ CH ₂ CH ₂ C ) ₄ , T alcohol 0 ₄ alcohol solution; the reaction component aqueous solution is water alcohol solution (0. lwt% ~ 100 wt%), with 35 % concentrated hydrochloric acid or 25 wt% concentrated ammonia water to adjust its pH It is 1 to 13.

In the preparation of the Sn0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is SnCl ₄ , Sn(0C3⁄4) ₄ , Sn(0CH ₂ CH ₃ ) ₄ , Sn{0CH(CH ₃ ) ₂ }^ Sn An alcohol solution of (0CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ ; an aqueous solution of the reaction component is an alcoholic solution of water (0.1 wt% to 100 wt%), using 35 % concentrated hydrochloric acid or 25 wt ° /. Concentrated ammonia water adjusts its pH to 1~13.

When preparing a Zr0 ₂ hollow sphere or a composite hollow sphere, the inorganic precursor solution is ZrCl ₄ , Zr(0CH ₃ ) ₄ , Zr (0C CH ₃ ) ₄ , Zr {0CH(C3⁄4) ₂ } ₄ , Zr (0C C CH ₂ C3⁄4) ₄ , Zr (S0 ₄ ) ₂ alcohol solution; the reaction component aqueous solution is water alcohol solution (0. Lwt%~10 (kt%), the pH is adjusted to 1~13 with 35wt% concentrated hydrochloric acid or 25wt%/concentrated ammonia water.

In the preparation of the A1 ₂ 0 ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is A1C1 ₃ , A1 (0CH ₃ ) ₃ , A1 (0CH ₂ CH ₃ ) ₃ , A1 {0CH(C ) ₂ } ₃ , Al (0CH ₂ CH ₂ C CH ₃ ) ₃ , Al ₂ (S0 ₄ ) ₃ alcohol solution; the reaction component aqueous solution is water alcohol solution (0. lwt% ~ 100wt%), with 35wt% hydrochloric acid or 25wt The concentrated ammonia water is adjusted to have a pH of 1 to 13.

In the preparation of a V ₂ 0 ₅ hollow sphere or a composite hollow sphere, the inorganic precursor solution is V0 (0CH ₃ ) ₃ , V0(0CH ₂ C ) ₃ , VO{0CH(CH ₃ ) ₂ } ₃ , V0 (0CH ₂ C C3⁄4C3⁄4) ₃ alcohol solution; the aqueous solution of the reaction component is an alcoholic solution of water (0. lwt ° / ~ ~ 100 wt%), with 35 ¥ « concentrated hydrochloric acid or 25wt ° /. Concentrated ammonia water adjusts its pH to 1~13.

In the preparation of the ZnO hollow sphere or the composite hollow sphere, the inorganic precursor solution is an alcohol solution of Zn(N0 ₃ ) ₂ , Zn (00CCH ₃ ) ₂ , ZnCl ₂ , Zn (CI ) ₂ ; It is a water or alcohol solution of alkali (0. 01wt ° / _a ~ 30wtt), such as sodium hydroxide, potassium hydroxide or ammonia.

In the preparation of the TO ₃ hollow spheres or the composite hollow spheres, the inorganic precursor solution is an aqueous solution of (NH ₄ ) ₆ H ₂ W ₁₂ 0 ₄₁ , NaW0 ₃ ; ~100wt%), the pH is adjusted to 1~13 with 35% concentrated hydrochloric acid or 25% concentrated ammonia water.

In the preparation of the Mo0 ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is an aqueous solution of Mo 0 ₃ 2 0; the aqueous solution of the reaction component is an aqueous alcohol solution (0. lwt% to 100 wt%), with a concentration of 35 % Hydrochloric acid or 25 wt% concentrated aqueous ammonia is adjusted to have a pH of 1 to 13.

In the preparation of Al (OH) ₃ or Mg (OH) ₂ hollow spheres or composite hollow spheres, the inorganic precursor solution is an aqueous solution of soluble aluminum, magnesium chloride or sulfate; the aqueous solution of the reaction component is alkali Aqueous solution (0.11% by weight to 30% by weight) such as sodium hydroxide, potassium hydroxide or ammonia.

In the preparation of biomineralized materials CaC0 ₃ , C _ai . (P0 ₄ ) _e (0H) ₂ , CaS0 ₄ , or BaS0 ₄ hollow sphere or composite hollow sphere, the inorganic precursor solution is Ca(0H) ₂ , CaCl ₂ , Ba(0H) ₂ , or BaCl ₂的水溶液; The aqueous solution of the reaction component is a solution of C0 ₃ ² —, P0—, SO—Na+, or K ⁺ salt or H ₂ C0 ₃ , H ₃ P0 ₄ , 3⁄450 ₄ (0. 01wt°/.~ 30wt%).

 In the preparation of a semiconductor sulfide hollow sphere or a composite hollow sphere, the inorganic precursor solution is an aqueous solution of a soluble salt of a corresponding metal cation, such as a chloride, a nitrate, or a sulfate; the aqueous solution of the reaction component is sodium sulfide, sulfur An aqueous solution of urea (0. 01wt ° / ~ ~ 30wt%).

 In the preparation of a semiconductor selenide or telluride hollow sphere or a composite hollow sphere, the inorganic precursor solution is an aqueous solution of a soluble salt of a metal cation such as chloride, nitrate or sulfate; and the aqueous solution of the reaction component is selenized. An aqueous solution of sodium or sodium hydride (0.11% by weight to 30% by weight). .

In the preparation of magnetic compounds such as Fe ₃ 0 ₄ , Fe ₂ 0 ₃ and ferrite hollow spheres or composite hollow spheres containing zinc, manganese, cobalt, nickel, copper, magnesium, the inorganic precursor solution is Fe ² An aqueous solution of a soluble salt of ⁺ , Fe ³⁺ , Zn ² \ Mn ²⁺ , Co ² \ Ni ²⁺ , Cu ²⁺ , Mg ²⁺ (such as chloride, nitrate, sulfate); An aqueous solution of an alkali (0.11% by weight to 30% by weight), such as sodium hydroxide, potassium hydroxide or aqueous ammonia, or a hydrazine hydrate solution (hrt%~6 (kt%)). In the preparation of a metal such as Au, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow spheres or composite hollow spheres, the metal ion salt solution is an aqueous solution of a corresponding metal ion soluble salt, such as perchlorate. , chloride, nitrate, sulfate; the reducing agent solution is an aqueous solution of a reducing agent, such as an aqueous solution of NaB, LiB (C ₂ H ₅ ) ₃ H, N ₂ .

 In the preparation of a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyparaphenylene acetylene and its derivative hollow sphere or composite hollow sphere, the polymer monomer solution is a water or alcohol solution of the corresponding monomer; The solution is an aqueous solution of potassium persulfate, ammonium persulfate or ferric chloride.

 In the preparation of a sensitive gel such as poly N-isopropylacrylamide, polyacrylic acid, polymethacrylic hollow spheres or composite hollow spheres, the polymer monomer solution is a monomeric N-isopropylacrylamide, Acrylic acid, methyl decenoic acid or its water or alcohol solution; the initiator solution is an aqueous solution of potassium persulfate or ammonium persulfate.

In the preparation of the multi-material composite hollow sphere, the composite includes inorganic, metal, organic composites such as Ti0 ₂ and SiO ₂ , Ti0^n SnO ₂ , TiO ₂ and ZnO, gold and silver, palladium and nickel, and the like. Also included are inorganic, metal and organic complexes such as titanium dioxide and triiron tetroxide, polyaniline and ferric oxide, polyacrylic acid and silver.

 The inert gas is nitrogen or argon or the like.

 The alcohol solution is methanol, ethanol, propanol, isopropanol, butanol or the like.

 The shell swelling polymerization method can be used to prepare high performance polymer hollow spheres or composite hollow spheres, such as crosslinked polystyrene, polyacrylate, polyurethane, phenolic resin, unsaturated polyester, epoxy resin, polyacyl. Imine, polyether ketone or polyether sulfone hollow sphere or composite hollow sphere.

 The cross-linking agent for preparing cross-linked polystyrene, polyacrylate hollow sphere or composite hollow sphere is azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide, peroxydicarbonate Isopropyl ester, potassium persulfate or ammonium persulfate; the monomer is styrene, divinylbenzene, methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate;

 The crosslinking agent for preparing the polyurethane hollow sphere or the composite hollow sphere is polyether diol, polyester diol or 1, 4-butanediol; the monomer is hexamethylene diisocyanate or toluene diisocyanate;

 The crosslinking agent for preparing the phenolic resin hollow sphere or the composite hollow sphere is phenol, o-cresol, p-cresol, resorcin or bisphenol A; the monomer is formaldehyde, trioxane, acetaldehyde, trimer Acetaldehyde or furfural;

 The crosslinking agent for preparing the unsaturated polyester hollow sphere or the composite hollow sphere is ethylene glycol, propylene glycol, 1, 3-butanediol, polyether diol or polyester diol; the monomer is bismuth maleate ;

 The crosslinking agent for preparing the epoxy resin hollow sphere or the composite hollow sphere is hexamethylene diisodecanoate, toluene diisocyanate, phthalic anhydride, phthalic anhydride, maleic anhydride, ethylenediamine, and hexan An amine or trimethyltetramine; the monomer is bisphenol A epoxy or phenolic epoxy;

 The crosslinking agent for preparing the polyimide hollow sphere or the composite hollow sphere is p-phenylenediamine or hexamethylenediamine; the monomer is bismaleic anhydride or pyromellitic anhydride;

The crosslinking agent for preparing the polyether ketone or the polyether sulfone hollow sphere or the composite hollow sphere is 4,4-difluorobenzophenone or 4,4-dichlorodiphenyl sulfone; the monomer is hydroquinone Or tetramethylbiphenyldiol. The organic solvent used to swell the polymer hollow spherical shell is chloroform, benzene, toluene, xylene, tetrahydrofuran, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, dimethyl Sulfone, acetone, cyclohexane. The composite hollow spheres and hollow spheres prepared by the invention have wide applications -

(1). Using a catalytic property of silver, platinum, palladium, nickel, etc., a high-performance catalyst can be prepared to form a hollow sphere of a catalyst material. The catalyst hollow sphere is composed of nanoparticles, and the large specific surface area also ensures the liquidity of the liquid gas.

 (2). Using its cavity as a capsule material, it can be applied to various fields of material transport and sustained release control, using magnetic materials and sensitive gels to obtain intelligent capsules; as a microreactor, researching substances Responsive materials are prepared by limiting the reaction or controlling their conditional reactivity.

 (3). It can be used as a whitening agent due to the high refractive index difference between the shell materials and the air; using pigments such as titanium oxide and iron oxide and ultraviolet absorption, it can be used as an anti-UV additive and Masterbatch; It can be used as a lightweight filler due to its low density. It is widely used in the plastics, coatings, inks, printing materials, paper and cosmetics industries. '

 (4) Semiconductors such as zinc oxide and cadmium sulfide can be used as solar cell materials by utilizing their ultraviolet light absorption and photoelectric conversion properties, and can also be used as photocatalytic materials, which are widely used in antibacterial deodorization, sewage treatment, and purification of exhaust gas. , Photolysis water, etc., can also be used as gas sensors, dielectric ceramics.

 (5). Can be used to prepare controllable polymer capsules. Through electrostatic adsorption and polymerization, complex sensing functional substances such as hydrogels, photosensitizers, phospholipid molecules and protein molecules can be combined in the polymer template pore channel to achieve intelligent switching processes.

 (6). Using the conductivity and redox reversibility of the conductive polymer, an electrode active material, an electrochemical catalytic active material, a metal anticorrosive material, a chemical or electrochemically adjustable gas separation membrane, an electrochromic element, a living body can be prepared. Sensors, etc.

 (7) Functional materials can also be used as insulating materials, thermal insulation materials, sound absorbing materials, conductive materials, ordered magnetic materials, photoelectric functional materials, and the like. The preparation method and product features of the invention are as follows:

 (1) The preparation method of the invention has wide adaptability, and can prepare a series of hollow spheres and composite hollow spheres of different materials and forms;

 (2) The hollow sphere and the composite hollow sphere of the present invention not only have good dispersibility, but also have good strength and dimensional stability;

(3) The size of the prepared hollow sphere and composite hollow sphere can be adjusted within the range of 10 ^{1 to} 10 ⁴ ;;

 (4) The shape of the hollow sphere and the composite hollow sphere is adjustable, and the composition and thickness of the casing are controllable;

(5) . The preparation process is simple and the conversion rate of raw materials is high. The present invention will be described in detail below with reference to the embodiments and the accompanying drawings:

DRAWINGS

 Figure 1. Schematic diagram of a polymer hollow sphere template applied in an embodiment of the present invention.

 Figure 2. Transmission electron micrograph of a polystyrene-polypropylene/titanium oxide composite hollow sphere of Example 1 of the present invention. Fig. 3. Transmission electron micrograph of a titanium dioxide hollow sphere of Example 1 of the present invention.

 Fig. 4. Scanning electron micrograph of a titanium oxide tetragonal iron oxide composite hollow sphere of Example 8 of the present invention.

 Figure 5 is a scanning electron micrograph of a burr type titanium dioxide/polystyrene-polyacrylic composite hollow sphere of Example 10 of the present invention.

 Figure 6. Transmission electron micrograph of a silica/titania double-layer hollow sphere of Example 19 of the present invention. detailed description

Example 1 Preparation of Polystyrene-Polyacrylic Acid/Titanium Dioxide Composite Hollow Sphere and Titanium Dioxide Hollow Sphere

 The polystyrene-polyacrylic hollow sphere template has a polystyrene outer layer of polystyrene and an inner layer of polyacrylic acid having an outer diameter of 500 rai and a shell thickness of 100 nm. 0. lg template particles were dispersed in lg tetrabutyl titanate, saturated adsorption for 4 hours, the hollow spheres adsorbed tetrabutyl titanate were sedimented by a high-speed centrifuge, and 10 g of water in ethanol (40 wt%) was added. The hydrolysis reaction was carried out for 4 hours to obtain a composite hollow sphere in which titanium dioxide was grown in the inner layer of the shell using polystyrene-polyacrylic acid hollow spheres as a template. The hollow sphere of this composite structure was removed from polystyrene and polyacrylic acid with chloroform to obtain hollow spheres of titanium dioxide. The results of transmission electron microscopy showed that the hollow titania sphere consisted of 30 50 nm particles with a shell thickness of 60 nm and the size of the cavity. 250nm

Or the prepared composite hollow spheres are sintered at 45 CTC for 2 hours to obtain hollow spheres of crystalline titania, and the XRD results indicate that the crystal form is anatase; the composite hollow spheres are sintered at 600 ° C for 2 hours to obtain crystalline titanium dioxide. Hollow spheres, XRD results show that the crystal form is anatase and rutile composite. Example 2 Preparation of polystyrene-polymethacrylic acid/magnetic ferroferric oxide composite hollow spheres and ferroferric oxide hollow spheres O. lg polystyrene-polymethacrylic acid hollow structure emulsion particles, the outer diameter of which is lOOOran, the thickness of the shell layer is 150nm, dispersed in lg of 25 « ferric chloride and 19%% ferrous chloride mixed solution, saturated adsorption for 4 hours, the polymer hollow spheres with adsorbed solution are centrifuged by high-speed centrifuge , redispersed in 10g of 15wt ° /. Ammonia water was hydrolyzed for 4 hours to obtain a composite hollow sphere in which polystyrene-polymethacrylic acid hollow spheres were used as a template and ferroferric oxide was grown in the inner layer of the shell. The hollow sphere of this composite structure was subjected to removal of polystyrene and polymethacrylic acid with chloroform to obtain a hollow sphere of triiron tetroxide. The results of transmission electron microscopy showed that the hollow triiron tetroxide consisted of 50-100 nm particles with a shell thickness of 200 nm and a cavity size of 400. Example 3 Polymethyl methacrylate-polyacrylic acid/calcium carbonate composite hollow sphere And preparation of calcium carbonate hollow spheres O. lg polymethyl methacrylate-polyacrylic acid hollow structure emulsion particles, the outer diameter of which is 100nm, the thickness of the shell layer is 20nm, dispersed in 15wt% calcium chloride solution, saturated adsorption for 4 hours, will be adsorbed The hollow spheres of the calcium chloride solution were centrifuged by a high-speed centrifuge, dispersed in 10 g of a 15 wt% aqueous solution of sodium carbonate, and the pH was adjusted to 9 with 25 wt% of ammonia water for 4 hours to obtain polymethyl methacrylate-poly. The acrylic hollow sphere is a composite hollow sphere in which the template calcium carbonate is grown in the inner layer of the shell. The composite hollow spheres were subjected to removal of polymethyl methacrylate and polyacrylic acid with chloroform to obtain hollow spheres of calcium carbonate. The results of transmission electron microscopy showed that the hollow calcium carbonate sphere consisted of 20 nm particles with a shell thickness of 20 nm and a cavity size of 20 nra. 'Example 4 Preparation of polystyrene-polyacrylic acid/cadmium sulfide composite hollow spheres and cadmium sulfide hollow spheres

 O. lg polystyrene-polyacrylic acid hollow structure emulsion particles, the outer diameter of 300nm, the thickness of the shell layer is 60nm, dispersed into 2 (kt% cadmium nitrate aqueous solution, saturated adsorption for 24 hours, will adsorb the solution The hollow spheres were centrifugally sedimented by a high-speed centrifuge, dispersed in 10 g of a 20 wt% aqueous solution of sodium sulfide, and reacted for 4 hours to obtain a composite hollow sphere in which cadmium sulfide was grown in the inner layer of the shell by using polystyrene-polyacrylic acid hollow spheres as a template. After the composite hollow spheres were removed from polystyrene and polyacrylic acid with tetrahydrofuran, a hollow sphere of sulfidation pain was obtained. The results of transmission electron microscopy showed that the hollow calcium carbonate sphere consisted of 30 nm particles with a shell thickness of 40 nm and a cavity size of 120 awake. Example 5 Preparation of Polystyrene-Poly-2-vinylpyridine/Silver Composite Hollow Sphere and Silver Hollow Sphere

0. lg polystyrene-poly 2 vinyl pyridine hollow structure emulsion particles, the outer diameter of 100 dishes, the thickness of the shell layer is 20nm, dispersed in 15wt% silver nitrate solution, saturated adsorption for 4 hours, will adsorb The polymer hollow spheres of the silver nitrate solution were sedimented by a high-speed centrifuge, dispersed in 10 _{g of} 20 t% hydrazine hydrate, and hydrolyzed for 4 hours to obtain a polystyrene-poly-2-vinylpyridine hollow sphere as a template. A composite hollow sphere of silver particles grown on the inner surface of the shell. After removing the polystyrene and the poly-2-vinylpyridine from the hollow sphere of this composite structure with tetrahydrofuran, silver particles of lOnm were obtained. Increasing the concentration of the silver nitrate solution allows the silver particles to form a continuous shell layer in the inner layer, and after removing the template, a hollow sphere composed of silver particles can be obtained. The silver hollow sphere is composed of lOnm particles having a shell thickness of 20 nm and a cavity size of 40 nm. Example 6 Preparation of polymethyl methacrylate-polyacrylic acid/poly N-isopropylacrylamide composite hollow spheres and poly N-isopropylacrylamide hollow spheres

Og isopropyl amide, 0. 5g of N-isopropyl acrylamide, 0. 5g of N-isopropyl acrylamide, 0. 5g of N-isopropyl acrylamide, 0 . 05gN, N-dimethylbisacrylamide. 0克。 After adding 0. 01g. The temperature was raised to 70 Torr, and the reaction was carried out for 8 hours with stirring to obtain a composite hollow sphere of polymethyl methacrylate-polyacrylic acid and poly-N-propyl acrylamide. This composite hollow sphere was subjected to removal of polymethyl methacrylate and polyacrylic acid with chloroform to obtain a hollow temperature-sensitive poly N-isopropylacrylamide hollow sphere. Example 7 Preparation of Polystyrene-Polyacrylic Acid/Polyaniline Composite Hollow Sphere and Polyaniline Hollow Sphere

 O. lg polystyrene-polyacrylic acid hollow structure emulsion particles, the outer diameter of which is 400nm, the thickness of the shell layer is 80nm, adding lg 22.8% aqueous ammonium persulfate solution, stirring for 4 hours, centrifuging and then dispersing to 10g 0克苯胺。 In water, 0. 8g aniline. The reaction was carried out at room temperature for 24 hours to obtain a polystyrene-polyacrylic acid/polyaniline composite hollow sphere. The hollow sphere of this composite structure was subjected to removal of polystyrene and polyacrylic acid with chloroform to obtain a polyaniline hollow sphere. EXAMPLE 8 Preparation of Polystyrene-Polyacrylic Acid/TiO2 Magnetic Tetrahydrate Composite Hollow Ball and Titanium Dioxide Tetraoxide Composite Hollow Ball

 The polystyrene-polyacrylic acid/titanium dioxide composite hollow sphere was prepared according to Example 1, and the composite particles were dispersed in lg of 25% iron chloride and 19% ferrous chloride mixed solution, and saturated for 4 hours. The polymer hollow spheres to which the solution was adsorbed were sedimented by a high-speed centrifuge, dispersed in 10 g of 15 wt% aqueous ammonia, and hydrolyzed for 4 hours to obtain a polystyrene-polyacrylic acid/titanium dioxide magnetic tetraoxide composite hollow sphere. The hollow sphere of this composite structure was subjected to removal of polystyrene and polyacrylic acid with chloroform to obtain a composite hollow sphere of titanium oxide and triiron tetroxide. Lg。 The polystyrene-polyacrylic acid/titanium dioxide composite hollow spheres, the composite particles 0. lg The aniline was added to the mixture. The ocyanamine was added to the mixture. The ocyanamine was added to the mixture. The reaction was carried out for 24 hours in an ice water bath to obtain a polystyrene-polyacrylic acid/titanium oxide polyaniline composite hollow sphere. The hollow sphere of this composite structure was subjected to removal of polystyrene and polyacrylic acid with chloroform to obtain a composite hollow sphere of titanium dioxide and polyaniline. Example 10 Preparation of burr type titanium dioxide/polystyrene-polymethacrylic acid composite hollow sphere and edgy type titanium dioxide hollow sphere

Taking an emulsion containing O. lg polystyrene-polymethacrylic polymer hollow spheres, the outer diameter of which is ΙΟΟΟΓΜ, the thickness of the shell layer is 150 nm, dispersed in 10 g of ethanol, and the addition of lg tetrabutyl titanate is divided twice. After 1 hour, the hydrolysis reaction was continued for 4 hours, and a hollow sphere of polystyrene-polymethacrylic acid polymer was used as a template. Titanium dioxide was grown on the inner layer of the shell and the channel and extended to form a burr. The hollow spheres of the composite structure were removed with polystyrene and polymethacrylic acid by chloroform to obtain burred titanium dioxide hollow spheres. The results of transmission electron microscopy showed that the hollow titanium dioxide spheres were composed of 50-100 nm particles with a shell thickness of 100 nm. The size of the cavity is 600 nm. The titanium dioxide burr is 50 to 200 nm long, 20 to 100 nm wide, and 10 to 150 nm high. Example 11 Preparation of burr-type silver/polystyrene-poly 4-vinylpyridine composite hollow spheres and burr-type silver hollow spheres An emulsion containing O. lg polystyrene-poly-4-vinylpyridine polymer hollow spheres having an outer diameter of 300 nm, a shell layer thickness of 60 nm, dispersed in 10 g of a 20 wt% hydrazine hydrate solution, and immersed for 24 hours. The hollow polymer spheres adsorbed with the hydrazine hydrate solution were centrifuged and sedimented by a high-speed centrifuge, and then dispersed in 20 g of a lwt% silver nitrate solution for 4 hours to obtain a hollow sphere of polystyrene-poly-4-vinylpyridine polymer. As a template, silver grows on the inner layer of the casing and the passage and protrudes from the surface to form a burr. The hollow sphere of this composite structure was subjected to removal of polystyrene and poly-4-vinylpyridine with tetrahydrofuran to obtain a burred silver hollow sphere. Example 12 Preparation of a blister-type polyaniline/polystyrene-polyacrylic composite hollow sphere and a burr-type polyaniline hollow sphere An emulsion containing 0.1 g of polystyrene-polyacrylic polymer hollow spheres having an outer diameter of 400 nm The thickness of the shell layer is 80 nm, dispersed in 5 g of 20% aqueous solution of ferric chloride, and saturated for 24 hours. The polymer composite hollow spheres to which the solution has been adsorbed are centrifugally sedimented by a high-speed centrifuge, dispersed in 10 g of water, and stirred. 0. 8g aniline was added in 4 times, each time interval was 1 hour, the reaction temperature was 25 ° C, and the reaction time was 24 hours. The polystyrene-polyacrylic acid polymer hollow sphere was used as a template, and polyaniline was grown in the inner layer and channel of the shell. And protruding from the surface to form a donkey. The hollow sphere of this composite structure was subjected to removal of polystyrene and polyacrylic acid with chloroform to obtain a burred polyaniline hollow sphere. Example 13 The outer surface of the shell was grown to form a silica/polystyrene-polyacrylic composite hollow sphere and a silica hollow sphere.

 0. lg polystyrene-polyacrylic acid polymer hollow sphere, the outer diameter of 8000nm, the thickness of the shell layer is 200nm, dispersed into 10g of ethanol, adding llg5% ammonia water and 2g tetraethyl silicate, hydrolysis reaction for 4 hours A composite hollow sphere in which silica is grown on the outer surface of the shell by using a polystyrene-polyacrylic hollow sphere as a template. After the composite hollow sphere was removed from polystyrene and polyacrylic acid with chloroform, a silica hollow sphere was obtained. The results of transmission electron microscopy showed that the hollow silica sphere consisted of 30 particles with a shell thickness of 200 nm. The size is 8000 nm.

Example 14 The shell surface was grown on the outer surface of the shell to prepare a gold/polystyrene-polyoxyethylene composite hollow sphere and a gold hollow sphere.

 The lg polystyrene-polyoxyethylene polymer hollow spheres having an outer diameter of 40 nra, a thickness of the shell layer of lOnm, dispersed in 10 g of water, adding lg of 5% hydrazine hydrate and 0.5 g of chloroauric acid, reacting for 2 hours A composite hollow sphere in which gold is grown on the outer surface of the shell is obtained by using a polystyrene-polyoxyethylene hollow sphere as a template. The composite hollow sphere was removed from polystyrene and polyoxyethylene by chloroform to obtain a gold hollow sphere. The results of transmission electron microscopy showed that the hollow gold sphere consisted of 5~10 nm particles with a shell thickness of 20 nm and the size of the cavity was 40nm. Example 15 Growth of shell layer on outer surface of shell, preparation of polyaniline/polystyrene-polymethacrylic acid composite hollow sphere and polyaniline hollow sphere

O. lg polystyrene-polymethacrylic acid hollow structure emulsion particles having an outer diameter of 400 nm, a shell layer having a thickness of 80 nm, and dispersed in 10 g of water. Put nitrogen in the reaction vessel, add 2g of 22.8% aqueous ammonium persulfate solution, stir After mixing for 30 minutes, another 0.5 g of aniline was added and reacted in an ice water bath for 24 hours to obtain a composite hollow sphere in which polyaniline was grown on the outer surface of the shell by using polystyrene jf_polymethacrylic acid hollow sphere as a template. The hollow sphere of this composite structure was subjected to removal of polystyrene and polymethacrylic acid with tetrahydrofuran to obtain a polyaniline hollow sphere having a cavity size of 400 nm. Example 16 Preparation of Silica/Titanium Dioxide Multilayer Composite Hollow Sphere and Its Double-Stranded Hollow Sphere

 The polystyrene-polyacrylic acid/ceria composite hollow sphere was prepared according to Example 1, and the composite particles were dispersed in 10 g of ethanol, and lg ethyl silicate and lg25% aqueous ammonia were added thereto, and the reaction temperature was 40 ° C. At 4 h, a silica/polystyrene-polyacrylic acid/titanium dioxide composite hollow sphere was prepared, which was grown in the inner layer of the polymer hollow sphere shell, and silica was grown on the outer surface of the shell. After removing polystyrene and polyacrylic acid with chloroform, a hollow sphere of silica titania double-layer structure, that is, a hollow sphere containing one cerium oxide in a silica hollow sphere, is obtained. Example 17 Preparation of Gold/Silica Multilayer Composite Hollow Sphere and Its Double-Stranded Hollow Sphere

0. lg polystyrene-polymethacrylic acid hollow structure emulsion particles, the outer diameter of which is lOOnm, the thickness of the shell layer is 20nm, dispersed to lg of 5 (kt% tetraethyl silicate in ethanol solution, saturated adsorption After 24 hours, the polymer hollow spheres with adsorbed solution were sedimented by high-speed centrifuge, dispersed in 10 g of 15 wt% ammonia water, and hydrolyzed for 4 hours to obtain polystyrene-polymethacrylic acid hollow spheres as a template for dioxide oxidation. A composite hollow sphere in which silicon is grown in the inner layer of the shell. The composite particles are redispersed into 10 g of an aqueous solution, and 6 _§ 30% of the chloroauric acid solution and 4 g of 5 (hrt% hydrazine hydrate solution are added, the reaction temperature is 40 Torr, and the reaction time is 4 h. That is, a gold/polystyrene-polyacrylic acid/silica composite hollow sphere is prepared, and the silica is grown in the inner layer of the polymer hollow sphere shell, and gold is grown on the outer surface of the shell. Polystyrene and polymethyl are removed by using tetrahydrofuran. After the acrylic acid, a hollow sphere of gold/silica double-layer structure, that is, a hollow sphere containing one silica in a gold hollow sphere is obtained. Example 18 Preparation of polyaniline/silver multilayer composite hollow sphere and double-layer hollow sphere thereof

0. lg polymethyl methacrylate-polyacrylic acid hollow structure emulsion particles, the outer diameter of 300nm, the thickness of the shell layer is 60nm, dispersed in lg 20wt% silver nitrate aqueous solution, saturated adsorption for 24 hours, will adsorb The polymer hollow spheres of the solution were sedimented by a high-speed centrifuge, dispersed in 10 g of a 15 wt% hydrazine hydrate solution, and reacted for 4 hours to obtain a polymethyl methacrylate-polyacrylic acid hollow sphere as a template, and silver was grown in the shell. A composite hollow sphere of the inner layer. The composite particles were redispersed into 10 g of an aqueous solution, and nitrogen gas was introduced thereto, and 0.5 g of aniline and 3 g of a 30 wt% aqueous solution of ammonium persulfate were added, and the mixture was placed in an ice water bath for 24 hours to obtain polyaniline/polymethyl methacrylate. Acrylic/silver composite hollow spheres, which are grown in the inner layer of the polymeric hollow sphere shell, while polyaniline is grown on the outer surface of the shell. After removing polystyrene and polymethacrylic acid with chloroform, a polyaniline/silver double-layer hollow sphere is obtained, that is, a hollow sphere containing one silver in the polyaniline hollow sphere. Example 19 Preparation of Silica/Titanium Dioxide Multilayer Composite Hollow Sphere and Concentric Double Layer Hollow Sphere 0. Ig polystyrene-if polymethacrylic acid hollow structure emulsion particles, the outer diameter of which is 400 letters, the thickness of the shell layer is 80nm, centrifuged with ethanol to remove the outer surface water, and then dispersed in 10g of ethanol, 4 times added 0. 5g tetrabutyl titanate, one hour apart, the reaction was continued for 4 hours, the reaction temperature was 40'C, and the polystyrene-polymethacrylic hollow sphere was used as a template, and the titanium dioxide was grown. A composite burr-like hollow sphere of the inner layer of the casing and the passage. Dispersing the composite particles into 10g of ethanol, adding 2g of ethyl silicate and lgl5% ammonia water, the reaction temperature is 40'C, and the reaction time is 4h, thereby preparing a silica/polystyrene-polymethacrylic acid/titanium dioxide composite hollow. The ball, the titanium dioxide is grown in the inner layer and the channel of the polymeric hollow sphere shell, and the silica is grown on the outer surface of the shell. After removing polystyrene and polymethacrylic acid with tetrahydrofuran, a hollow sphere of silica titania double-layer structure is obtained, that is, a hollow sphere containing a titanium dioxide in a silica hollow sphere, and a hollow titanium dioxide column is connected between the two hollow spheres, and the hollow is hollow. The ball cannot move in the outer hollow sphere, and the two hollow spheres are concentric. Example 20 Preparation of Titanium Dioxide/Platinum Multilayer Composite Hollow Sphere and Concentric Double Layer Hollow Sphere

O. lg polystyrene-polymethacrylic acid hollow structure emulsion particles having an outer diameter of 200 Å, a shell layer having a thickness of 50 nm, and dispersed at 1 _g 20 wt ° /. The sodium borohydride aqueous solution was immersed for 24 hours, and the outer surface solution was removed by centrifugation, and then dispersed in 10 g of water, and 4 mL of 20 wt/ was added in 4 portions. Chloroplatinic acid, one hour at a time, the reaction is continued for 8 hours, and the reaction temperature is 20 ° C. The polystyrene-polymethacrylic acid hollow sphere is used as a template to obtain a composite burr of platinum grown in the inner layer and the channel of the shell. Hollow ball. Dispersing the composite particles into 10 g of ethanol, adding 2 g of tetrabutyl titanate and lg water, the reaction temperature is 40 Torr, and the reaction time is 4 h, thereby preparing a titanium dioxide/polystyrene-polymethacrylic acid/platinum composite hollow sphere, the platinum It grows in the inner layer and channel of the polymer hollow sphere shell, while titanium dioxide grows on the outer surface of the shell. After removing polystyrene and polymethacrylic acid with tetrahydrofuran, a hollow sphere of ruthenium dioxide platinum double-layer structure is obtained, that is, a hollow sphere containing platinum in a hollow sphere of titanium dioxide, and a platinum metal column is connected between the two hollow spheres, and the inner hollow sphere is connected. Can not move in the outer hollow ball, the two hollow balls are concentric. Example 21 Preparation of Titanium Dioxide/Polyaniline Multilayer Composite Hollow Sphere and Concentric Double Layer Hollow Sphere

 The burr-like polyaniline/polystyrene-polyacrylic composite hollow sphere was prepared according to Example 12, and the composite particles were dispersed in 10 g of ethanol, and lg tetrabutyl titanate and lg water were added thereto, and the reaction temperature was 60 ° C. The reaction time was 4 h, that is, a titanium dioxide/polystyrene-polyacrylic acid/polyaniline composite hollow sphere was prepared, and the polyaniline was grown in the inner layer and the channel of the polymer hollow sphere shell, and the titanium dioxide was grown on the outer surface of the shell. After removing polystyrene and polyacrylic acid with tetrahydrofuran, a hollow sphere of titanium dioxide polyaniline double-layer structure is obtained, that is, a hollow sphere containing a polyaniline in a hollow sphere of titanium dioxide, and a polyaniline column is connected between the two hollow spheres, and the inner hollow sphere cannot be outside. The hollow ball moves, and the two hollow balls are concentric. Example 22 Preparation of Titanium Dioxide Multilayer Composite Hollow Sphere and Concentric Double Layer Hollow Sphere

Take a dry powder of lg polystyrene-polyacrylic acid hollow structure, the outer diameter of which is 400 nm, and the thickness of the shell layer is LOOnm, dispersed in 5g concentrated sulfuric acid for sulfonation treatment for 2 hours, centrifugal cleaning to obtain sulfonated modified polymer hollow sphere, the shell is the outer layer is sulfonated polystyrene, the middle layer is polystyrene, the inner layer is poly The three-layer structure of acrylic acid, so that the inner and outer layers of the shell are hydrophilic, and there are hydrophilic channels in the middle. The modified polymer hollow sphere was immersed in 1 g of 50% tetrabutylammonate titanate solution, soaked for 24 hours, centrifuged, and then added to 10 g of 40% water in butanol solution, 40 ° C After reacting for 6 hours, a titanium dioxide/polystyrene-polyacrylic multilayer composite hollow sphere was obtained, and titanium dioxide was grown on the inner layer, the channel and the outer layer of the polymer hollow spherical shell. The hollow sphere of this composite structure was sintered at 45 CTC for 2 hours to remove polystyrene and polyacrylic acid, thereby obtaining a hollow sphere of titanium dioxide double-layer structure. Example 23 Preparation of Silver Multilayer Composite Hollow Sphere and Concentric Double Layer Hollow Sphere

 Take O. lg polystyrene-polymethacrylic acid hollow structure dry powder, the outer diameter is 400nm, the thickness of the shell layer is lOOnm, dispersed in 5g concentrated sulfuric acid for sulfonation treatment for 2 hours, centrifugal cleaning to obtain sulfonation modification The polymer hollow sphere has a three-layer structure in which the outer layer is sulfonated polystyrene, the intermediate layer is polystyrene, and the inner layer is polymethacrylic acid, so that the inner layer and the outer layer of the shell are hydrophilic, and there is Hydrophilic channel. The modified polymer hollow sphere was immersed in 1 g of 20% silver nitrate aqueous solution, soaked for 24 hours, centrifuged, and then added to 10 g of 30% hydrazine hydrate solution, and reacted at 20 ° C for 6 hours to obtain silver/poly. A styrene-polymethacrylic multilayer composite hollow sphere, silver is grown in the inner layer, the channel and the outer layer of the polymeric hollow sphere shell. The hollow sphere of this composite structure was subjected to removal of polystyrene and polymethacrylic acid with N, N-dimethylformamide to obtain a silver double-layer hollow sphere. Example 24 Preparation of polyaniline multilayer composite hollow spheres and concentric double-layer hollow spheres

 0. lg polystyrene polyacrylic acid hollow structure dry powder, the outer diameter of 400nm, the thickness of the shell layer is lOOnm, dispersed in 5g concentrated sulfuric acid sulfonation treatment for 2 hours, centrifugal cleaning to obtain sulfonated modified polymer hollow The ball has a three-layer structure in which the outer layer is sulfonated polystyrene, the intermediate layer is polystyrene, and the inner layer is polyacrylic acid. Therefore, the inner layer and the outer layer of the shell are hydrophilic, and there is a hydrophilic passage in the middle. The modified polymer hollow sphere was immersed in 1 g of 30% ferric chloride solution, soaked for 24 hours, centrifuged, and then added to 10 g of water, added with 0.5 g of aniline, and the pH of the reaction solution was adjusted with concentrated hydrochloric acid. The value was 1-2, and the reaction was carried out in an ice water bath for 24 hours to obtain a polyaniline/polystyrene-polyacrylic multilayer composite hollow sphere, and the polyaniline was grown in the inner layer, the channel and the outer layer of the polymer hollow sphere shell. The hollow sphere of this composite structure was subjected to removal of polystyrene and polyacrylic acid with N, N-dimethylformamide to obtain a polyaniline bilayer hollow sphere. Example 25 Polybutyl acrylate was swelled and polymerized in a shell layer to prepare a polymer composite hollow sphere

 The octadecyl group contains 0.2% of dodecyl group in water, and is filled with nitrogen. Sodium sulfonate, adding 0. 2g of butyl acrylate and 2mg of azobisisobutyronitrile, swelled by magnetic stirring at room temperature for 8 hours, and heated at 80 ° C for 18 hours to obtain a polystyrene-polymethacrylic hollow sphere as a template. , a polymer composite hollow sphere of polybutyl acrylate grown in a shell.

Claims

 Claims

A method for preparing a hollow sphere and a composite hollow sphere by a template method, characterized in that the method for preparing a growth material in a polymer hollow sphere template shell is as follows:

 Lwt%~40. Owt%, so that the polymer particles are immersed in the 0. lwt%~40. The inorganic precursor solution penetrates into the cavity of the hollow sphere template of the polymer, and after centrifugation, the solution not infiltrated into the hollow cavity of the polymer hollow sphere template is centrifugally washed away; and then the obtained polymer hollow sphere containing the inorganic precursor solution is obtained. The mixture is added to the aqueous solution of the reaction mixture under stirring; the concentration of the template particles in the reaction solution is kept at 0. lwt%~40. Owt%, the reaction temperature is 0 ° C to 100 ° C, the reaction is completed, and the mixture is centrifuged to obtain a polymerization. a composite hollow sphere in which an inorganic material is grown in the inner layer of the hollow spherical shell; or

 0重量%的无机物。 The aqueous solution of the reaction solution is infiltrated into the polymer hollow sphere template particle cavity, and then the polymer hollow sphere containing the reaction component aqueous solution is added to the concentration of 10. 0wt%~60. In the precursor solution, the concentration of the template particles in the reaction solution is kept at 0. hrt%~40. (kt%, reaction temperature 0°C~100°C, the reaction is completed, and the mixture is centrifuged to obtain the inner layer of the polymer hollow spherical shell. a composite hollow sphere that grows inorganic matter; or

 l 重量%〜40. (kt%, kt%~40. (kt%, kt%~40. The metal ion salt solution is infiltrated into the cavity of the polymer hollow sphere template, and after the equilibrium is reached, the solution not penetrating into the cavity of the hollow polymer template is centrifuged and washed; then the obtained polymer hollow sphere containing the metal ion salt solution is Lwt%~60. The temperature of the template particles in the reaction solution is kept at 0. lwt%~40. 0wt°/., the reaction temperature is 0°C~10 (in the kt% reducing agent solution). TC, the reaction is completed, and the centrifugal cleaning is performed to obtain a composite hollow sphere in which the inner layer of the polymer hollow spherical shell grows metal; or

 First, 0.10%%~60. 0%^% of the reducing agent solution is infiltrated into the hollow cavity template particle cavity, and then the obtained polymer hollow ball containing the reducing agent sputum is added to the concentration of 10 under stirring. 0重量%〜60。 (kt% of the metal ion salt solution, the concentration of the template particles in the control solution is maintained at 0. lwt% ~ 40. 0wt%, reaction temperature (TC ~ 100 ° C, the reaction is completed, centrifugal cleaning , obtaining a composite hollow sphere of metal grown in the inner layer of the polymer hollow spherical shell; or

Lwt%~40 l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l 0wt%, the polymer monomer solution is infiltrated into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution not infiltrated into the cavity of the polymer hollow sphere template is centrifugally washed away; and then the obtained polymer-containing monomer solution is obtained. Lwt%〜40。 The weight of the template is maintained at 0. lwt%~40 0wt%, reaction temperature 0 ° C ~ 10 (TC, the reaction is completed, centrifugal cleaning, that is, a composite hollow sphere obtained by growing organic matter in the inner layer of the polymer hollow spherical shell; or

01重量%〜30. 0wt% initiator solution is infiltrated into the hollow cavity template particle cavity of the polymer, and then the obtained polymer hollow sphere containing the initiator solution is added to the concentration of 5^%~4 under stirring. 1⁄2« of polymer monomer solution, in The inert gas is introduced into the reaction vessel, and the concentration of the template particles in the reaction solution is controlled to be maintained at 0. lwt%~40wt%, the reaction temperature is 01:~100°C, the reaction is completed, and the mixture is centrifuged to obtain the organic matter of the inner layer of the polymer hollow sphere. Composite hollow sphere; (2). The polymer template obtained by the step (1.1) and the step (1.2) and the hollow sphere of the inorganic or metal composite are respectively placed in a sintering furnace, and air is passed, 0.1 to 10 ° C /min the speed is raised to 300~700 °C to burn, respectively, to obtain inorganic or metal hollow spheres;

 Alternatively, the polymer template obtained by the step (1.1), the step (1.2), and the step (1.3) and the hollow spheres of the inorganic, metal or organic compound are respectively extracted by using a selective solvent to remove the template polymer, respectively, to obtain an inorganic substance. , metal or organic hollow sphere; the outer diameter of the polymer hollow sphere template particles is 0.02 WI! ~ lOMm, the cavity volume is 10 to 95% of the entire microsphere; the inner hydrophilic polymer of the polymer hollow sphere template comprises polystyrenesulfonic acid, polymethacrylic acid, polyacrylic acid, polyvinyl alcohol, Polyamides, polyvinylpyrrole, poly(2-vinylpyridine), poly(4-vinylpyridine), polyhydroxyethyl methacrylate, polyvinyl ester, polyoxyethylene or polyvinyl ammonium chloride ;

 The outer lipophilic polymer of the polymeric hollow sphere template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, polymethyl Acrylic acid cinnamic acid ethyl ester, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly(tert-butyl acrylate), polyoxypropylene, polydimethylsilane, polyvinyl butyrate or polyisobutylene;

The selective solvent for removing the polymer template is chloroform, toluene, tetrahydrofuran, N,N-dimethylformamide; when preparing the SiO ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is An alcohol solution of Si (0CH ₃ ) ₄ , Si (0CH ₂ CH ₃ ) ₄ , Si{0CH(C3⁄4) ₂ } ₄ , Si(0CH ₂ C CH ₂ CH ₃ ) ₄ , N3⁄4Si0 ₃ ; 0. lwt% ~ 100wt% water alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~13;

In the preparation of the Ti0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is TiCl ₄ , Ti(0CH ₃ ) ₄ , Ti(0C3⁄4C3⁄4) ₄ , Ti{0CH(C3⁄4) ₂ } ₄ , Ti (0C) Mercury in CH ₂ C ) ₄ , TiOS 0 ₄

 Lwt°/。 The liquid of the reaction component is a concentration of 0. lwt ° /. ~100wt% water alcohol solution, the concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~13;

In the preparation of the Sn0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is SnCl ₄ , Sn(0CH ₃ ) ₄ , Sn (0C3⁄4CH ₃ ) ₄ , Sn {OCH (CH ₃ ) J ₄ , Sn ( _{0CH 2 CH 2 CH 2 CH 3} ) ₄ in an alcohol solution; concentration of reaction components aqueous 0. lwt% ~ 100wt ° /. Water alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its _P H value of 1~13;

In the preparation of a Zr0 ₂ hollow sphere or a composite hollow sphere, the inorganic precursor solution is ZrCl ₄ , Zr(0C ) ₄ , Zr(0C3⁄4CH , Zr{0CH(CH ₃ ) ₂ } ₄ , Zr (0CH ₂ CH ₂ CH ₂ C3⁄4) ₄ Zr (S0 ₄ ) ₂ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 10 (kt / water of alcohol solution, with a concentration of 35wt ° / concentrated hydrochloric acid or concentration of 25wt% thick Ammonia water adjusts its pH value:!~ 13;

In the preparation of the A1 ₂ 0 ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is A1C1 ₃ , A1(0CH ₃ ) ₃ , A1 (0CH ₂ C3⁄4) ₃ , A1 {0CH(C3⁄4) ₂ } ₃ , Al (0CH ₂ CH ₂ CH ₂ C3⁄4) ₃ , A1 ₂ (S0 ₄ ) ₃ alcohol solution; Alcohol solution of %~100wt% water, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt ° /. Concentrated ammonia water adjusts its pH value to 1~13;

In the preparation of a V ₂ 0 ₅ hollow sphere or a composite hollow sphere, the inorganic precursor solution is V0 (0C ) ₃ , V0 (0CH ₂ CH ₃ ) ₃ , V0 {0CH(CH ₃ ) ₂ } VO ( 0CH ₂ CH ₂ CH ₂ C3⁄4) ₃ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100wt% water in an alcohol solution, the concentration of 35rt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~ 13 _;

In the preparation of the ZnO hollow sphere or the composite hollow sphere, the inorganic precursor solution is an alcohol solution of Zn(N0 ₃ ) ₂ , Zn (00CCH ₃ ) ₂ , ZnCl ₂ , Zn (C10 ₄ ) ₂ ; The aqueous solution is a water or alcohol solution having a concentration of 0.1% by weight to 30% by weight of sodium hydroxide, potassium hydroxide or ammonia;

In the preparation of the W0 ₃ hollow spheres or the composite hollow spheres, the inorganic precursor solution is an aqueous solution of (M ₄ ) ₆ H ₂ W ₁₂ 0 ₄₁ , NaW0 ₃ ; the aqueous solution of the reaction component is a concentration of 0. Iw1: ~ 100wt% The alcoholic solution of water is adjusted to a pH of 1 to 13 with a concentration of 35 wt% concentrated hydrochloric acid or a concentration of 25 wt% concentrated ammonia water _;

In the preparation of the Mo0 ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is a Mo0 ₃ 23⁄40 aqueous solution; the reaction component aqueous solution is an alcohol solution having a concentration of 0.1 wt% to 100 wt% water, and a concentration of 35 wt% concentrated hydrochloric acid. Or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~13 _;

In the preparation of Al (0H) or Mg (OH) ₂ hollow spheres or composite hollow spheres, the inorganic precursor solution is an aqueous solution of soluble aluminum, magnesium chloride or sulfate; the aqueous solution of the reaction component is a concentration of 0. 01wt%~30wt% sodium hydroxide, potassium hydroxide or ammonia water;

When preparing the biomineralized material CaC0 ₃ , Ca ₁₀ (P0 ₄ )e (OH) ₂ , CaS0 ₄ , or BaS0 ₄ hollow sphere or composite hollow sphere, the inorganic precursor solution is C _a (0H) ₂ , CaCl _2, Ba (aq 0H> ₂ or BaCl _2; the aqueous reaction components containing ^{_{C0 3 2 -, P0 4 3}} -, SO- of Na ⁺ or K ⁺ salt thereof, or a concentration of 0. 01wt% ~

An aqueous solution of 30 wt% 3⁄4 C0 ₃ , P0 ₄ , H ₂ S0 ₄ ;

 01wt%~ The concentration of the aqueous solution of the reaction solution is 0. 01wt%~ 30% by weight aqueous solution of sodium sulfide or thiourea;

 01重量%。 The composition of the solution of the aqueous solution of the solution is 0.10% by weight of the aqueous solution of the solution of the metal cations of the soluble chloride, nitrate, sulfate; ~30wt% aqueous solution of sodium selenide or sodium telluride;

When the magnetic compound Fe ₃ 0 ₄ , Fe ₂ 0 ₃ or a ferrite hollow sphere or a composite hollow sphere containing zinc, manganese, cobalt, nickel, copper or magnesium is prepared, the inorganic precursor solution is Fe ^{2+ .} 01wt°。 The concentration of the aqueous solution of the reaction component is 0. 01wt °, Fe ³⁺ , Zn ²⁺ , Mn ²⁺ , Co ² \ Ni ²⁺ , Cu ² \ Mg ²⁺ soluble chloride, nitrate, sulphate aqueous solution; /. ~3 (kt /. aqueous solution of sodium hydroxide, potassium hydroxide or ammonia, or a concentration of lwt% ~ 60wt ^e / oK combined solution;

In the preparation of metal Au, A _g , Pt, Pd, Pb, Ni, Co, Cu, Fe hollow spheres or composite hollow spheres, the gold The ionic salt solution is an aqueous solution of the corresponding metal ion soluble perchlorate, chloride, nitrate, sulfate; the reducing agent solution is an aqueous solution of NaBH ₄ , LiB (C ₂ H ₅ ) ₃ H or N ₂ H ₄ ;

 In the preparation of a conductive polymer polyaniline, polypyrrole, polythiophene, polyparaphenylene acetylene and derivatives thereof hollow spheres or composite hollow spheres, the polymer monomer solution is a water or alcohol solution of the corresponding monomer; initiator The solution is an aqueous solution of potassium persulfate, ammonium persulfate or ferric chloride;

 In preparing a sensitive gel poly-N-isopropylacrylamide, polyacrylic acid, polymethacrylic hollow sphere or composite hollow sphere, the polymer monomer solution is N-isopropylacrylamide, acrylic acid, A a base acrylic acid or a water or alcohol solution thereof; the initiator solution is an aqueous solution of potassium persulfate or ammonium persulfate;

 The inert gas is nitrogen or argon;

 The alcohol solution is methanol, ethanol, propanol, isopropanol, butanol.

2. The method according to claim 1, characterized in that: the composite inorganic hollow spheres or hollow spheres _{comprising: Ti0 2, Si0 2, Sn0} 2, Zr0 2, A1 2 0 3, V 2 0 5 , ZnO, W0 ₃ , Mo0 ₃ , Al (0H) ₃ or Mg (0H) ₂ ; hollow spheres or composite hollow spheres of biomineralized materials include: CaC0 ₃ , Ca ₁₀ (P0 ₄ ) e (0H) ₂ , 8&50 ₄ or & _{4 4;} hollow sphere or composite hollow sphere of semiconductor material comprises: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; hollow sphere or composite hollow sphere of magnetic compound comprises: Fe ₃ 0 ₄ , Fe ₂ 0 ₃ or ferrite containing zinc, manganese or cobalt; hollow or composite hollow spheres of metal include: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe; hollow sphere or composite of organic matter The hollow spheres include: polyaniline, polypyrrole, polythiophene or polyparaphenylene vinylene and derivatives thereof, poly N-isopropylacrylamide, polyacrylic acid or polymethacrylic acid.

The method according to claim 1, wherein the step (1), the step (1.2), and the step (1.3) are respectively performed before the step (2) is performed. The composite hollow sphere is used as a template, and the steps (1.1), the step (1.2) and the step (1.3) are further repeated, respectively, to carry out a cyclic reaction, and when two or more cycles of the reaction form the same substance, the compound is added. The shell of the hollow sphere is thick; or

 The composite hollow sphere obtained in the step (1.2) or the step (1.3) is used as a template particle of the step (1.1) to carry out a cyclic reaction; or

 The composite hollow sphere obtained in the step (1.1) or the step (1.3) is used as a template particle of the step (1.2) to carry out a cyclic reaction; or

 The composite hollow sphere obtained in the step (1.1) or the step (1.2) is used as a template particle of the step (1.3) to carry out a cyclic reaction;

 When two or more cycles are reacted to form different kinds of substances, a composite hollow sphere of a plurality of substances is obtained.

4. A method for preparing a hollow sphere and a composite hollow sphere by a template method, characterized in that a hollow sphere template in a polymer Steps for preparing the inner layer of the shell and the hydrophilic channel growth material:

 Lwt%〜40. Owt%, the aqueous solution of the reaction component is infiltrated into the polymer hollow sphere. The polymer hollow sphere template particles are immersed in the aqueous solution of the reaction component, and the template particles are kept in the aqueous solution of the reaction component at a concentration of 0. lwt%~40. The cavity of the template is centrifuged to remove the solution that has not penetrated into the hollow cavity of the polymer hollow template, and then the obtained polymer hollow sphere containing the aqueous solution of the reaction component is added to the alcohol of the inorganic precursor under stirring. Lwt%〜40. Owt%,反应温度01 The reaction temperature is maintained at 0. 0wt%~l0. 0w1:% of a constant concentration; : ~ 100 ° C, the reaction is completed, centrifugal cleaning, the hollow template of the polymer template and the inorganic material with the surface of the burr-like substance is obtained, the hydrophilic channel is complexed, expanded and even protruded from the sphere, and the inner layer of the shell is continuously formed. Material; or

Lwt%〜40. 0wt%, the reducing agent solution is infiltrated into the polymer hollow spheres. The weight of the template is kept in the solution of the reducing agent solution. The cavity of the template is centrifuged to remove the solution that has not penetrated into the hollow cavity of the polymer hollow template; then the obtained polymer hollow sphere containing the reducing agent solution is added to the metal ion salt solution under the mixing, metal The ionic salt is maintained at a constant concentration of 0. 01wt%~ 10. 0%%; the concentration of the template particles in the reaction solution is kept at 0. lwt%~40. 0wt%, the reaction temperature is 0 °C~10 ( TC, the reaction is completed, centrifugal cleaning, that is, a polymer template with a ruthenium-like substance and a hollow sphere compounded with a metal, the hydrophilic channel is multiplexed, expanded or even protruded from the sphere, and the inner layer of the shell generates a continuous material; Lwt%〜40. 0重量%的使剂剂。 In the initiator solution, the concentration of the template particles in the solution is maintained at 0. lwt%~40. 0wt%, the initiator Solution infiltrated into polymer hollow The cavity of the ball template is centrifuged to remove the solution that has not penetrated into the hollow cavity of the polymer hollow template; then the obtained polymer hollow sphere containing the initiator solution is added to the polymer monomer solution under stirring. Lwt%~40 The concentration of the template particles in the reaction solution is maintained at 0. lwt%~40, the concentration of the template particles in the reaction solution is maintained at 0. lwt%~40 0wt%, reaction temperature 0°C~100°C, after completion of the reaction, centrifugal cleaning, the hollow template of the polymer template with the organic material on the surface of the enamel-like substance is obtained, and the hydrophilic channel is reshaped, expanded or even stretched. Out of the sphere, the inner layer of the shell generates a continuous material;

(2) The polymer template obtained in the step (1) and the inorganic material, the metal composite hollow sphere is placed in a sintering furnace, and air is passed, and the temperature is raised to 0.1 to 1 (TC/min to 300~700). °C burning to obtain inorganic or metallic hollow spheres with burrs on the surface; or

The hollow template of the polymer template obtained in the step (1) and the inorganic material, the metal and the organic compound are extracted by using a selective solvent to remove the template polymer, thereby obtaining a surface-burred inorganic, metal or organic hollow sphere; 02Mn! The outer diameter of the polymer hollow sphere template particles is 0. 02Mn! ~ lOMffl, the cavity volume is 10~95% of the entire microsphere; The inner hydrophilic polymer of the polymer hollow sphere template comprises polystyrenesulfonic acid, polymethacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide, polyvinylpyrrole, poly(2-vinylpyridine) ), poly(4-vinylpyridine), polyhydroxyethyl methacrylate, polyvinyl ester, polyoxyethylene or polyvinyl ammonium chloride;

 The outer lipophilic polymer of the polymeric hollow sphere template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, polymethyl Acrylic acid cinnamic acid ethyl ester, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly(tert-butyl acrylate), polyoxypropylene, polydimethylsilane, polyvinyl butyrate or polyisobutylene;

The selective solvent for removing the polymer template is chloroform, toluene, tetrahydrofuran or N, N-dimethylformamide; when preparing the SiO ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is An alcohol solution of Si (0CH ₃ ) ₄ , Si (0CH ₂ CH ₃ ) ₄ , Si{0CH(CH ₃ ) ₂ } ₄ , S1(0CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ or N3⁄4Si0 ₃ ; The concentration is 0. lwt%~ 100wt/. The alcoholic solution of water is adjusted to a pH of 1 to 13 with a concentration of 35 wt% concentrated hydrochloric acid or a concentration of 25 wt% concentrated ammonia water _;

In the preparation of the Ti0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is TiCl ₄ , Ti(0C3⁄4) ₄ , Ti (0CH ₂ CH ₃ ) ₄ , Ti {OCH (CH ₃ ) J ₄ , Ti (0C C¾CH ₂ C¾) alcoholic solution of TiOS0 ₄ or _4; aqueous reaction components at a concentration of 0. lwt% ~100wt% aqueous alcohol solution, concentrated hydrochloric acid with a concentration of 35wt% or concentration 25w1;% concentrated aqueous ammonia pH adjustment 1~ 13;

In the preparation of the Sn0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is SnCl ₄ , Sn(0C ) ₄ , Sn (0CH ₂ CH ₃ ) ₄ , Sn {OCH (CH ₃ ) ₂ } ₄ , An alcohol solution of Sn (0CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ ; the aqueous solution of the reaction component is a concentration of 0. lwt% ~ 10 (kt / water) alcohol solution, adjusted with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water Its pH is 1~13 _;

In the preparation of the Zr0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is ZrCl ₄ , Zr(0CH ₃ ) ₄ , Zr(0CH ₂ CH ₃ ) ₄ , Zr{0CH(CH ₃ )J ₄ , Zr (0C CH ₂ CH ₂ C ) ₄ , Zr (S0 ₄ ) ₂ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100wt% water alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated Ammonia water adjusts its pH to 1-13;

In the preparation of the A1 ₂ 0 ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is A1C1 ₃ , A1(0CH ₃ ) ₃ , A1(0C3⁄4C ) ₃ , A1{0CH(CH ₃ ) ₂ } ₃ , Al (0CH ₂ CH ₂ CH ₂ CH ₃ ) ₃ , A1 ₂ (S0 ₄ ) ₃ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100wt% water in an alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia water adjusts its pH value to 1~13;

In the preparation of a V ₂ 0 ₅ hollow sphere or a composite hollow sphere, the inorganic precursor solution is VO(OCH ₃ ) ₃ , VO(OCH ₂ C 3⁄4) ₃ , V0{0CH(CH ₃ ) , V0 (0CH ₂ An alcohol solution of CH ₂ CH ₂ CH ₃ ) ₃ ; an aqueous solution of the reaction component is an alcohol solution having a concentration of 0.1% to 100% water, and a concentration of 35 wt%/. Concentrated hydrochloric acid or a concentration of 25wt ° /. Concentrated ammonia water adjusts its pH value to 1~13;

In the preparation of the ZnO hollow sphere or the composite hollow sphere, the inorganic precursor solution is an alcohol solution of Zn(N0 ₃ ) ₂ , Zn(O0CCH ₃ ) ₂ , ZnCl ₂ , Zn(C10 ₄ ) ₂ ; The aqueous solution is a water or alcohol solution having a concentration of 0.0 bt% to 30% by weight of sodium hydroxide, potassium hydroxide or ammonia;

In the preparation of the W0 ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is (NH ₄ ) ₆ 11 ₂ 0 ₄₁ or ₃ . The aqueous solution of the reaction component is an alcohol solution having a concentration of 0. Iw1 100 wt% water, and the pH is adjusted to 1 13 by a concentration of 35 wt% hydrochloric acid or a concentration of 25 vrt% concentrated aqueous ammonia.

In the preparation of the Mo0 ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is a Mo0 ₃ 2H ₂ 0 aqueous solution; the reaction component aqueous solution is a concentration of 0.1 l _W t% 100 wt% water in an alcohol solution, with a concentration of 35 wt. % concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value to 13 _;

In the preparation of Al (OH) ₃ or Mg (OH) ₂ hollow spheres or composite hollow spheres, the inorganic precursor solution is a soluble aluminum or magnesium chloride or sulfate aqueous solution; the reaction component aqueous solution is a concentration of 0. 01wt% 30wt% aqueous solution of sodium hydroxide, potassium hydroxide or ammonia;

When preparing the biomineralized material CaC0 ₃ Ca _I0 (P0 ₄ ) ₆ (0H) ₂ , &50 ₄ or BaS0 ₄ hollow sphere or composite hollow sphere, the inorganic precursor solution is Ca(0H) ₂ CaCl ₂ Ba (0H) ₂ or an aqueous solution of BaCl ₂ ; the aqueous solution of the reaction component is a concentration of 0. 01 30^% containing C0 ₃ ² - P0 ₄ ³ - S0 ₄ ² - Na ⁺ or K + salt, or H ₂ C0 ₃ H ₃ P0 An aqueous solution of ₄ H ₂ S0 ₄ ; in the preparation of a semiconductor sulfide hollow sphere or a composite hollow sphere, the inorganic precursor solution is an aqueous solution of a soluble chloride, nitrate or sulfate of the corresponding metal cation; 0浓度1% 30 «Sodium sulfide or thiourea in water;

 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ % 30%% aqueous solution of sodium selenide or sodium hydride;

In the preparation of the magnetic compound Fe ₃ 0 ₄ Fe ₂ O ₃ or a ferrite hollow sphere or a composite hollow sphere containing zinc, manganese, cobalt, nickel, copper or magnesium, the inorganic precursor solution is Fe ²⁺ Fe ^3wt Zn ² \ Mn ² \ Co ² \ Ni ²⁺ Cu ² \ Mg ²⁺ soluble chloride, nitrate or sulphate aqueous solution; the reaction component aqueous solution is a concentration of 0. 01wt» / 3 (kt% hydrogen An aqueous solution of sodium oxide, potassium hydroxide or ammonia, or a hydrazine hydrate solution having a concentration of 1^« 60%;

In the preparation of a metal Au Ag Pt Pd Pb Ni 'Co Cu Fe hollow sphere or a composite hollow sphere, the metal ion salt solution is an aqueous solution of a corresponding metal ion soluble perchlorate, chloride, nitrate, sulfate; The solution is an ice solution of NaBH ₄ LiB (C _{2 3⁄4} ) ₃ H or N ₂ H ₄ ;

 In the preparation of a conductive polymer polyaniline, polypyrrole, polythiophene, polyparaphenylene acetylene and derivatives thereof hollow spheres or composite hollow spheres, the polymer monomer solution is a water or alcohol solution of the corresponding monomer; initiator The solution is an aqueous solution of potassium persulfate, ammonium persulfate or ferric chloride;

 In the preparation of the sensitive gel poly N-isopropyl acrylamide, polyacrylic acid, polymethacrylic hollow sphere composite hollow sphere, the polymer monomer solution is N-isopropyl acrylamide, acrylic acid, A a base acrylic acid or a water or alcohol solution thereof; the initiator solution is an aqueous solution of potassium persulfate or ammonium persulfate;

 The inert gas is nitrogen or argon;

The alcohol solution is methanol, ethanol, propanol, isopropanol, butanol.

The method according to claim 4, characterized in that: the composite inorganic hollow spheres or hollow spheres _{comprising: Ti0 2, Si0 2, Sn0} 2, Zr0 2, A1 2 0 3, V 2 0 5 , ZnO, W0 ₃ , Mo0 ₃ , A1 (0H) ₃ or Mg (0H) ₂ ; hollow spheres or composite hollow spheres of biomineralized materials include: CaC0 ₃ , Ca ₁₀ (P0 ₄ )e (OH) ₂ , 8&30 ₄ or &_304; semiconductor material hollow spheres or composite hollow sphere comprising: CdS, ZnS, PbS, CuS , CoS, FeS, CdTe, CdSe or the ZnSe; hollow sphere magnetic compound or composite hollow sphere comprising: Fe ₃ 0 _4, Fe ₂ 0 ₃ or ferrite containing zinc, manganese or cobalt; hollow or composite hollow spheres of metal include: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe; hollow sphere or composite of organic matter The hollow spheres include: polyaniline, polypyrrole, polythiophene or polyparaphenylene vinylene and derivatives thereof, poly N-isopropylacrylamide, polyacrylic acid or polymethacrylic acid.

6. A method for preparing a hollow sphere and a composite hollow sphere by a template method, characterized in that the method for preparing a material for growing a surface of a polymer hollow sphere template shell is:

 The polymer hollow sphere template particles are dispersed in an alcohol solution, the inorganic precursor solution and the aqueous solution of the reaction component are added, and the concentration of the inorganic precursor in the reaction liquid is controlled to be 0.01 Vrt% to 30 wt%, and the final concentration of the aqueous solution of the reaction component is determined. 0wt%〜50wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell; After the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere in which an inorganic substance is grown on the outer surface of the hollow shell of the polymer; the polymer template is removed to obtain an inorganic hollow sphere; or

 01wt%〜30wt%, template particles, the concentration of the metal ion salt in the reaction solution is 0. 01wt%~30wt%, the concentration of the reducing agent is 0. 01wt%~30wt%, the template particle is dispersed in the water, the metal ion salt solution and the reducing agent solution are added. The concentration is 0. lwt% ~ 40wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell; after the reaction is completed, centrifugal cleaning, that is, in the polymer a composite hollow sphere of metal grown on the outer surface of the hollow spherical shell; removing the polymer template to obtain a metal hollow sphere; or

01重量%〜2(kt%, 引 initiated, the polymerization of the polymer monomer monomer and the initiator solution is controlled. The concentration of the template is 0. 01wt%~ 20wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0°C~100°C, and the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell layer. After the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere of a polymer and an organic material grown on the outer surface of the hollow shell of the polymer; the template polymer is removed to obtain an organic hollow sphere; and the outer diameter of the hollow sphere template particle of the polymer is 0. 02Ρίΐ!~10Pm, the cavity volume is 10~95% of the whole microsphere _; the inner hydrophilic polymer of the polymer hollow sphere template includes polystyrenesulfonic acid, polymethacrylic acid, polyacrylic acid, Polyvinyl alcohol, polyamide, polyvinylpyrrole, poly(2-vinylpyridine), poly(4-vinylpyridine), polyhydroxyethyl methacrylate, polyvinyl ester, polyoxyethylene or polyethylene Ammonium chloride.

The outer lipophilic polymer of the polymeric hollow sphere template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, polymethyl Acrylic acid cinnamic acid ethyl ester, Polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polybutyl acrylate, polyoxypropylene, polydimethylsilyl, polyvinyl butyrate or polyisobutylene;

The selective solvent for removing the polymer template is chloroform, toluene, tetrahydrofuran or N, N-dimethylformamide; when preparing the SiO ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is Si (0CH ₃ ) ₄ , Si (0C3⁄4CH ,

_{Si {0CH (C) 2}} 4, 51 (0 (¾ (¾ (¾) alcoholic solution of N¾Si0 ₃ or _4; aqueous reaction components at a concentration of 0. lwt% ~

100wt°/. The alcoholic solution of water is adjusted to a pH of 1 to 13 with a concentration of 35 wt% concentrated hydrochloric acid or a concentration of 25 wt% concentrated aqueous ammonia;

In the preparation of the Ti0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is TiCl ₄ , Ti(0CH ₃ ) ₄ ,

_{Ti (0CH 2 CH 3) 4} , Ti {OCH (CH 3) J 4, Ti (0CH 2 CH 2 CH 2 CH 3) ₄ or alcoholic solution of TiOS0 _4; aqueous reaction components at a concentration of 0. lwt% ~ lOOwty . The alcoholic solution of water is adjusted to a pH of 1~ with a concentration of 35 % concentrated hydrochloric acid or a concentration of 25 wt% concentrated ammonia water.

13;

In the preparation of the Sn0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is SnCl ₄ , Sn(0CH ₃ ) ₄ , Sn (0CH ₂ CH ₃ ), Sn {OCH (CH ₃ ) ₂ } ₄ or An alcohol solution of Sn (0CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ ; an aqueous solution of the reaction component is an alcohol solution having a concentration of 0.1 wt% to 100 wt% of water, and the pH is adjusted by a concentration of 35 wt% concentrated hydrochloric acid or a concentration of 25 wt% concentrated ammonia water. 1 to 13;

In the preparation of the Zr0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is ZrCl ₄ , Zr(0C3⁄4) ₄ , Zr (0CH ₂ CH ₃ ) ₄ , Zr {OCH (CH ₃ ) ₂ } ₄ , Zr (0CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ or Zr (S0 ₄ ) ₂ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100wt% water in an alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt % concentrated ammonia water adjusts its pH value to 1~13;

In the preparation of the A1A hollow sphere or the composite hollow sphere, the inorganic precursor solution is A1C1 ₃ , A1(0CH ₃ ) ₃ , A1(0CH ₂ CH ₃ ) ₃ , A1{0CH(CH ₃ ) ₂ } ₃ , A1 (0C C CH ₂ CH ₃ ) ₃ or A1 ₂ (S0 ₄ ) ₃ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100wt% water in an alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% Concentrated ammonia water adjusts its pH value to 1~13;

In the preparation of a V ₂ 0 ₅ hollow sphere or a composite hollow sphere, the inorganic precursor solution is V0(0C3⁄4) ₃ , V0(0CH ₂ CH ₃ ) ₃ , V0{0CH(CH ₃ )J ₃ or V0 ( 0CH ₂ C3⁄4CH ₂ CH ₃ ) ₃ alcohol solution; the reaction component aqueous solution is a concentration of 0. l _w t% ~ 100 _W t% water in an alcohol solution, the concentration of 35w « concentrated hydrochloric acid or a concentration of 25wt3⁄43⁄4 ammonia water to adjust its _P H value 1 to 13;

In the preparation of the ΖηΟ hollow sphere or the composite hollow sphere, the inorganic precursor solution is an alcohol solution of Zn(N0 ₃ ) ₂ , Zn(00CC ) ₂ , ZnCl ₂ or Zn(C10 ₄ ) ₂ ; a water or alcohol solution having a concentration of 0.0 rt% to 30% by weight of sodium hydroxide, potassium hydroxide or ammonia;

W0 ₃ in the preparation of a composite hollow sphere or hollow sphere, the inorganic precursor solution is an aqueous solution (Li _{4) 612 041} or NaTO _3; the concentration of the reaction solution as component 0. lwt~100 _W t / _K of Alcohol solution, with a concentration of 35wt% 3⁄43⁄4 hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~13;

In the preparation of hollow spheres or Mo0 ₃ composite hollow sphere, the inorganic precursor solution of aqueous Mo0 ₃ 2H ₂ 0; the concentration of the reaction solution as component 0. lwt ° /. ~10 (kt ° / water alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia Water adjustment pH value of 1~13;

In the preparation of A1 (0H) ₃ or Mg (0H) ₂ hollow spheres or composite hollow spheres, the inorganic precursor solution is an aqueous solution of soluble aluminum, magnesium chloride, and sulfate; 01wt%~30wt% aqueous solution of sodium hydroxide, potassium hydroxide or ammonia;

In the preparation of biomineralized materials CaC0 ₃ , C _ai . (P0 ₄ ) ₆ (0H) ₂ , CaS0 ₄ , or BaS0 ₄ hollow sphere or composite hollow sphere, the inorganic precursor solution is Ca(0H) ₂ , CaCl ₂ , Ba (0H) ₂ or BaCl ₂ The aqueous solution of the reaction component is a Na+ or Κ+ salt containing CO/—, P0—, SO, or an aqueous solution having a concentration of 0.01 wt% 〜30 wt»/^ 3⁄4 C0 ₃ , P0 ₄ or H ₂ S0 ₄ ;

 0lwt%〜30w1。 The solution of the aqueous solution of the solution is a solution of the corresponding metal cations of the soluble chloride, nitrate or sulphate; : % aqueous solution of sodium sulfide or thiourea;

 01wtwt。 The solution of the aqueous solution of the solution is a concentration of 0. 01wt %~ 30wt/M® sodium or sodium hydride solution;

In the preparation of the magnetic compound Fe ₃ 0 ₄ or F 0 ₃ or a ferrite hollow sphere or a composite hollow sphere containing zinc, manganese, cobalt, nickel, copper or magnesium, the inorganic precursor solution is Fe ²⁺ , a solution of a soluble chloride, a nitrate or a sulfate of Fe ³⁺ , Zn ²⁺ , Mn ² \ Co ² \ Ni ² Cu ²⁺ or Mg ²⁺ ; a concentration of the aqueous solution of the reaction component is 0. 0lw1: %~30wt% An aqueous solution of sodium hydroxide, potassium hydroxide or aqueous ammonia, or a hydrazine hydrate solution having a concentration of from 1% by weight to 60% by weight;

In the preparation of metal Au, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow spheres or composite hollow spheres, the metal ion salt solution is a corresponding metal ion soluble perchlorate, chloride, nitrate Or an aqueous solution of a sulfate; the reducing agent solution is an aqueous solution of NaBH ₄ , LiB (C ₂ ) ₃ H or N ₂ H ₄ ; in preparing a conductive polymer polyaniline, polypyrrole, polythiophene, polyparaphenylene acetylene and its derivatives When the hollow sphere or the composite hollow sphere is used, the polymer monomer solution is a water or alcohol solution of the corresponding monomer; the initiator solution is an aqueous solution of potassium persulfate, ammonium persulfate or ferric chloride;

 In the preparation of a sensitive gel poly-N-isopropylacrylamide, polyacrylic acid, polymethacrylic hollow sphere or composite hollow sphere, the polymer monomer solution is a monomer N-isopropyl acrylamide, acrylic acid , methacrylic acid or its water or alcohol solution; the initiator solution is an aqueous solution of potassium persulfate or ammonium persulfate;

 The inert gas is nitrogen or argon.

 The alcohol solution is methanol, ethanol, propanol, isopropanol, butanol.

7. The method according to claim 6, characterized in that: the composite inorganic hollow spheres or hollow spheres _{comprising: Ti0 2, Si0 2, Sn0} 2, Zr0 2, A1 2 0 3, V 2 0 5 , Zn0, W0 ₃ , Mo0 ₃ , Al (0H) ₃ or Mg (0H) ₂ ; hollow spheres or composite hollow spheres of biomineralized materials include: C _a C0 ₃ , Ca ₁₀ (P04) ₆ (0H) ₂ , BaS0 ₄ or CaS0 _4; hollow sphere of semiconductor material Or composite hollow spheres include: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; hollow spheres or composite hollow spheres of magnetic compounds include: Fe ₃ 0 ₄ , Fe ₂ 0 ₃ or zinc, manganese, Cobalt ferrite; metal hollow sphere or composite hollow sphere includes: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe _; organic hollow sphere or composite hollow sphere includes: polyaniline, polypyrrole, Polythiophene or polyparaphenylene vinylene and its derivatives, poly N-isopropylacrylamide, polyacrylic acid or polymethacrylic acid.

A method for preparing a hollow sphere and a composite hollow sphere by a template method, characterized in that the method for preparing a double-layered hollow sphere of an eccentric structure -

Lwt%〜40. Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, Owt%, The inorganic precursor solution is infiltrated into the cavity of the hollow sphere template of the polymer, and after reaching equilibrium, the solution not infiltrated into the hollow cavity of the polymer hollow sphere is centrifuged; then the obtained polymer containing the inorganic precursor solution is hollow The weight of the template particles in the reaction solution is maintained at 0. lwt%~40. (kt%, reaction temperature 0 ° C ~ 100 ° C, the reaction is completed, centrifugal cleaning, ie Obtaining a composite hollow sphere in which an inorganic substance is grown in an inner layer of a polymer hollow spherical shell; or

 0重量%的无机物。 The aqueous solution of the reaction solution is infiltrated into the polymer hollow sphere template particle cavity, and then the polymer hollow sphere containing the reaction component aqueous solution is added to the concentration of 10. 0wt%~60. In the precursor solution, the concentration of the template particles in the reaction solution is maintained at 0. lwt%~40. 0wt%, the reaction temperature is 0°C~100°C, the reaction is completed, and the centrifugal cleaning is performed to obtain the inner layer growth of the polymer hollow spherical shell. Composite hollow sphere of inorganic matter; or

 Lwt%~40. 0wt%, making metal, the metal particles are immersed in the 0. lwt%~40. 0wt%, the metal The ionic salt solution penetrates into the cavity of the hollow sphere template of the polymer, and after centrifuging, the solution that has not penetrated into the hollow cavity of the polymer hollow sphere is centrifuged and washed; then the obtained polymer hollow sphere containing the metal ion salt solution is stirred under stirring 0wt°/。 Add to 0. 01wt%~60. 0wt°/. In the reducing agent solution, the concentration of the template particles in the reaction solution is maintained at 0. lwt%~40. 0wt%, the reaction temperature is 0 ° C ~ 10 (TC, the reaction is completed, centrifugal cleaning, that is, the polymer hollow spherical shell is obtained a composite hollow sphere of metal growth; or

 0wt 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 %wt0~40. (kt%, reaction temperature 0 ° C ~ 100 ° C, the reaction is completed, centrifugal cleaning, 0%% of the metal ion salt solution, the concentration of the template particles in the control solution is maintained at 0. lwt% ~ 40. (kt%, reaction temperature 0 ° C ~ 100 ° C, the reaction is completed, centrifugal cleaning, Obtaining a composite hollow sphere of metal grown in the inner layer of the polymer hollow spherical shell; or

Lwt%~40. 0wt 0. lwt%~40. 0wt 0. lwt%~40. 0wt 0. lwt%~40. 0wt %, the polymer monomer solution is infiltrated into the cavity of the polymer hollow sphere template, and after reaching equilibrium, the solution not infiltrated into the cavity of the hollow polymer template is centrifuged; then the polymerization of the obtained polymer-containing monomer solution is carried out; 1wt%~ The concentration of the template particles in the reaction solution is maintained at 0. 1wt%~

40. Owt%, reaction temperature 0 ° C ~ 10 (TC, the reaction is completed, centrifugal cleaning, that is, a composite hollow sphere of the inner growth organic matter of the polymer hollow spherical shell; or

01重量%~30. 0wt% initiator solution is infiltrated into the hollow cavity template particle cavity of the polymer, and then the obtained polymer hollow sphere containing the initiator solution is added to the concentration of 5 _W t%~40 under stirring. _W i:% polymer in a monomer solution; in the reaction vessel into an inert gas, controlling the concentration of particles in the reaction mixture is maintained at a template 0. lwt% ~ 40wt%, the reaction temperature of 0 ° C ~ 100 ° C, the reaction After completion, centrifugal cleaning, obtaining a composite hollow sphere of organic matter in the inner layer of the polymer hollow sphere;

(2) Dispersing the composite hollow sphere of the inner layer-grown inorganic material obtained in the step (1.1) in an alcohol solution, adding the inorganic precursor and the aqueous solution of the reaction component, and controlling the concentration of the inorganic precursor in the reaction solution. Lwt%〜40wt°/. The concentration of the template particles is 0. lwt%~40wt°/. , the reaction temperature is 0 ° C ~ 100 。. C, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell; after the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere which grows inorganic substances on the outer surface and the inner layer of the hollow shell of the polymer;

 01wt%〜3(kt%, kt%, kt%, kt%, 3%, kt%, 3% The concentration of the reducing agent is 0. 01wt%~ 30wt%, the concentration of the template particles is 0. lwt ° /. ~ 40wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction product is deposited on the outer surface of the hollow shell of the polymer, forming Continuous shell; after completion of the reaction, centrifugal cleaning, that is, a composite hollow sphere in which metal and inner layer growth inorganic substances are grown on the outer surface of the polymer hollow spherical shell;

 Dissolving the inner hollow inorganic composite hollow sphere obtained in the step (1.1) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the concentration of the polymer monomer in the reaction liquid. 01重量%〜20重量%, The initiator concentration is 0. 01wt%~20wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0 °C~100 °C, the reaction product is deposited in the polymer hollow The outer surface of the spherical shell forms a continuous shell; after the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere in which an organic substance and an inner layer of inorganic substances are grown on the outer surface of the polymer hollow spherical shell;

 01wt%~ The concentration of the inorganic precursor in the reaction solution is 0. 01wt%~ 30wt%, the final concentration of the aqueous solution of the reaction component is 0. lwt%~50wt%, the concentration of the template particles is 0. lwt% ~ 40wt%, the reaction temperature is 0'C ~ 100 ° C, the reaction product is deposited in the polymer hollow The outer surface of the spherical shell forms a continuous shell layer; after the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere which grows inorganic substances and inner layer growing metal on the outer surface of the polymer hollow spherical shell;

 01重量%〜30重量%的再生剂浓度。 The concentration of the metal ion salt in the reaction solution is 0. 01wt%~30wt%, reducing agent concentration Lwt%〜40wt/。 The concentration of the template particles is 0. lwt% ~ 40wt /. , the reaction temperature is 0 ° C ~ 100 ° C, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell; after the reaction is completed, centrifugal cleaning, the metal is grown on the outer surface and inner layer of the hollow shell of the polymer Composite hollow sphere; or

Dispersing the inner hollow metal composite hollow sphere obtained in the step (1.2) in water, and introducing inertness into the reaction vessel O. 01wt°/. The concentration of the initiator is 0. 01wt%~20wt%, the concentration of the initiator is 0. 01wt ° /. Lwt°/。 The concentration of the template particles is 0. lwt ° /. ~40wt°/. , the reaction temperature is 0 ° C ~ 100 ° C, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell; after the reaction is completed, centrifugal cleaning, the organic matter and the inner layer are grown on the outer surface of the hollow shell of the polymer a composite hollow sphere of growing metal; or

 01wt%~ The concentration of the inorganic precursor in the reaction solution is 0. 01wt%~ 30重量%, The final concentration of the aqueous solution of the reaction component is 0. lrt% ~ 50wt%, the concentration of the template particles is 0. lwt% ~ 40wt%, the reaction temperature is 0 Ό ~ 100. C, the reaction product is deposited on the outer surface of the hollow shell of the polymer, 'forming a continuous shell layer; after the reaction is completed, centrifugal cleaning, that is, a composite hollow sphere for growing inorganic substances and inner layer growing organic matter on the outer surface of the hollow shell of the polymer; Or

 01重量%〜30重量%, reducing agent concentration, the concentration of the metal ion salt in the reaction solution is controlled by the concentration of the metal ion salt in the reaction solution. 0wt°/。 The concentration of the template particles is 0. lwt ° /. 〜40wt%, reaction temperature 0°C~10(TC, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell; after the reaction is completed, centrifugal cleaning, the metal is grown on the outer surface of the hollow shell of the polymer a composite hollow sphere with an inner layer of organic matter; or

Dissolving the composite hollow sphere of the inner layer growing organic body obtained in the step (1.3) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the concentration of the polymer monomer in the reaction liquid. 01重量%〜20wt%, initiator concentration 0. 01wt%-20wt%, the concentration of the template particles is 0. lwt% ~ 40wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction product is deposited in the polymer hollow sphere The singularity of the outer diameter of the polymer hollow sphere template is 0. 02Mm ~10f3⁄4, the cavity volume is 10~95% of the whole microsphere _; the inner hydrophilic polymer of the polymer hollow sphere template comprises polystyrenesulfonic acid, polymethacrylic acid, polyacrylic acid, polyvinyl alcohol, Polyamides, polyvinylpyrrole, poly(2-vinylpyridine), poly(4-vinylpyrene!3⁄4), polyhydroxyethyl methacrylate, polyvinyl ester, polyoxyethylene or polyvinyl chloride Ammonium

 The outer lipophilic polymer of the polymeric hollow sphere template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, polymethyl Acrylic acid cinnamic acid ethyl ester, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polybutyl acrylate, polyoxypropylene, polydimethylsilyl, polyvinyl butyrate or polyisobutylene;

The selective solvent for removing the polymer template is chloroform, toluene, tetrahydrofuran or N, N-dimethylformamide; when preparing the SiO ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is An alcohol solution of Si (0CH ₃ ) ₄ , Si (0CH ₂ CH ₃ ) ₄ , Si {0CH (CH ₃ ) ₂ } ₄ , Si (0CH ₂ CH ₂ C CH ₃ ) ₄ , N3⁄4Si0 ₃ ; The concentration of 0. lwt% ~ 100wt% water alcohol solution, the concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its _P H value of 1~13;

In the preparation of the Ti0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is TiCl ₄ , Ti (0C3⁄4) ₄ , _{Ti (0CH 2 CH 3) 4} , Ti {0CH (CH 3) 2} 4, Ti (0CH 2 CH 2 C CH 3) alcoholic solution of _{4, TiOS0 4;} the reaction components to an aqueous solution of a concentration of 0. lwt ° / fl ~100wt°/. Aqueous solution of water with a concentration of 35wt»/. Concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~13;

In the preparation of the Sn0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is SnCl ₄ , Sn(0C3⁄4) ₄ , Sn(0CH ₂ C ) ₄ , Sn{0CH(CH ₃ ) ₂ } ₄ , Sn The alcohol solution of (0CH ₂ CH ₂ C3⁄4CH ₃ ) ₄ ; the aqueous solution of the reaction component is an alcohol solution having a concentration of 0.1 wt% to 100 wt% of water, and the pH is adjusted by a concentration of 35 _W t% 3⁄4 hydrochloric acid or a concentration of 25 wt% concentrated ammonia water. 1 to 13;

In the preparation of the Zr0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is ZrCl ₄ , Zr(0C3⁄4) ₄ , Zr(0C C ) ₄ , Zr{0CH(CH ₃ ) ₂ } ₄ , Zr ( 0CH ₂ C CH ₂ CH ₃ ) ₄ , Zr (S0 ₄ ) ₂ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100wt% water alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water Adjust its pH value to 1~13;

In the preparation of the A1 ₂ 0 ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is A1C1 ₃ , A1(0C3⁄4) ₃ , A1(0CH ₂ CH ₃ ) ₃ , A1{0CH(CH ₃ ) ₂ } ₃ , Al (0CH ₂ CH ₂ C3⁄4C) ₃ , A1 ₂ (S0 ₄ ) ₃ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100vrty ^ J alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt % concentrated ammonia water adjusts its pH value to 1~13;

In the preparation of a V ₂ 0 ₅ hollow sphere or a composite hollow sphere, the inorganic precursor solution is V0(0CH ₃ ) ₃ , V0(0C3⁄4CH ₃ ) ₃ , V0{0CH(CH ₃ ) , V0(0CH ₂ CH ₂ CC) alcoholic solution of _3; component of the reaction solution at a concentration of 0. lwt% ~100wt% aqueous alcohol solution, the adjusted value of _P H 1~13 with concentrated hydrochloric acid concentration of 35wt% or 25wt% concentration of concentrated aqueous ammonia;

In the preparation of the ZnO hollow sphere or the composite hollow sphere, the inorganic precursor solution is an alcohol solution of Zn(N0 ₃ ) ₂ , Zn(00CC3⁄4) ₂ , ZnCl ₂ , Zn(C10 ₄ ) ₂ ; The concentration is 0.01wt»/. ~30% by weight of water or alcohol solution of sodium hydroxide, potassium hydroxide or ammonia;

W0 ₃ in the preparation of a composite hollow sphere or hollow sphere, the inorganic precursor solution of (NH ₄₎ an aqueous solution of ₂ W ₁₂ 0 _{41, NaW0 3} of _e H; reaction components at a concentration of 0. lwt~100wt% aqueous solution of water The alcohol solution was used at a concentration of 35 wt ° /. Concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~13;

In the preparation of the MoO ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is a Mo0 ₃ 2H ₂ 0 aqueous solution; the reaction component aqueous solution is a concentration of 0. lwt%~10 (kt% water in an alcohol solution, using a concentration 35w1* concentrated hydrochloric acid or a concentration of 25w « concentrated ammonia water to adjust its pH value of 1~13;

 In the preparation of Al (0H) or Mg (OH) hollow spheres or composite hollow spheres, the inorganic precursor solution is an aqueous solution of soluble aluminum or magnesium chloride or sulfate; the aqueous solution of the reaction component is 0.01 wt%. ~30wt% sodium hydroxide, potassium hydroxide or ammonia water;

When preparing the biomineralized material CaC0 ₃ , Ca ₁₀ (P0 (0H) ₂ , CaS0 ₄ , or BaS0 ₄ hollow sphere or composite hollow sphere, the inorganic precursor solution is Ca(0H) ₂ , CaCl ₂ , An aqueous solution of Ba(0H) ₂ or BaCl ₂ ; the aqueous solution of the reaction component is a Na ⁺ or K ⁺ salt containing C0 ₃ ² -, P0, S0 ₄ ² - or a concentration of 0.01 wt% to 30 wt% H ₂ C0 ₃ , An aqueous solution of H ₃ P0 ₄ , H ₂ S0 ₄ ; in the preparation of a semiconductor sulfide hollow sphere or a composite hollow sphere, the inorganic precursor solution is a corresponding metal cation An aqueous solution of sodium chloride or thiourea; a concentration of 0. 01wt%~30rt% of an aqueous solution of sodium sulfide or thiourea;

 01重量%。 The composition of the solution of the aqueous solution of the solution is 0.10% by weight of the aqueous solution of the solution of the metal cations of the soluble chloride, nitrate, sulfate; ~30wt% aqueous solution of sodium selenide or sodium telluride;

In the preparation of the magnetic compound Fe ₃ 0 ₄ , Fe ₂ 0 ₃ or a ferrite hollow sphere or a composite hollow sphere containing zinc, manganese, cobalt, nickel, copper or magnesium, the inorganic precursor solution is Fe ² Fe ^{3 \ ZrT, Mn 2 \ Co} 2 \ Ni 2 Cu 2 \ Mg 2+ soluble chloride, nitrate, sulfate aqueous solution; concentration of the reaction components to an aqueous solution of 0. 01wt /. ~30 _W t% aqueous solution of sodium hydroxide, potassium hydroxide or ammonia, or a concentration of lwt%~60wt ° /. Hydrazine hydrate solution;

In the preparation of metal Au, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow spheres or composite hollow spheres, the metal ion salt solution is a corresponding metal ion soluble perchlorate, chloride, nitrate An aqueous solution of a sulfate; the reducing agent solution is an aqueous solution of NaBH ₄ , LiB (C ₂ H ₅ ) ₃ H or N ₂ H ₄ ;

 In the preparation of a conductive polymer polyaniline, polypyrrole, polythiophene, polyparaphenylene acetylene and derivatives thereof hollow spheres or composite hollow spheres, the polymer monomer solution is a water or alcohol solution of the corresponding monomer; initiator The solution is an aqueous solution of potassium persulfate, ammonium persulfate or ferric chloride;

 In preparing a sensitive gel poly-N-isopropylacrylamide, polyacrylic acid, polymethacrylic hollow sphere or composite hollow sphere, the polymer monomer solution is N-isopropylacrylamide, acrylic acid, A a base acrylic acid or a water or alcohol solution thereof; the initiator solution is an aqueous solution of potassium persulfate or ammonium persulfate;

 The inert gas is nitrogen or argon;

 The alcohol solution is methanol, ethanol, propanol, isopropanol or butanol.

9. The method according to claim 8, characterized in that: the composite inorganic hollow spheres or hollow spheres _{comprising: Ti0 2, Si0 2, Sn0} 2, Zr0 2, A1 2 0 3, V 2 0 5 , Zn0, W0 ₃ , Mo0 ₃ , Al (0H) ₃ or Mg (0H) _2; hollow spheres or composite hollow spheres of biomineralized materials include: CaC0 ₃ , Ca ₁₀ (P0 ₄ )e(OH) ₂ , BaS0 ₄ or CaS0 _4; the hollow sphere or composite hollow sphere of the semiconductor material comprises: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; the hollow sphere or composite hollow sphere of the magnetic compound comprises: Fe ₃ 0 ₄ , Fe ₂ 0 ₃ or ferrite containing zinc, manganese or cobalt; hollow or composite hollow spheres of metal include: Au, A _g , Pt, Pd, Pb, Ni, Co, Cu or Fe; hollow spheres of organic matter or The composite hollow spheres include: polyaniline, polypyrrole, polythiophene or polyparaphenylene vinylene and derivatives thereof, poly N-isopropylacrylamide, polyacrylic acid or polymethacrylic acid.

10. A method for preparing a hollow sphere and a composite hollow sphere by a template method, characterized in that the method for preparing a two-layer hollow sphere of concentric structure -

(1. 1) Soaking the polymer hollow sphere template particles in the aqueous solution of the reaction component, the template particles are kept thick in the solution 0wt%〜40. 0wt%, the reaction component aqueous solution is infiltrated into the cavity of the polymer hollow sphere template, after reaching equilibrium, the solution not infiltrated into the hollow cavity template cavity is centrifuged and washed; 01重量%〜10. (1⁄21% of a constant concentration; control; the polymer hollow sphere containing the aqueous solution of the reaction component is added to the alcohol solution of the inorganic precursor, the inorganic precursor is maintained by a constant supplement at 0. 01wt%~10. The concentration of the template particles in the reaction solution is maintained at 0. lwt%~40. 0wt%, the reaction temperature is 0°C~10 (TC, the reaction is completed, and the mixture is centrifuged to obtain a polymer template with a surface of the burr-like substance and the inorganic compound. Hollow sphere; or

 Lwt%〜40. The reducing agent solution is infiltrated into the polymerization. The concentration of the template particles in the solution is 0. lwt%~40. The cavity of the hollow sphere template is centrifuged to remove the solution that has not penetrated into the cavity of the hollow polymer template, and then the obtained polymer hollow sphere containing the reducing agent solution is added to the metal ion salt solution under stirring. Lwt%~40. 0wt%, reaction temperature 0°C, the concentration of the template particles in the reaction solution is maintained at 0. lwt%~40. 0wt%, reaction temperature 0°C, the constant concentration of the metal ion salt is maintained at 0. 01wt%~10. ~10 (TC, the reaction is completed, centrifugal cleaning, that is, the hollow template of the polymer template with the surface of the burr-like substance and the metal; or

 Lwt% 40. (kt%) kt% 40. (kt%) kt% 40. (kt%) , the initiator solution is infiltrated into the cavity of the hollow polymer template of the polymer, after the equilibrium is reached, the solution not infiltrated into the cavity of the hollow polymer template is centrifuged, and then the obtained polymer hollow sphere containing the initiator solution is stirred. The catalyst monomer is added to the polymer monomer solution, and the polymer monomer is maintained at a constant concentration of 0.01%~10. (1⁄21 °/.); an inert gas is introduced into the reaction vessel to control the template in the reaction solution. The concentration of the particles is maintained at 0. lwt%~40. 0wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction is completed, centrifugal cleaning, that is, the hollow template of the polymer template and the organic compound with the surface of the burr-like substance is obtained;

(2) Dispersing the composite hollow spheres of the inner layer and the channel growth inorganic material obtained in the step (1.1) in an alcohol solution, adding an inorganic precursor solution and an aqueous solution of the reaction component, and controlling the inorganic precursor in the reaction liquid. Lwt°/. The final concentration of the aqueous solution of the reaction component is 0. lwt ° /. 〜50wt%, the concentration of the template particles is 0. lwt% ~ 4 (kt%, reaction temperature 0 ° C ~ 10 (TC, the reaction product deposited on the outer surface of the polymer hollow sphere shell, forming a continuous shell; reaction is completed, Centrifugal cleaning, that is, a composite hollow sphere in which an inorganic substance is grown on the outer surface, the inner layer and the channel of the hollow shell of the polymer; the polymer template is removed to obtain a double-layered inorganic hollow sphere, that is, the hollow sphere contains a hollow sphere, and the obtained In the inorganic hollow sphere, there is an inorganic column connected between the two hollow spheres, the inner hollow sphere cannot move in the outer hollow sphere, and the two hollow spheres are concentric; or the inner layer and the channel obtained by the step (1.1) are hollow composite hollow. The weight of the template particles is 0. 01wt%~3C rt%, the concentration of the reducing agent is 0. 01wt°/.~30wt%, and the concentration of the template particles is 0. 1wt%~40wt ° /., reaction temperature 0 ° C ~ 10 (TC, the reaction product is deposited on the outer surface of the polymer hollow spherical shell to form a continuous shell; after the reaction is completed, centrifugal cleaning, that is, in the polymer hollow ball a composite hollow sphere in which metal and inner layer and channel growth inorganic substance are grown on the outer surface of the casing; The double-layered metal-inorganic hollow sphere, that is, the hollow metal sphere contains an inorganic hollow sphere, and the obtained double-layer hollow sphere has an inorganic column connected between the two hollow spheres, and the inorganic hollow sphere cannot be in the hollow metal sphere. Internal movement, two hollow balls concentric; or

 Dispersing the inner layer and the channel-forming inorganic composite hollow sphere obtained in the step (1.1) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the polymer single in the reaction liquid. 01重量%〜20wt%, initiator concentration 0. 01wt%~20wt%, the concentration of the template particles is 0. lwt% ~ 40wt%, the reaction temperature is 0 ° C ~ 100 Ό, the reaction product is deposited in the polymer hollow The outer surface of the spherical shell forms a continuous shell layer; after the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere in which an organic substance and an inner layer and a channel are grown on the outer surface of the hollow shell of the polymer; the polymer template is removed to obtain a double layer structure. The organic-inorganic hollow sphere, that is, the organic hollow sphere contains an inorganic hollow sphere, and the obtained double-layer hollow sphere has an inorganic column connected between the two hollow spheres, and the inorganic hollow sphere cannot move in the hollow sphere of the organic matter, Hollow ball concentric; or

 The weight of the inorganic precursor in the reaction liquid is 0. 01wt. The weight of the inorganic precursor in the reaction liquid is 0. 01wt %〜30wt%, the final concentration of the aqueous solution of the reaction component is 0. lwt%~50wt%, the concentration of the template particles is 0. lwt% ~ 40wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction product is deposited in the polymerization The outer surface of the hollow spherical shell forms a continuous shell layer; after the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere in which an inorganic substance and an inner layer and a channel growth metal are grown on the outer surface of the polymer hollow spherical shell; The layer structure inorganic material-metal hollow sphere, that is, the inorganic hollow sphere contains a metal hollow sphere, and the obtained double-layer hollow sphere has a metal column connected between the two hollow spheres, and the metal hollow sphere cannot move in the inorganic sphere, two Hollow ball concentric; or

 01wt%〜30wt%, reduction of the concentration of the metal ion salt in the reaction solution is controlled to reduce the concentration of the metal ion salt in the reaction solution, the metal ion salt solution and the reducing agent solution are added in the step (1. 2). 01wt°/。 The concentration of the agent is 0. 01wt ° /. 〜 30wt%, the concentration of the template particles is 0. lwt% ~ 40wt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell; reaction is completed, centrifugal cleaning , that is, a composite hollow sphere in which metal and inner layer and channel growth metal are grown on the outer surface of the hollow shell of the polymer; the polymer template is removed to obtain a double-layered metal hollow sphere, that is, the metal hollow sphere contains a metal hollow sphere, The two-layer hollow ball has a metal column connected between the two hollow balls, and the inner metal hollow ball cannot move in the outer hollow ball, and the two hollow balls are concentric; or

Dispersing the composite hollow sphere of the inner layer and the channel growth metal obtained in the step (1.2) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the polymer monomer in the reaction liquid. 01wt度/。 The concentration of 0. 01wt% ~ 20wt%, the initiator concentration of 0. 01wt ° /. Lwt%〜40wt°/。 〜20wt%, the concentration of the template particles is 0. lwt% ~ 40wt ° /. , the reaction temperature is 0 ° C ~ 100 °c, the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell; after the reaction is completed, centrifugal cleaning, the organic matter and the inner layer are grown on the outer surface of the hollow shell of the polymer a composite hollow sphere of a channel-grown metal; removing the polymer template to obtain a two-layer structure organic-metal hollow sphere, that is, the organic hollow sphere contains a hollow metal sphere, and the obtained double-layer hollow sphere has a metal pillar between the two hollow spheres Connected, metal hollow spheres cannot be hollow in organic matter In-ball movement, two hollow balls concentric; or

 The weight of the inorganic precursor in the reaction liquid is 0. 01wt. The weight of the inorganic precursor in the reaction liquid is 0. 01wt %〜30wt%, The final concentration of the aqueous solution of the reaction component is 0. lw «~5 (kt ° /., the concentration of the template particles is 0. lwt% ~ 40wt ° /., the reaction temperature 0 ° C ~ 100 ° C, The reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell layer; after completion of the reaction, centrifugal cleaning is performed to obtain a composite hollow sphere in which an inorganic substance, an inner layer and a channel-grown organic substance are grown on the outer surface of the hollow sphere of the polymer; The template is obtained by obtaining a two-layer structure inorganic-organic hollow sphere, that is, the inorganic hollow sphere contains an organic hollow sphere, and the obtained double-layer hollow sphere has an organic column connected between the two hollow spheres, and the organic hollow sphere cannot be in the inorganic substance. In-ball movement, two hollow balls concentric; or

 01wt%〜30重量%, The concentration of the metal ion salt in the reaction liquid is 0. 01wt%~30wt%, the metal ion salt concentration in the reaction liquid is controlled. The concentration of the reducing agent is 0. 01wt%~30wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0°C~100°C, and the reaction product is deposited on the outer surface of the hollow shell of the polymer to form a continuous shell. After the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere in which metal and inner layer and channel-grown organic matter are grown on the outer surface of the polymer hollow spherical shell; the polymer template is removed to obtain a double-layered metal-organic hollow sphere, that is, metal The hollow sphere contains an organic hollow sphere, and the obtained double-layer hollow sphere has an organic column connected between the two hollow spheres, and the organic hollow sphere cannot move in the hollow sphere of the metal, and the two hollow spheres are concentric; or

 Dispersing the composite hollow sphere of the inner layer and the channel growth organic material obtained in the step (1.3) in water, introducing an inert gas into the reaction vessel, adding the polymer monomer and the initiator solution, and controlling the polymer monomer in the reaction liquid. 01重量%〜20重量%, The initiator concentration is 0. 01wt%~20wt%, the concentration of the template particles is 0. lwt%~40wt%, the reaction temperature is 0°C~100°C, and the reaction product is deposited on the polymer. The outer surface of the hollow spherical shell forms a continuous shell layer; after the reaction is completed, centrifugal cleaning is performed to obtain a composite hollow sphere which grows organic matter on the outer surface of the hollow shell of the polymer and the inner layer and the channel; the polymer template is removed to obtain a double-layer structure organic hollow The ball, that is, the organic hollow ball contains an organic hollow ball, and the obtained double-layer hollow ball has an organic column connected between the two hollow balls, and the inner hollow ball cannot move in the outer hollow ball, and the two hollow balls are concentric. The outer diameter of the polymer hollow sphere template particles is 0. 02|JB! 〜 10 , the cavity volume is 10 to 95% of the entire microsphere; the inner hydrophilic polymer of the polymer hollow sphere template comprises polystyrene sulfonic acid, polymethacrylic acid, polyacrylic acid, polyvinyl alcohol, Polyamides, polyvinylpyrrole, poly(2-vinylpyridine), poly(4-vinylpyridine), polyhydroxyethyl methacrylate, polyvinyl ester, polyoxyethylene or polyvinyl ammonium chloride ;

The outer lipophilic polymer of the polymeric hollow sphere template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, polymethyl Acrylic acid cinnamic acid ethyl ester, polymethyl acrylate, polyethyl acrylate ', polybutyl acrylate, polybutyl acrylate, polyoxypropylene, polydimethyl silicon Bismuth, polyvinyl butyrate or polyisobutylene;

The selective solvent for removing the polymer template is chloroform, toluene, tetrahydrofuran or N, N-dimethylformamide; when preparing the SiO ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is Al (0CH ₃ ) ₄ , Si (0CH ₂ CH ₃ ) ₄ , Si{0CH(CH ₃ ) ₂ } ₄ , 31(00« _3⁄4 : _3⁄4 ( _3⁄4 ) ₄ or ₂ 3:10 ₃ alcohol solution; reaction group Lwt%〜

Concentrated hydrochloric acid or a concentration of 25wt ° /. Concentrated ammonia water adjusts its pH value to 1~13;

In the preparation of the Ti0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is TiCl ₄ , Ti(0CH ₃ ) ₄ , Ti(0CH ₂ C ) ₄ , Ti{0CH(CH ₃ ) , Ti(0CH ₂ CH ₂ CH ₂ CH _{3) 4} or alcoholic solution of TiOS0 _4; aqueous reaction components at a concentration of 0. lwt% ~100wt% aqueous alcohol solution, and its pH was adjusted with concentrated hydrochloric acid concentration of 35wt% or 25wt% concentration of concentrated aqueous ammonia 1 to 13;

In the preparation of the Sn0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is SnCl ₄ , Sn(0CH ₃ ) ₄ , Sn (0CH ₂ CH ₃ ), Sn {OCH (CH ₃ ) ₂ } ₄ or An alcohol solution of Sn (0CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ ; an aqueous solution of the reaction component is an alcohol solution having a concentration of 0.1 wt% to 100 wt% of water, and the pH is adjusted by a concentration of 35 w «concentrated hydrochloric acid or a concentration of 25 wt% concentrated aqueous ammonia. 1 to 13;

In the preparation of a Zr0 ₂ hollow sphere or a composite hollow sphere, the inorganic precursor solution is ZrCl ₄ , Zr(0CH ₃ ) ₄ , Zr(0CH ₂ CH ₃ ) ₄ , Zr{0CH(CH ₃ ) ₂ } ₄ , 21> (0 ( _3⁄4 ( _3⁄4 ( _3⁄4 ( _3⁄4 ) ₄ or Zr (S0 ₄ ) ₂ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100w « water alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid Or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~13;

In the preparation of the A1 ₂ 0 ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is A1C1 ₃ , A1(0CH ₃ ) ₃ , A1(0CH ₂ C ) ₃ , A1{0CH(CH ₃ )J ₃ , Al (0CH ₂ CH ₂ CH ₂ C3⁄4) ₃ or A1 ₂ (S0 ₄ ) ₃ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100wt% water in an alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia water adjusts its pH value of 1~13;

In the preparation of a V ₂ 0 ₅ hollow sphere or a composite hollow sphere, the inorganic precursor solution is V0(0CH ₃ ) ₃ , V0(0CH ₂ CH ₃ ) ₃ , V0 {OCH (CH ₃ ) ₂ } ₃ or An alcohol solution of V0 (0C3⁄4CH ₂ CH ₂ CH ₃ ) ₃ ; an aqueous solution of the reaction component is an alcohol solution having a concentration of 0.1 wt% to 100 wt% of water, and the pH is adjusted by a concentration of 35 wt% concentrated hydrochloric acid or a concentration of 25 wt% concentrated ammonia water. ~13 _;

In preparing the ZnO hollow sphere or the composite hollow sphere, the inorganic precursor solution is an alcohol solution of Zn(N0 ₃ ) ₂ , Zn(00CCH ₃ ) ₂ , ZnCl ₂ or Zn(C10 ₄ ) ₂ ; The aqueous solution has a concentration of 0.01% by weight to 30% by weight. Water or alcohol solution of sodium hydroxide, potassium hydroxide or ammonia;

Lwt〜100重量%的水的含量。 In the preparation of the W0 ₃ hollow spheres or the composite hollow spheres, the inorganic precursor solution is (NH ₄ ) ₆ 1 ^ ₁₂ 0 ₄₁ or NaW0 ₃ aqueous solution; Alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~13;

In the preparation of hollow spheres or Mo0 ₃ composite hollow sphere, the inorganic precursor solution of aqueous Mo0 ₃ 2¾0; aqueous reaction component concentration 0. lwt% ~100wt ° /. Water alcohol solution, the concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~13; In the preparation of Al (OH) or Mg (OH) ₂ hollow spheres or composite hollow spheres, the inorganic precursor solution is an aqueous solution of soluble aluminum, magnesium chloride, and sulfate; the aqueous solution of the reaction component is at a concentration of 0. 01wt%~30wt% aqueous solution of sodium hydroxide, potassium hydroxide or ammonia;

When preparing the biomineralized material CaC0 ₃ , (3⁄4.(Ρ0 ₄ ) ₆ (0Η) ₂ , CaS0 ₄ , or BaS0 ₄ hollow sphere or composite hollow sphere, the inorganic precursor solution is Ca(0H) ₂ An aqueous solution of CaCl ₂ , Ba (0H) ₂ or BaCl ₂ ; the aqueous solution of the reaction component is a Na ⁺ or K + salt containing C0 ₃ ² —, P0 , SO, or a concentration of 0.01% to 3 (1⁄41% of H _{2 )} An aqueous solution of C0 ₃ , H ₃ P0 ₄ or H ₂ S0 ₄ ;

 01〜%〜 The concentration of the aqueous solution of the reaction solution is 0. 01^%~ 30% by weight of an aqueous solution of sodium sulfide or thiourea;

 01wtwt。 The solution of the aqueous solution of the solution is a concentration of 0. 01wt »/. ~ 30wt% aqueous solution of sodium selenide or sodium telluride;

When the magnetic compound FeA^F 0 ₃ or a ferrite hollow sphere or a composite hollow sphere containing zinc, manganese, cobalt, nickel, copper or magnesium is prepared, the inorganic precursor solution is Fe ²⁺ , Fe Zn ^{2 \ Mn 2 Co 2 Ni 2 \} Cu 2 ¾¾ Mg 2+ soluble chloride, nitrate or sulfate aqueous solution; concentration of the reaction components aqueous 0. 01wt% ~30wt% sodium hydroxide, potassium hydroxide or aqueous ammonia An aqueous solution, or a hydrazine hydrate solution having a concentration of from 5% to 60% by weight;

In the preparation of metal Au, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow spheres or composite hollow spheres, the metal ion salt solution is a corresponding metal ion soluble perchlorate, chloride, nitrate Or an aqueous solution of a sulfate; the reducing agent solution is an aqueous solution of NaB3⁄4, LiB(C ₂ H _S ) ₃ H or N ₂ H ₄ ;

 In the preparation of a conductive polymer polyaniline, polypyrrole, polythiophene, polyparaphenylene acetylene and derivatives thereof hollow spheres or composite hollow spheres, the polymer monomer solution is a water or alcohol solution of the corresponding monomer; initiator The solution is an aqueous solution of potassium persulfate, ammonium persulfate or ferric chloride;

 In the preparation of a sensitive gel poly-N-isopropylacrylamide, polyacrylic acid, polymethacrylic hollow sphere or composite hollow sphere, the polymer monomer solution is a monomer N-isopropyl acrylamide, acrylic acid , methacrylic acid or its water or alcohol solution; the initiator solution is an aqueous solution of potassium persulfate or ammonium persulfate;

 The inert gas is nitrogen or argon;

 The alcohol solution is methanol, ethanol, propanol, isopropanol, butanol.

11. The method according to claim 10, characterized in that: the composite inorganic hollow spheres or hollow spheres _{comprising: Ti0 2, Si0 2, Sn0} 2, Zr0 2, A1 2 0 3, V 2 0 s , Zn0, W0 ₃ , Mo0 ₃ , Al (0H) ₃ or Mg (0H) _2; hollow spheres or composite hollow spheres of biomineralized materials include: CaC0 ₃ , Ca ₁₀ (P0 ₄ ) _e (0H) ₂ , 8&50 ₄ or & 30 _{4 ;} hollow spheres or composite hollow spheres of semiconductor materials include: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; The hollow sphere or composite hollow sphere of the object comprises: FeA, Fe ₂ 0 ₃ or ferrite containing zinc, manganese and cobalt; the hollow sphere or composite hollow sphere of the metal comprises: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe; organic hollow spheres or composite hollow spheres include: polyaniline, polypyrrole, polythiophene or polyparaphenylene vinylene and its derivatives, poly N-isopropyl acrylamide, polyacrylic acid or polymethacrylic acid .

12. A method for preparing a hollow sphere and a composite hollow sphere by a template method, characterized in that the preparation method of the double-layer hollow sphere is as follows:

 01wt%〜60. 0wt°/。 The modified polymer hollow sphere was immersed in a concentration of 0. 01wt%~60. 0wt ° /. In the inorganic precursor solution, the modified polymer hollow spheres are kept at a concentration of 0. lwt%~40. (kt%, the inorganic precursor solution is infiltrated into the cavity and hydrophilicity of the modified polymer hollow sphere After the layer is reached, the solution that has not penetrated into the cavity is centrifuged and washed, and then the obtained modified polymer hollow sphere containing the inorganic precursor solution is added to the aqueous solution of the reaction component under stirring to control the reaction liquid. The weight of the modified polymer hollow sphere of the inorganic precursor solution is maintained at 0. lwt%~40. Owt%, the reaction temperature is 0 ° C ~ 100 ° C, the reaction is completed, centrifugal cleaning, that is, the polymer and the inorganic substance are obtained. Multi-layer composite hollow sphere; a double-layered inorganic hollow sphere can be obtained by removing a template polymer with a selective solvent; or

 01wt%〜 The weight of the modified polymer hollow sphere containing the aqueous solution of the reaction component is added to the concentration of 0. 01wt%~ Lwt%〜40. 0wt%, reaction temperature 0°C~100', the concentration of the modified polymer hollow spheres containing the aqueous solution of the reaction component in the reaction solution is maintained at 0. lwt%~ 40. 0wt%, reaction temperature 0°C~100' C, the reaction is completed, centrifugal cleaning, to obtain a multi-layer composite hollow sphere of polymer and inorganic; using a selective solvent to remove the template polymer, a two-layer inorganic hollow sphere can be obtained; or

 Lwt%~40. 0wt%, making metal, the metal polymer is immersed in a 0. lwt%~40. 0wt%, making metal The ionic salt solution penetrates into the cavity and the hydrophilic layer of the modified polymer hollow sphere, and after the equilibrium is reached, the uninfiltrated solution is centrifugally washed away; then the obtained modified polymer hollow sphere containing the metal ion salt solution is added under stirring. Lwt%~40. 0wt%, reaction temperature 0°, 0. 0wt%, 40°%, reaction temperature 0° C~100 ° C, the reaction is completed, centrifugal cleaning, that is, a multi-layer composite hollow sphere of polymer and metal is obtained; and the template polymer is removed by a selective solvent to obtain a double-layered metal hollow sphere; or

 0. 01wt%~60. 0wt% of the reducing agent solution is infiltrated into the hollow cavity of the modified polymer hollow sphere particles and the hydrophilic layer, and then the obtained modified polymer hollow sphere containing the reducing agent solution is added under stirring. Lwt»/。 The concentration of the modified polymer hollow spheres containing the reducing agent solution in the reaction solution was maintained at 0. lwt» /. 〜40. 0wt%, reaction temperature 0 ° C ~ 100 ° C, the reaction is completed, centrifugal cleaning, to obtain a polymer and metal multilayer composite hollow sphere; with a selective solvent to remove the template polymer, can be obtained two-layer structure metal Hollow ball; or

The weight of the modified polymer hollow spheres in these solutions is maintained at 0. vt%~40. 0wt, the concentration of the modified polymer hollow spheres in the solution is 0. vt%~40. 0wt %, infiltrating the polymer monomer solution into the modified polymer The cavity and the hydrophilic layer of the hollow sphere are centrifuged to remove the solution which has not penetrated into the hollow cavity of the modified polymer, and then the obtained modified polymer hollow sphere containing the polymer monomer solution is stirred. 0wt l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l %~40. 0wt%, reaction temperature 0°C~100°C, after completion of the reaction, centrifugal cleaning, to obtain a multilayer composite hollow sphere of polymer and organic matter; removing the template polymer with a selective solvent to obtain a double layer Structured organic hollow sphere; or

 01wt%〜30. 0wt% initiator solution is infiltrated into the cavity and hydrophilic layer of the modified polymer hollow sphere, and then the obtained modified polymer hollow sphere containing the initiator solution is added to the concentration under stirring Lwt%~40w The concentration of the modified polymer hollow spheres containing the initiator solution in the reaction solution is maintained at 0. lwt%~40w «, the reaction temperature is 0 ° C ~ 100 ° C, the reaction is completed, centrifugal cleaning, to obtain a multi-layer composite hollow sphere of polymer and organic matter; using a selective solvent to remove the template polymer, a two-layer organic hollow sphere can be obtained;

 The outer diameter of the modified polymer hollow sphere template particles is 0. 02μπ! ~ lO, the cavity volume is 10~95% of the whole microsphere, and the inner and outer surfaces are hydrophilic polymers;

 The hydrophilic polymer of the modified polymer hollow sphere template includes polystyrenesulfonic acid, polymethacrylic acid, polyacrylic acid, polyvinyl alcohol, polyamide, polyvinylpyrrole, poly(2-vinylpyridine) ), poly(4-vinylpyridine), polyhydroxyethyl methacrylate, polyvinyl ester, polyoxyethylene or polyvinyl ammonium chloride;

 The selective solvent for removing the polymer template is chloroform, toluene, tetrahydrofuran, hydrazine, hydrazine-dimethylformamide or the like.

In the preparation of the SiO ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is Si (0CH ₃ ) ₄ , Si (OCH ₂ CH ₃ ) ₄ , Si {0CH (C ) ₂ } ₄ , 51 (0 ( _3⁄4 ( _3⁄4 ( _3⁄4 ) ₄ or _3⁄4 0 ₃ alcohol solution; the aqueous solution of the reaction component is a concentration of 0. lwt%~ 100wt ° /. Alcohol solution of water, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water Adjust its pH value to 1~13;

In the preparation of the Ti0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is TiCl ₄ , Ti (OC 3⁄4) ₄ , Ti (0CH ₂ CH ₃ ) ₄ , Ti {0CH(C 3⁄4) ₂ } ₄ , Ti (0C C¾CH ₂ CH _{3) 4} or alcoholic solution of TiOS0 _4; aqueous reaction components at a concentration 0. 1 wt% ~ 100wt% aqueous alcohol solution of concentrated hydrochloric acid with a concentration of 35wt% or concentration 25wt ° / ¾¾ ammonia to adjust the pH The value is 1 to 13;

In the preparation of the Sn0 ₂ hollow sphere or the composite hollow sphere, the inorganic precursor solution is SnCl ₄ , Sn (0C3⁄4) ₄ , Sn (0CH ₂ CH ₃ ) , Sn {OCH (CH ₃ ) ₂ } ₄ or Sn An alcohol solution of (0CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ ; an aqueous solution of the reaction component is an alcohol solution having a concentration of 0.1 wt% to 100 wt% of water, and the pH is adjusted by a concentration of 35 wt% concentrated hydrochloric acid or a concentration of 25 wt% concentrated aqueous ammonia. 1~ 13;

In the preparation of a Zr0 ₂ hollow sphere or a composite hollow sphere, the inorganic precursor solution is ZrCl ₄ , Zr (0C3⁄4) ₄ , Zr (0C3⁄4CH ₃ ) ₄ , Zr {OCH (CH ₃ ) ₂ } ₄ , Zr ( 0CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ or Zr (S0 ₄ ) ₂ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100wt% water in an alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated Ammonia water adjusts its pH 1 to 13;

In the preparation of the A1 _{2 3 3} hollow sphere or the composite hollow sphere, the inorganic precursor solution is A1C1 ₃ , A1 (0C3⁄4) ₃ , Al (0CH ₂ CH ₃ ) , Al {OCH (CH ₃ ) J ₃ , Al (0CH ₂ CH ₂ CH ₂ CH ₃ ) ₃ or Al ₂ (S0 ₄ ) ₃ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100wt% water in an alcohol solution, with a concentration of 35wt% concentrated hydrochloric acid or concentration 25wt% concentrated ammonia water adjusts its pH value to 1~13;

In the preparation of a V ₂ 0 ₅ hollow sphere or a composite hollow sphere, the inorganic precursor solution is V0(0C3⁄4) ₃ , V0(0C3⁄4CH ₃ ) ₃ , V0 {OCH (CH ₃ ) ₂ } ₃ or V0 (0CH) ₂ CH ₂ CH ₂ CH ₃ ) ₃ alcohol solution; the reaction component aqueous solution is a concentration of 0. lwt% ~ 100% water in an alcohol solution, the concentration of 35wt% concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~ 13;

In the preparation of the ZnO hollow sphere or the composite hollow sphere, the inorganic precursor solution is an alcohol solution of Zn(N0 ₃ ) ₂ , Zn (00CC3⁄4) ₂ , ZnCl ₂ or Zn (C10 ₄ ) ₂ ; 0重量。〜30wt ° /. Water or alcohol solution of sodium hydroxide, potassium hydroxide or ammonia;

In the preparation of the W0 ₃ hollow spheres or the composite hollow spheres, the inorganic precursor solution is an aqueous solution of (NH ₄ ) ₆ ^0 ₄₁ or ^0 0 ₃ ; the aqueous solution of the reaction component is a concentration of 0. Iw1: ~ 100wt ° / . An alcoholic solution of water at a concentration of 35 wt ° /. Concentrated hydrochloric acid or a concentration of 25wt% concentrated ammonia water to adjust its pH value of 1~13;

In the preparation of the Mo0 ₃ hollow sphere or the composite hollow sphere, the inorganic precursor solution is a Mo0 ₃ 2H ₂ 0 aqueous solution; the reaction component aqueous solution is an alcohol solution having a concentration of 0.1 lw «~100 wt% water, with a concentration of 35 wt% Concentrated hydrochloric acid or a concentration of 25wt ^e /. Concentrated ammonia water adjusts its pH value to 1~13;

In the preparation of Al (0H) ₃ or Mg (0H) ₂ hollow spheres or composite hollow spheres, the inorganic precursor solution is an aqueous solution of soluble aluminum, magnesium chloride, and sulfate; the aqueous solution of the reaction component is at a concentration of 0. 01wt%~30wt% ice solution of sodium hydroxide, potassium hydroxide or ammonia water;

In the preparation of biomineralized materials CaC0 ₃ , C. (P0 ₄ ) ₃ (0H) ₂ , CaS0 ₄ , or BaS0 ₄ hollow sphere or composite hollow sphere, the inorganic precursor solution is Ca(0H) ₂ , CaCl ₂ , Ba(0H) ₂ or BaCl ₂ The aqueous solution of the reaction component is a Na ⁺ or K + salt containing C0 ₃ ² —, P0 , SO, or a concentration of 0. 0^ %~30 % of H ₂ C0 ₃ , H ₃ P0 ₄ or H ₂ S0 ₄ Aqueous solution

 01%〜30。 The aqueous solution of the solution is a solution of the aqueous solution of the corresponding metal cations, a nitrate or a sulphate; ^% aqueous solution of sodium sulfide or thiourea;

 01wtwt。 The solution of the aqueous solution of the solution is a concentration of 0. 01wt %~ 30wt% aqueous solution of sodium selenide or sodium telluride;

When the magnetic compound Fe ₃ 0 ₄ or Fe ₂ 0 ₃ or a ferrite hollow sphere or a composite hollow sphere containing zinc, manganese, cobalt, nickel, copper or magnesium is prepared, the inorganic precursor solution is Fe ^{2+ .} , Fe ³ \ Zn ² aq ^{\ Mn 2 \ Co 2+, Ni} 2+, Cu 2+ or Mg ²⁺ soluble chloride, nitrate or sulfate; aqueous reaction components at a concentration of 0. 01wt% ~30wt % sodium hydroxide, hydrogen An aqueous solution of potassium oxide or aqueous ammonia, or a hydrazine hydrate solution having a concentration of 1% to 60%;

In the preparation of metal Au, Ag, Pt, Pd, Pb, Ni, Co, Cu, Fe hollow spheres or composite hollow spheres, the metal ion salt solution is a corresponding metal ion soluble perchlorate, chloride, nitrate Or an aqueous solution of a sulfate; the reducing agent solution is an aqueous solution of NaB, 1^8 (( _{2 3⁄4} ) ₃ 11 or 1 ^;

 In the preparation of a conductive polymer polyaniline, polypyrrole, polythiophene, polyparaphenylene acetylene and derivatives thereof hollow spheres or composite hollow spheres, the polymer monomer solution is a water or alcohol solution of the corresponding monomer; initiator The solution is an aqueous solution of potassium persulfate, ammonium persulfate or ferric chloride; '

 In the preparation of a sensitive gel poly-N-isopropylacrylamide, polyacrylic acid, polymethacrylic hollow sphere or composite hollow sphere, the polymer monomer solution is a monomer N-isopropyl acrylamide, acrylic acid , methacrylic acid or its water or alcohol solution; the initiator solution is an aqueous solution of potassium persulfate or ammonium persulfate;

 The inert gas is nitrogen or argon;

 The alcohol solution is methanol, ethanol, propanol, isopropanol or butanol.

13. The method according to claim 12, characterized in that: the composite inorganic hollow spheres or hollow spheres _{comprising: Ti0 2, Si0 2, Sn0} 2, Zr0 2, A1 2 0 3, V 2 0 5 , ZnO, W0 ₃ , Mo0 ₃ , Al (0H) ₃ or M _g (0H) ₂ ; hollow spheres or composite hollow spheres of biomineralized materials include: CaC0 ₃ , Ca ₁₀ (P0 ₄ ) ₆ (0H) ₂ , BaS0 ₄ or CaS0 _4; hollow sphere or composite hollow sphere of semiconductor material includes: CdS, ZnS, PbS, CuS, CoS, FeS, CdTe, CdSe or ZnSe; hollow sphere or composite hollow sphere of magnetic compound includes: Fe ₃ 0 ₄ , Fe ₂ 0 ₃ or ferrite containing zinc, manganese or cobalt; hollow or composite hollow spheres of metal include: Au, Ag, Pt, Pd, Pb, Ni, Co, Cu or Fe; hollow spheres of organic matter or The composite hollow spheres include: polyaniline, polypyrrole, polythiophene or polyparaphenylene vinylene and derivatives thereof, poly N isopropyl acrylamide, polyacrylic acid or polymethacrylic acid.

14. A method for preparing hollow spheres and composite hollow spheres by a template method, characterized in that polymer hollow sphere template particles are dispersed in an aqueous solution of a reaction component, monomers and crosslinkers are added, or monomers and crosslinks are obtained. And an organic solvent, swell the polymer hollow sphere template shell by a monomer or an organic solvent, and introduce the monomer and the initiator into the polymer hollow spherical shell layer, and then perform polyaddition, polycondensation or ring-opening polymerization in the reaction O. 01wt%〜10wt% The concentration of the crosslinker is 0. 1wt%~20wt%, the concentration of the crosslinker is 0. 01wt%~10wt%, the concentration of the reactant is 0. lwt%~20wt%, the concentration of the crosslinker is 0. 01wt%~10wt% , a concentration of the organic solvent 0wt% ~20wt%, the reaction temperature is 20 ° C~250 ° _C; the reaction is completed, centrifugal cleaning, polymer hollow spheres obtained composite hollow sphere and an organic substance; the outer hollow sphere polymeric particles template The diameter is 0. 02μπ! ~ 10Mm, the cavity volume is 10~95° / ₀ of the whole microsphere _; the inner hydrophilic polymer of the polymer hollow sphere template comprises polystyrenesulfonic acid, polymethacrylic acid, polyacrylic acid, polyethylene Alcohol, polyamide, polyvinylpyrrole, poly(2-vinylpyridine), poly(4-vinylpyridine), poly Hydroxyethyl methacrylate, polyvinyl ester, polyoxyethylene or polyvinyl ammonium chloride;

 The outer lipophilic polymer of the polymeric hollow sphere template comprises polystyrene, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, polymethyl Acrylic acid cinnamic acid ethyl ester, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly(tert-butyl acrylate), polyoxypropylene, polydimethylsilane, polyvinyl butyrate or polyisobutylene;

 The organic solvent used to swell the polymer hollow spherical shell is chloroform, benzene, toluene, xylene, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Sulfone, acetone or cyclohexanone;

 The inert gas is nitrogen or argon;

 The cross-linking agent for preparing cross-linked polystyrene, polyacrylate hollow sphere or composite hollow sphere is azobisisobutyronitrile, azobisisoheptanenitrile, dibenzoyl peroxide, peroxydicarbonate Isopropyl ester, potassium persulfate or ammonium persulfate; the monomer is styrene, divinylbenzene, methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate;

 The crosslinking agent for preparing the polyurethane hollow sphere or the composite hollow sphere is polyether diol, polyester diol or 1, 4-butanediol; the monomer is hexamethylene diisocyanate or toluene diisocyanate;

 The crosslinking agent for preparing the phenolic resin hollow sphere or the composite hollow sphere is phenol, o-cresol, p-cresol, resorcin or bisphenol A; the monomer is formaldehyde, trioxane, acetaldehyde, trimer Acetaldehyde or furfural;

 The crosslinking agent for preparing the unsaturated polyester hollow sphere or the composite hollow sphere is ethylene glycol, propylene glycol, 1, 3-butanediol, polyether diol or polyester diol; the monomer is maleic anhydride;

 The crosslinking agent for preparing the epoxy resin hollow sphere or the composite hollow sphere is hexamethylene diisocyanate, toluene diisocyanate, phthalic anhydride, phthalic anhydride, maleic anhydride, ethylenediamine, hexamethylenediamine or tri Methyltetramine; monomer is bisphenol A epoxy or phenolic epoxy;

 The crosslinking agent for preparing the polyimide hollow sphere or the composite hollow sphere is p-phenylenediamine or hexamethylenediamine; the monomer is bismaleic anhydride or pyromellitic anhydride;

 The crosslinking agent for preparing the polyether ketone or the polyether sulfone hollow sphere or the composite hollow sphere is 4, 4-difluorobenzophenone or 4, 4-dichlorodiphenyl sulfone; the monomer is hydroquinone Or tetramethylbiphenyldiol.