CN1927913A - Chemical preparation method of hollow polymer microsphere with controllable open pores - Google Patents
Chemical preparation method of hollow polymer microsphere with controllable open pores Download PDFInfo
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Abstract
The invention discloses a chemical preparation method of hollow polymer microspheres with controllable openings. The method is completed in two steps: the reaction monomer is first lightly polymerized under certain reaction condition to form one coating layer on the surface of the template, and the coating layer is further polymerized to shrink its volume to form the outer casing with holes. The obtained microspheres with holes are further put in corrosive liquid of template components, and the template components are diffused out through the holes on the shell and are centrifuged off, so that the hollow polymer microspheres with holes are formed. The invention has the advantages of high kernel removing speed and solvent saving. The obtained hollow polymer microspheres with the openings can be used as a container for loading certain substances, and the openings are sealed to protect or control the release of the substances in the hollow polymer microspheres; can also be used as a micro-reactor to improve the reaction efficiency; and can be further functionalized to obtain intelligent materials or added with auxiliary monomers for molecular recognition.
Description
Affiliated field the present invention relates to material science, particularly has the chemical preparation process of the hollow polymer microsphere of controllable opening.
The background technology hollow polymer microsphere all has in a lot of fields widely and uses with its superior characteristic.As in medical science and field of biology: hollow polymer microsphere can be used as drug delivery system, cushion effectively is sent to lesions position or realizes that controlled delivery of pharmaceutical agents discharges; Hollow polymer microsphere can also be used for biomacromolecule, as micro encapsulation, migration and release, gene therapy and the preparation blood substitute etc. of protein, enzyme and nucleic acid.At material science: because the density of hollow polymer microsphere less than solid, can effectively reduce the density of matrix material as the filler of polymer composites; Hollow polymer microsphere can be given the coating opacity as the filler of coating; When using, can also improve the gloss of papery, perhaps be used for rubber toughened plastics technology as papermaking material.Catalyst field: hollow polymer microsphere can be used for the protection of hydridization type Preparation of catalysts and photosensitive component.Hollow polymer microsphere also can be used as microreactor and uses, the preparation inorganic nanoparticles.In addition, hollow polymer microsphere also can be used as UV light absorber, is used for cosmetic industry protection skin and hair and is not subjected to uv-radiation.
Therefore, the preparation of hollow polymer always is one of research focus of polymer science.The method for preparing hollow polymer microsphere that present people have been developed mainly contains following three kinds: self-assembly method, template and microemulsion/dispersion copolymerization method.Wherein template is the simplest method for preparing tiny balloon, adopt this method can obtain uniform monodisperse hollow microballoon easily, and can further adjust inner chamber size and outer wall thickness by the particle diameter and the follow-up monomeric consumption of control nuclear template, obtain being fit to the hollow polymer microsphere of demand.Utilize template to prepare tiny balloon and have two types: the first allows the polyelectrolyte that has opposite charges in the self-assembly successively of spherical template surface, reaches the thick back of the shell that needs removal of solvents template; Another kind of template is at template surface chemical bonding polymerizable or crosslinkable molecular layer, and initiated polymerization or crosslinked dissolves template again.As seen, for obtaining hollow polymer microsphere, it is necessary utilizing suitable removal of solvents template.Conventional method is by the micropore on the shell nuclear consitution to be diffused out, these micropores generally very little (＜10nm), the nuclear consitution diffusion slowly also can be trapped in the micropore sometimes, makes its obstruction.If when needing synthetic thicker relatively highly cross-linked ghost, this process becomes veryer long, does not have workability substantially.Other has the solvent of stoning, and often toxicity is very big, by micropore to shell ooze bubble for a long time, can make casing deformation, influence its performance performance.Therefore, how optimizing the stoning mode, to shorten the stoning time be a major challenge that template faces.
In the application facet of hollow polymer microsphere, also having is the micropore that utilizes on the outer wall greatly.Micropore narrow and small, totally unfavorable to the performance of tiny balloon performance.The hollow polymer microsphere of perforate shows better practicality and more wide application prospect as the substitute of the hollow polymer microsphere with sealing shell.Research about this respect is at the early-stage, and slower development, still is in phenomenon and describes the stage.Can obtain the polymer microballoon of perforate by the emulsifying agent consumption in the control self assembling process such as report in the articles of people on 2005 " Langmuir " such as Masayoshi Okubo; Utilize the method for physics to synthesize the hollow polystyrene microsphere of perforate and studied its loading features in the article of Xia Younan on 2005 " Nature materials ".Because the two preparation method's restriction, all uncontrollable and moiety of the thickness of shell and perforate quantity is single not to possess any specific function.But the preparation method of the hollow polymer microsphere that has controllable opening who therefore develops a kind of functionalization is significant.
In recent decades, in order to improve marking ability, the morphology control of molecularly imprinted polymer has been attracted large quantities of investigators.The patent of invention of University Of Tianjin in 2003 application discloses a kind of preparation method of molecularly imprinted polymer microballoon, and (publication number is: CN 1390862A).It has adopted following step: (1) places water with Natvosol; (2) function monomer and target molecule are placed water; (3), stir with linking agent, initiator and mixing diluents; (4) above-mentioned three kinds of solution are mixed, seal after feeding nitrogen, stir with the constant speed of 300～400rpm at 65～80 ℃ of constant temperature and promptly got the imprinted polymer microballoon in 6～10 hours.But because effectively the molecular imprinting site mainly is present on surface or the very shallow one deck shell, the polymer microballoon of the marking just causes the waste significantly target molecule of costliness (especially for).As further development, people utilize template to synthesize large quantities of nucleocapsid structure polymer microballoons (solid) that have only marking shell.Yet, as the extension of nucleocapsid structure microballoon and in theory the hollow imprinted polymer microballoon of marking better effects if be not in the news as yet.Because the density of imprinted polymer is more taller than general cross-linked polymer, make the component of nuclear only diffuse out quite difficulty by the micropore of marking shell.
The summary of the invention goal of the invention: at the weak point that present testing program exists, the present invention utilizes template to synthesize the hollow polymer microsphere that has controllable opening first, and for the first time the hollow polymer microsphere functionalization of perforate is used for molecular imprinting.Described method is a chemical synthesis, at first prepares shell nucleocapsid structure microballoon with holes, immerses then to allow nuclear diffuse out by the shell perforate in the nuclear consitution corrosive fluid and micropore on the shell.The thickness that this invention not only can be controlled shell can also change the quantity of perforate.In addition, also can add auxiliary monomer or change function monomer in reaction, the perforate tiny balloon that obtains having various specific functions has increased its practicality in every field greatly.
Technical scheme of the present invention is: a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening, comprise with spheroidal particle and make template, adopt the method for finishing allow specific function group on the spherical template surface band, it is characterized in that the forming process of perforate comprises following two steps among the present invention:
Function monomer and linking agent being dissolved in 50 milliliters the acetonitrile makes its concentration be respectively 0.002～0.008 mol, 0.010～0.030 mol, add massfraction again and be initiator and 30 milligrams of spherical template of 2～4%, seal behind the logical nitrogen deoxidation, be warming up to 40～45 ℃ of reactions 8～15 hours, form low polymeric coating layer on the spherical template surface, it is the first step reaction;
The reaction of second step is that reaction system is warmed up to 55～65 ℃ of reactions 24 hours again, the volumetric shrinkage of the coating layer on spherical template surface in the crosslinking polymerization process, formed shell with holes, remain in reaction monomers in the solution and be adsorbed on and carry out polymerization on the shell again, finally formed the nucleocapsid structure polymer microballoon that has perforate;
Gained nucleocapsid structure polymer microballoon is distributed in the corrosive fluid of spherical template centrifugally after 4 hours, the component of spherical template diffuses out by centrifugal by the perforate on the shell, and washed twice just obtains the hollow polymer microsphere of perforate again.The perforate quantity of the hollow polymer microsphere of gained perforate and outer casing thickness can be controlled by proportioning and the total amount adjusted between the follow-up monomer.
Wherein spherical template is rich in the polystyrene sphere of carboxyl for the surface; Can add auxiliary monomer such as TNT in the reaction monomers, change the shell performance; Function monomer is functional monoene class monomer: acrylamide (AAM) or 4-vinylpridine; Linking agent is a polyenoid class monomer ethyleneglycol dimethacrylate methyl esters (EGDMA), and initiator is oil-soluble initiator azo-bis-isobutyl cyanide (AIBN).
The hollow polymer microsphere of perforate can load indicate molecule, drug molecule, biomolecules as container, or the quantum dot of packing into, nanoparticle, and perforate can be closed with some intelligent material its inner material is protected or sustained release.Beneficial effect with respect to prior art:
One: with respect to template of the prior art: nuclear consitution is very slow by the micropore diffusion on the sealing shell, needs cost plenty of time and solvent and influences the performance of shell.And method provided by the invention can make nuclear consitution remove by perforate, and not only stoning speed is fast, the saving solvent, and the performance of shell is unaffected, has expanded its Application Areas greatly.Among the present invention, the forming process of perforate comprises following two steps in the chemical preparation process process of the hollow polymer microsphere of perforate:
Function monomer and linking agent being dissolved in 50 milliliters the acetonitrile makes its concentration be respectively 0.002～0.008 mol, 0.010～0.030 mol, add massfraction again and be initiator and 30 milligrams of spherical template of 2～4%, seal behind the logical nitrogen deoxidation, be warming up to 40～45 ℃ of reactions 8～15 hours, form low polymeric coating layer on the spherical template surface, it is the first step reaction;
The reaction of second step is that reaction system is warmed up to 55～65 ℃ of reactions 24 hours again, the volumetric shrinkage of the coating layer on spherical template surface in the crosslinking polymerization process, formed shell with holes, remain in reaction monomers in the solution and be adsorbed on and carry out polymerization on the shell again, finally formed the nucleocapsid structure polymer microballoon that has perforate;
The nucleocapsid structure polymer microballoon that gained is had a perforate is distributed in the corrosive fluid of spherical template centrifugal after 4 hours, and the component of spherical template diffuses out by centrifugal by the perforate on the shell, and washed twice just obtains the hollow polymer microsphere of perforate again.
Its two: in the method provided by the present invention, having the quantity of hollow polymer microsphere perforate of controllable opening and the thickness of shell can control, therefore can be by optimizing the hollow polymer microsphere that reaction conditions obtain being fit to needs.Another big advantage of method provided by the present invention is to add the perforate hollow polymer microsphere that auxiliary monomer obtains having certain specific function.Such as adding the hollow imprinted polymer microballoon that a certain amount of TNT can the anamorphic zone perforate.And the function monomer among the present invention is acrylamide (AAM), also can be 4-vinylpridine.As seen, method provided by the present invention is general, and usage range is quite extensive.
Its three: compare with the closed hollow microballoon, solvent can be diffused into the hollow polymer microsphere inside of perforate rapidly, make internal surface become effective equally, so just make effective surface area enlarge one times, improved the characteristic of the hollow polymer microsphere of perforate with outside surface.The result of molecular imprinting shows that the tiny balloon of perforate has bigger adsorptive power and binding kinetics faster.Fig. 8 has illustrated that institute's synthetic has the molecular imprinting characteristic of the perforate hollow polymer microsphere of TNT marking point.As seen, the hollow polymer microsphere that the hollow imprinted polymer microballoon that has perforate is perforate has higher saturated extent of adsorption, is 2.17 times of closed hollow microballoon; And having association rate faster, is 9.44 times of solid imprinted polymer microballoon
Its four: the hollow polymer microsphere of gained perforate can also be as container; load other materials; such as indicating molecule, drug molecule, biomolecules; also can pack into quantum dot, nanoparticle, and perforate can be closed with some intelligent material the material of its inside is protected or sustained release.
Description of drawings
Fig. 1 is the formation schematic diagram of mechanism of the hollow polymer microsphere of gained perforate of the present invention.
Fig. 2 is the stereoscan photograph that the polystyrene sphere of carboxyl is rich on surface of the present invention.
Fig. 3 is the stereoscan photograph of the resulting intermediate product-shell of the present invention nucleocapsid structure microballoon with holes.
Fig. 4 is the transmission electron microscope photo that the present invention has the nucleocapsid structure microballoon of perforate.
Fig. 5 is the scanning and transmission (insertion) electromicroscopic photograph of the present invention's hollow polymer microsphere of having perforate.
Fig. 6 is the stereoscan photograph that shell of the present invention has the hollow polymer microsphere of two perforates.
Fig. 7 is the stereoscan photograph that the present invention changes function monomer gained perforate hollow polymer microsphere.
Fig. 8 is the molecular imprinting performance chart that synthetic of the present invention has TNT marking point perforate hollow polymer microsphere.
Further explain embodiment with reference to the accompanying drawings
Fig. 1 is the formation schematic diagram of mechanism of the hollow polymer microsphere of gained perforate of the present invention.In Fig. 1 according to the volumetric shrinkage phenomenon in the cross-linking polymerization process, utilize the little spheres as template of vinylbenzene, adopt two-step reaction method, obtained nucleocapsid structure polymer microballoon with holes, further it is placed in the corrosive fluid of nuclear consitution, just obtains the hollow polymer microsphere of perforate.
The vinylbenzene bead must be modified, and makes the surface be with extraordinary functional group, is beneficial to next step and is reflected at its surface generation.What the present invention adopted is at pure styrene bead surface graft vinylbenzene and acrylic acid multipolymer, make its surface coverage carboxyl, help like this add function monomer and promptly have amino acrylamide and be adsorbed on the phenylethylene micro ball surface, make to be reflected at its surface and to take place;
Two-step reaction is meant and at first allows reaction soln be in lesser temps, carries out slight polymerization in reasonable time, forms an integument on the phenylethylene micro ball surface, and the thickness of this skim is most important, needs carefully control.Be warmed up to comparatively high temps then, the further polymerization of adsorption layer on vinylbenzene bead surface, because the volumetric shrinkage in the crosslinking polymerization process, thin layer can not encase phenylethylene micro ball more fully, so formed shell with holes.In reaction thereafter, remain in reaction monomers in the solution and be adsorbed on again and carry out polymerization on the shell, therefore can adjust the outer casing thickness of thus obtained microsphere by the consumption of control reaction monomers.
Further be placed in the corrosive fluid of polystyrene getting microballoon, styrene polymer diffuses out by the perforate on the shell, so just formed the hollow polymer microsphere of perforate.
Fig. 2 is an even monodispersed vinylbenzene bead template of the present invention owing to adopted kind emulsion synthesis method, on the pure styrene bead grafting vinylbenzene and acrylic acid multipolymer, so carboxyl is rich on gained vinylbenzene bead surface.
Fig. 3 is the resultant microballoon that gets intermediate product-nucleocapsid structure with holes of the present invention.Can coat the shell that one deck has perforate on the spherical template surface through two-step reaction method.Can clearly see the existence of perforate on the scanned photograph, but because angular relation, the perforate that is not each microballoon can show.As seen, nucleocapsid structure microballoon with holes is made up of two portions: intermediary spherical template and the shell that has perforate.
Fig. 4 further proves the nucleocapsid structure that gained is with holes with transmission electron microscope.Hickie on the black disk is the performance that perforate exists.As seen the existence of perforate is not a some phenomena, but the general character of all microballoons.
Fig. 5 is a corrosive fluid tetrahydrofuran (THF) of the gained nucleocapsid structure being put into polystyrene, through centrifugal and disperse the hollow polymer microsphere of gained perforate several times.Compare with Fig. 2, difference is that intermediary nuclear template is removed, promptly obtains the hollow microballoon with holes of perforate.Illustration on Fig. 5 is the transmission photo of the hollow polymer microsphere of perforate, and its shape characteristic is high-visible.
Fig. 6 changes the reaction monomers proportioning and synthetic has the hollow polymer microsphere of two perforates.
Fig. 7 is the hollow polymer microsphere that changes the resultant perforate of function monomer.This result shows can be by changing the performance that function monomer changes the hollow polymer microsphere of perforate, to be fit to the needs of different field in method provided by the present invention.
Fig. 8 is the molecular imprinting characteristic that institute's synthetic has the perforate hollow polymer microsphere of TNT marking point: wherein Fig. 8 A is the saturated absorption curve of three kinds of molecule marking materials: (a) be the hollow imprinted polymer microballoon that has perforate; (b) be hollow imprinted polymer microballoon with sealing shell; (c) be solid marking microballoon.As seen, the hollow imprinted polymer microballoon that has perforate has higher saturated extent of adsorption, is 2.17 times of closed hollow microballoon.
Fig. 8 B has the hollow imprinted polymer microballoon (a) of perforate and the curve of adsorption kinetics of solid marking microballoon (b), and the former has association rate faster, is 9.44 times of the latter.
Embodiment: a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening, comprise with polystyrene sphere and make spherical template, adopt no soap kind emulsion polymerization way, at first synthetic monodispersed pure styrene bead, coat one deck vinylbenzene and acrylic acid multipolymer on its surface again, the polystyrene sphere surface just is covered with carboxyl like this, can adsorb institute and add the function monomer acrylamide, and polyreaction is taken place on the spherical template surface.The forming process of perforate comprises following two steps among the present invention:
Function monomer acrylamide (AAM) and linking agent ethyleneglycol dimethacrylate methyl esters (EGDMA) being dissolved in 50 milliliters the acetonitrile makes its concentration be respectively 0.006 mol, 0.024 mol, add massfraction again and be 3% initiator Diisopropyl azodicarboxylate (AIBN) and 30 milligrams vinylbenzene bead, seal behind the logical nitrogen deoxidation, be warming up to 43 ℃ of reactions 12 hours, form low polymeric coating layer on the spherical template surface, it is the first step reaction;
The reaction of second step is that reaction system is warmed up to 50 ℃ of reactions 24 hours again, the volumetric shrinkage of the coating layer on spherical template surface in the crosslinking polymerization process, formed shell with holes, remain in reaction monomers in the solution and be adsorbed on and carry out polymerization on the shell again, finally formed the nucleocapsid structure polymer microballoon that has perforate;
The nucleocapsid structure polymer microballoon that gained is had a perforate is distributed in the corrosive fluid tetrahydrofuran (THF) of polystyrene centrifugal after 4 hours, styrene polymer diffuses out by centrifugal by the perforate on the shell, and washed twice just obtains the hollow polymer microsphere of perforate again.
If keep the reaction monomers total amount constant, the proportioning of function monomer and linking agent is adjusted into 1: 2, just can synthesize the hollow polymer that has two perforates; If keep the proportioning constant reaction monomers total amount is added to be twice then that the thickness of shell becomes 35nm by original 20nm.
Reaction monomers can add auxiliary monomer, changes the shell performance.As adding an amount of TNT, the imprinted polymer that the rigidity that not only can improve shell can also form TNT carries out molecular recognition.Function monomer also can be changed to other different function monomer 4-vinylpridine.
The hollow polymer microsphere of perforate can load indicate molecule, drug molecule, biomolecules as container, or the quantum dot of packing into, nanoparticle, and perforate can be closed with some intelligent material its inner material is protected or sustained release.Be immersed in the aqueous solution of rhodamine B 12 hours as the tiny balloon with perforate, stirred 5 hours fast adding an amount of toluene and styrene polymer, rhodamine B just is enclosed in tiny balloon inside.
Embodiment: according to the volumetric shrinkage in the cross-linking polymerization process, utilize vinylbenzene to make template, adopt two-step reaction can obtain the core-shell particles of perforate, the processing of process corrosive fluid just obtains the hollow polymer microsphere of perforate.
1, the vinylbenzene bead is synthetic: for the carboxyl-content that increases the bead surface has adopted the letex polymerization of no soap kind.1g vinylbenzene (St) is added in the distilled water of 92ml, make initiator with 0.005g ammonium persulphate (APS) and be warming up to 80 ℃ of reactions 0.5 hour in 3 hours again 70 ℃ of reactions.Again transfer to 70 ℃, with vinylformic acid (AA 0.898ml, drop rate: 0.02g/min), vinylbenzene (St 9.9ml, drop rate: 0.1g/min) and ammonium persulphate (APS 0.045g is dissolved in the 10ml water, drop rate: 0.1g/min) dropwise add, reacted again 5 hours.The resulting polymers microballoon is distributed in the ethanol through three centrifuge washings.
2, the two-step reaction of nucleocapsid structure microballoon with holes: function monomer acrylamide (AAM) and linking agent ethyleneglycol dimethacrylate methyl esters (EGDMA) are dissolved in the acetonitrile of 50ml and make its concentration be respectively 0.002～0.008mol/l, 0.010～0.030mol/l, adding massfraction again is 2～4% initiator Diisopropyl azodicarboxylate (AIBN) and the ethanolic soln that contains 30 milligrams of vinylbenzene beads, seals behind the logical nitrogen deoxidation.Be warming up to 40～45 ℃ of reactions 8～15 hours, and then be warmed up to 55～65 ℃ of reactions 24 hours, promptly get the nucleocapsid structure polymer microballoon that has perforate.
3, the formation of tiny balloon with holes: the nucleocapsid structure polymer microballoon that gained is had a perforate is distributed in the tetrahydrofuran (THF) centrifugal after 4 hours, and washed twice just obtains the hollow polymer microsphere of perforate again.
Obviously, those skilled in the art can be to the present invention: the chemical preparation process that has a hollow polymer microsphere of controllable opening carries out various changes and modification and does not break away from the spirit and scope of the present invention.If of the present invention like this these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (9)
1, a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening, comprise with spheroidal particle and make template, adopt the method for finishing allow specific function group on the spherical template surface band, it is characterized in that the forming process of perforate of the present invention comprises following two steps:
1.1 function monomer and linking agent being dissolved in 50 milliliters the acetonitrile makes its concentration be respectively 0.002～0.008 mol, 0.010～0.030 mol, add massfraction again and be initiator and 30 milligrams of spherical template of 2～4%, seal behind the logical nitrogen deoxidation, be warming up to 40～45 ℃ of reactions 8～15 hours, form low polymeric coating layer on the spherical template surface, it is the first step reaction;
1.2 the reaction of second step is that reaction system is warmed up to 55～65 ℃ of reactions 24 hours again, the volumetric shrinkage of the coating layer on spherical template surface in the crosslinking polymerization process, formed shell with holes, remain in reaction monomers in the solution and be adsorbed on and carry out polymerization on the shell again, finally formed the nucleocapsid structure polymer microballoon that has perforate;
The nucleocapsid structure polymer microballoon that gained is had a perforate is distributed in the corrosive fluid of spherical template centrifugal after 4 hours, and the component of spherical template diffuses out by centrifugal by the perforate on the shell, and washed twice just obtains the hollow polymer microsphere of perforate again.
2, a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening according to claim 1, it is characterized in that: the quantity of the hollow polymer microsphere perforate of said perforate can be controlled by the proportioning of adjusting between the follow-up monomer.
3, a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening according to claim 1 is characterized in that: the perforate quantity of the hollow polymer microsphere of said perforate and outer casing thickness can be controlled by proportioning and the total amount adjusted between the follow-up monomer.
4, a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening according to claim 1 is characterized in that: said spherical template is rich in the polystyrene sphere of carboxyl for the surface.
5, a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening according to claim 1 is characterized in that: can add auxiliary monomer such as TNT in the said reaction monomers, carry out molecular recognition.
6, a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening according to claim 1 is characterized in that: said function monomer is functional monoene class monomer: acrylamide (AAM) or 4-vinylpridine.
7, a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening according to claim 1 is characterized in that: said linking agent is a polyenoid class monomer ethyleneglycol dimethacrylate methyl esters (EGDMA).
8, a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening according to claim 1 is characterized in that: said initiator is oil-soluble initiator azo-bis-isobutyl cyanide (AIBN).
9, a kind of chemical preparation process that has the hollow polymer microsphere of controllable opening according to claim 1; it is characterized in that: the hollow polymer microsphere of said perforate can load as container and indicate molecule, drug molecule, biomolecules; or the quantum dot of packing into, nanoparticle, and perforate can be closed with some intelligent material its inner material is protected or sustained release.
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| CN101787143B (en) * | 2010-01-22 | 2012-02-08 | 武汉理工大学 | Method for preparing layer-by-layer self-assembled protein-imprinted polymer of chitosan |
| CN105860123A (en) * | 2016-05-16 | 2016-08-17 | 昆明理工大学 | Method of preparing temperature-resistant and organic-solvent-resistant polymeric microsphere with non-permeable surface |
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| US5599889A (en) * | 1994-08-16 | 1997-02-04 | Stoever; Harald D. H. | Method of forming polymer microspheres |
| SE9903958D0 (en) * | 1999-11-02 | 1999-11-02 | Boerje Sellergren | Porous materials for selective binding or transport of molecular guests |
| CN1164619C (en) * | 2002-06-26 | 2004-09-01 | 天津大学 | Process for preparing microspheres of molecular blot polymer in water medium |
| CN100464833C (en) * | 2004-11-11 | 2009-03-04 | 中国科学院化学研究所 | Template process of preparing hollow ball and composite hollow ball |
| CN1266172C (en) * | 2004-11-25 | 2006-07-26 | 南开大学 | Monodispersity nano/micron polymer microsphere resin and method for preparing same |
| CN1654493A (en) * | 2005-01-11 | 2005-08-17 | 天津大学 | Method for preparing monodispersed large grain-size hollow styrene-acrylic polymer microsphere in low soap system |
| CN1736576A (en) * | 2005-08-08 | 2006-02-22 | 清华大学 | Method for preparing large-cavity soap-free submicro polymer microsphere |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101787143B (en) * | 2010-01-22 | 2012-02-08 | 武汉理工大学 | Method for preparing layer-by-layer self-assembled protein-imprinted polymer of chitosan |
| CN105860123A (en) * | 2016-05-16 | 2016-08-17 | 昆明理工大学 | Method of preparing temperature-resistant and organic-solvent-resistant polymeric microsphere with non-permeable surface |
| CN109908872A (en) * | 2018-02-01 | 2019-06-21 | 常州大学 | A kind of micro-gel particles of bowl structure and its preparation method and application |
| CN109908872B (en) * | 2018-02-01 | 2021-08-24 | 常州大学 | Microgel particles with bowl-shaped structure and preparation method and application thereof |
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