CN102070152A - Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof - Google Patents
Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses functionalized homogeneous particle porous silicon dioxide microspheres and a preparation method and application thereof. The preparation method comprises the following steps of: (1) pre-preparing homogeneous particle porous polymer microspheres with determined components, particle diameters and apertures, and performing surface functionalized treatment on the porous polymer microspheres to obtain the functionalized homogeneous particle porous polymer microspheres; (2) dispersing the functionalized porous polymer microspheres in aqueous solution and adding silicon dioxide precursor to prepare silicon dioxide/polymer intermediate composite microspheres; (3) heating the silicon dioxide/polymer intermediate composite microspheres to remove the polymer to obtain the homogeneous particle porous silicon dioxide microspheres; and (4) performing surface modification on the homogeneous particle porous silicon dioxide microspheres by using a chemical reagent to form a functionalized group, wherein the particle diameter of the functionalized homogeneous particle porous silicon dioxide microspheres is within the range of between 1.7 and 100 microns; and the mesoporous aperture of the functionalized homogeneous particle porous silicon dioxide microspheres is within the range of between 20 and 1,000 angstroms. The functionalized homogeneous particle porous silicon dioxide microspheres can be used as chromatographic filler for efficiently analyzing and separating organic molecules and biological molecules.
Description
Technical field
The invention belongs to column packing technology of preparing and Application Areas thereof in the liquid chromatography technology, be specifically related to a kind of micron-sized functionalization all preparation method and the application of grain porous silica microballoon.
Background technology
Micron-sized porous silica microballoon is in analysis, catalysis and a lot of fields such as separate and all have a wide range of applications.Because its higher physical strength, heat-resisting, solvent-proof performance, be often used as catalyzed conversion, enzyme is fixed and the support skeleton of liquid chromatography.Along with the development of high-efficient liquid phase chromatogram technology, need accurately control the size and the aperture structure of porous silica microballoon, and size requires to be controlled between 3 to 10 microns, hole surface needs certain hydrophobicity.With regard to chromatographic property, all grain porous silica microballoon owing to the physical property of its uniform particle diameter, is much better than the silicon dioxide microsphere of those size distribution broads in application process.Therefore, the controlled equal grain porous silica microballoon of size and aperture structure is the first-selected column packing in the liquid chromatography technology.At present, adopt traditional sol-gel method can prepare the equal grain silicon dioxide microsphere of tens nanometers, but be difficult to above 1 micron to the hundreds of nanometer.Therefore, the equal grain porous silica microballoon of synthesizing micron-grade is the emphasis problem of current research always.
Chinese patent application 200810019069.3 discloses the method that a kind of composite shuttering legal system is equipped with mesoporous silicon dioxide micro-sphere on July 9th, 2008, the steps include: that compound concentration is the ammonia soln of 1.8～3.0MOL/L, in ammonia soln, add template and co-template, stirring and dissolving; To go up step gained mixing solutions and be heated to 30～80 ℃,, finish after reacting 5～6H under the constant agitation speed again to the positive tetraethyl orthosilicate of mixed solution and dripping calculated amount; Obtain the former powder of mesoporous silicon oxide after will going up step gained mixture drying; 5～6 hours removed template methods of the former powder roasting of silicon-dioxide with oven dry promptly get and can obtain the silicon dioxide microsphere that particle diameter is the meso-hole structure about the 80-500 nanometer, and particle diameter is less than 1 micron.
Chinese patent application 200810202772.8 discloses a kind of preparation method of mesoporous silicon dioxide micro-sphere of controllable aperture on April 22nd, 2009, with novel four-head quaternary cationics is structure directing agent, under alkaline condition, in alcohol-water system, pass through the sol-gel method synthesizing mesoporous silicon dioxide microsphere.The particle diameter of the porous silica microballoon that obtains is approximately 1 micron.
Deng (Chem. Master., 1995,10,1623-1626) announced a kind of method that in quaternary ammonium salt and ether, prepares mesoporous microsphere, the microspherulite diameter that obtains is distributed between 2 to 6 microns.(J. Chromatography A such as Shi, 2009,1216,7388-7393) announced a kind of method that in polyethylene oxide, prepares the porous silica microballoon, because it is very wide that the microspherulite diameter of gained distributes, before being applied to high performance liquid chromatography, must sieve and remove macrobead and small-particle.
The polymer microsphere template relevant with the disclosure prepare porous microsphere method (referring to Adv.Mater:2002,14,1768-1772; U.S. Pat 2006088470A1) be to be template with the expanded polystyrene microballoon, with spending the night after the salt acid soak, add the inorganics presoma, hydrolysis-condensation reaction is removed the polymer template and is obtained the porous, inorganic microballoon.But adopt the size of the porous, inorganic microballoon that this method obtains to dwindle 20-50% than original template microsphere, its productive rate nearly about 40%.
Therefore the preparation method who inquires into a kind of equal grain porous silica microballoon of micron-sized, particle diameter controllable aperture is that firm key issue is demanded in the liquid chromatography stuffing field urgently.
Summary of the invention
The object of the invention is to provide all grain porous silica microballoons of a kind of functionalization, it is inhomogeneous or particle diameter is too small or problem such as can not be controlled in mesoporous aperture to have solved the microspherulite diameter that the porous silica method for preparing microsphere obtains in the prior art, the present invention can effectively control aperture, structure and the pattern of microballoon when guaranteeing porous silica microballoon homogeneous sphere diameter.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
A kind of functionalization is grain porous silica microballoon all, it is characterized in that described microballoon prepares by the following method:
(1) prepares composition, particle diameter, the definite equal grain porous polymer microsphere in aperture in advance, and equal grain porous polymer microsphere is carried out surface-functionalized processing, obtain all grain porous polymer microspheres of functionalization;
(2) the equal grain of a functionalization porous polymer microsphere is dispersed in the solution, adds the preparation of silicon-dioxide presoma then and form the middle complex microsphere of silicon-dioxide/polymkeric substance;
(3) complex microsphere was removed the organic polymer material in the middle of heating made silicon-dioxide/polymkeric substance, obtained all grain porous silica microballoons;
(4) use chemical reagent that equal grain porous silica microballoon is carried out finishing, form the functionalization group, promptly form all grain porous silica microballoons of functionalization at an equal grain porous silica microsphere surface;
The particle diameter of the equal grain of described functionalization porous silica microballoon is in 1.7 μ m～100 mu m ranges; The mesoporous aperture of the equal grain of described functionalization porous silica microballoon is in 20～1000 scopes.
The present invention also provides a kind of all methods of grain porous silica microballoon of functionalization that prepare, and it is characterized in that said method comprising the steps of:
(1) prepares composition, particle diameter, the definite equal grain porous polymer microsphere in aperture in advance, and equal grain porous polymer microsphere is carried out surface-functionalized processing, obtain all grain porous polymer microspheres of functionalization;
(2) the equal grain of a functionalization porous polymer microsphere is dispersed in the aqueous solution, adds the preparation of silicon-dioxide presoma then and form the middle complex microsphere of silicon-dioxide/polymkeric substance;
(3) complex microsphere was removed the organic polymer material in the middle of heating made silicon-dioxide/polymkeric substance, obtained all grain porous silica microballoons;
(4) use chemical reagent that equal grain porous silica microballoon is carried out finishing, form the functionalization group, promptly form all grain porous silica microballoons of functionalization at an equal grain porous silica microsphere surface.
Preferably, in the described method steps (1) all the grain porous polymer microsphere be selected from the single polymers or the copolymer microsphere of methacrylic ester, vinylbenzene and derivative thereof.
Preferably, in the described method steps (1) all the particle diameter of grain porous polymer microsphere in 1.7 μ m～100 mu m ranges.
Preferably, the particle diameter of the equal grain porous silica microballoon in the described method steps (3) is in 1.7 μ m～100 mu m ranges; The mesoporous aperture of described equal grain porous silica microballoon is in 20～1000 scopes.
Preferably, the surface-functionalized processing of polymer microballoon is to adopt the polymerisation process that atomic migration causes (atom transfer radical polymerization ATRP) finishes in the described method steps (1).
Preferably, the surface-functionalized processing of polymer microballoon is to adopt the polyreaction (redox polymerization) of redox initiation to finish in the described method steps (1).
Preferably, the surface-functionalized group of polymer microballoon is an amido in the described method steps (1), and described amido is selected from primary amine, secondary amine and tertiary amine.
On the other hand, the present invention provides all application of grain porous silica microballoon aspect the isolated or purified compound of a kind of functionalization again, it is characterized in that the chromatographic column column packing of the equal grain of described functionalization porous silica microballoon as the separation and purification instrument.
Preferably, described application comprises that the principle of utilizing liquid chromatography separates chromatographic column or analyze as stationary phase the method for one or more soluble compounds.
Preferably, described application comprises flows through chromatographic column to the liquor that contains to be separated or analysis of compounds, then the step that the compound to be separated or that analyze that is adsorbed on the stationary phase is eluted.
The all application of grain porous silica microballoon aspect analysis or separation organic compound or biomacromolecule of a kind of functionalization provided by the invention.
Preferably, the equal grain of described functionalization porous silica microballoon is as chromatographic column filler or solid phase extraction column stuffing.Preferably, described application comprises that the principle of utilizing liquid chromatography separates chromatographic column or analyze the method for the organic and biomolecules of one or more solubilities as stationary phase.
Technical solution of the present invention is used for obtaining a kind of suitable liquid chromatography, have accurate size and aperture structure, and the monodisperse silica microspheres of functionalization, the functionalized polymer microsphere that adopts a kind of known size and the equal grain with vesicular structure is as the structure guiding material, allow the presoma of silicon-dioxide be penetrated in the functionalized polymer microsphere, under ammonia-catalyzed, form silicon-dioxide/polymer composite microsphere, remove the structure guiding material, obtain the high equal grain porous silica microballoon of productive rate, its structure is corresponding with structure guiding material polymer microballoon, its particle diameter is consistent with the porous polymer microsphere of structure guiding, and the equal grain porous silica microballoon to gained carries out finishing then.
Method of the present invention can effectively be controlled aperture, structure and the pattern of microballoon when guaranteeing silicon dioxide microsphere homogeneous sphere diameter.Concrete, the present invention prepares the method for the functionalized SiO 2 microballoon of equal grain, and described silicon dioxide microsphere is globulate roughly, and most of silicon dioxide microspheres have the aperture; This method at first prepares the polymer microballoon with vesicular structure that pre-determines particle diameter and aperture, and it is carried out surface-functionalized, and the functionalization that obtains having vesicular structure is the grain porous polymer microsphere all.Secondly, the polymer microballoon of functionalization is dispersed in the aqueous solution, adds the silicon-dioxide precursor then, form silicon-dioxide under suitable condition, generate the middle complex microsphere of silicon-dioxide/polymkeric substance.Once more, remove functionalized polymer from middle mixture, obtain porous silica spheres, the size of porous silica spheres is corresponding with the equal particle/polymer microballoon of functionalization.At last porous silica spheres is carried out finishing, introduce the functionalization group.
Spheroidal microsphere polymer microballoon with vesicular structure comprises the single polymers and the copolymer microsphere of methacrylic ester, vinylbenzene and derivative thereof.The particle diameter of spheroidal microsphere polymer microballoon with vesicular structure from 1.7 μ m to 100 μ m.All the particle diameter of grain silicon dioxide microsphere from 1.7 μ m to 100 μ m; Aperture from 20 to 1000.The described equal particle/polymer microballoon of functionalization with vesicular structure is by atomic migration initiated polymerization method (atom transfer radical polymerization, ATRP) finish, also can form by the polyreaction (redox polymerization) of redox initiation.
In this article, a dust or equal 1/10000000000th meter, or 1/10th nanometers; One nanometer or nm equal part per billion meter; One micron or μ m equal micron.Porous polymer microsphere, porous silica microballoon, middle mixture are porous material.
Preparation method's the first step is the spherical polymer microballoon that preparation has vesicular structure, then this polymer microballoon is carried out finishing, obtains the polymer microballoon of functionalization.
As the polymer microballoon of structure guiding material is porous, crosslinked or do not have crosslinked.The diameter of polymer microballoon is in the 1.7-100 micrometer range.
Above-mentioned polymer microballoon is meant any can reaction with chemical reagent, carry out functionalization, and the infiltration of oxide presoma forms the organic polymer microballoon of silicon-dioxide, used herein is polystyrene and polyacrylate(s) and derivative thereof, as poly (glycidyl methacrylate) microballoon, poly (methyl methacrylate) micro-sphere, polystyrene microsphere, poly (glycidyl methacrylate)-Ethylene glycol dimethacrylate copolymerization microsphere, polystyrene-glycidyl methacrylate and copolymerization microsphere, polystyrene-divinylbenzene microspheres etc.
Above-mentioned polymer microballoon can be commercially available or prepare by polyreaction; Polyreaction comprises letex polymerization, emulsifier-free emulsion polymerization, micro-emulsion polymerization, mini-emulsion polymerization, dispersion polymerization, suspension polymerization and seeding polymerization.
Surface-functionalized processing in the step (1) is meant with using chemical reagent to introduce the functionalization group by chemical reaction, used chemical reagent comprises any can reaction with polymer microballoon, introduce the reagent of functionalization group, the functional group of introducing is such as chlorine, bromine, iodine, amino, hydroxyl, carboxyl, carboxylicesters or epoxy group(ing), or the combination of above group.The chemical reagent that is suitable for for example but is not limited to bischlormethyl ether, dihydroxymethyl amine, N, N-dimethyl-ethylenediamine, quadrol, hexanediamine-[1,6], tetramino methane, polyvinylamine, ammoniacal liquor, polyoxyethylene and derivative thereof.The functionalization group comprises that separate base repeats or depend on the part of long-chain or short chain, as oxyethyl group in the oligopolymer or polyethylene oxide, and amino in the oligopolymer or polyvinylamine, the hydroxyl in the oligopolymer or polyvinyl alcohol or the like.Vinyl polymer based on, but be not limited to polystyrene, polyacrylic ester, and the derivative that comprises the functionalization group that can be connected to the polymer microballoon surface by atomic migration initiated polymerization or redox reaction.The atomic migration initiated polymerization has a detailed description and relevant references in U.S. Pat 6071980.Redox initiation is meant that monomeric polymerization is by oxidising agent and goes back that the transfer of electronics causes such process between the original reagent.At Journal of Applied Polymer Science, Volume 42, and Issue 11, and pages 2885 – 2891,1991. have reported the example of cerium ion as redox initiator.Anti-for the atomic migration initiated polymerization, have nanometer and before the polymer microballoon polymerization of micrometer structure, may contain the halogen atom group.For the redox initiate polymerization reaction, have nanometer and before the polymer microballoon polymerization of micrometer structure, may contain, but be not limited to hydroxyl, thiol group, aldehyde radical, thiohydroxy, amino etc.Before the polymerization, redox reaction may be by water, and cause on the polymer microballoon surface of monomer phase or functionalization.
Step (2) comprises the polymer microballoon after the surface-functionalized processing is distributed in the aqueous solution of ethanol and ammoniacal liquor, then oxide precursor is joined in the aqueous suspension that contains polymer microballoon, used alcohol comprises methyl alcohol, ethanol, Virahol and ethylene glycol etc. is alcohol similarly, oxide precursor for example, but be not limited to, methyl silicate, tetraethoxy, positive silicic acid propyl ester, butyl silicate, alkyl trimethoxysilane, the alkyl triethoxyl silane, alkyl three second propyl silanes, dialkyl group dimethoxy silane, dialkyl group diethoxy silane (alkyl can be the alkyl that contains 1-24 carbon atom chain length), phenyltrimethoxysila,e, phenyl triethoxysilane, amine propyl trimethoxy silicane, epoxypropyl Trimethoxy silane and two or more mixtures.Under experiment condition disclosed by the invention, the silicon-dioxide presoma is penetrated in the porous polymer microsphere of functionalization, generates silicon-dioxide/polymer composite microsphere.
Structure guiding material in step (3) the intermediate polymer microballoon is decomposes at high temperature, and temperature is controlled at 200-1500 usually
0
C removes polymkeric substance and generates porous silica thing microballoon.
By chemical process various functional group graftings are comprised to these functional groups of silicon dioxide microsphere surface during the finishing of step (4), but be not limited to, the alkyl of different chain length, particularly those surpass the combination of alkyl, amino, hydroxyl, carboxyl, sulfonic group, carboxylicesters, sulfonate groups and any above group of 6 carbon atoms.
The method that technical solution of the present invention also provides chromatographic column that the microballoon that above-mentioned preparation method obtains is equipped with in a use to carry out separation and purification.The separation principle of liquid phase chromatography is exactly to utilize the difference of affinities such as the partition ratio of various materials to be separated in the solid-liquid two-phase, adsorptive power to carry out isolating.Use liquid-flow that external force will contain sample mutually by stationary phase, when the mixture flow of carrying in the moving phase during through stationary phase, each component and stationary phase hole surface in the mixture interact.Because each component is in character and structural difference in the mixture, different with size, the power of the reactive force that produces between the stationary phase hole surface, along with moving of moving phase, mixture is in two alternate partition equilibriums through repeated multiple times, the asynchronism(-nization) that makes each component be fixed mutually to keep and separating, the particle diameter and the aperture structure of the equal grain porous silica microballoon that present method stationary phase uses can accurately be controlled by the polymer microballoon of structure guiding material, and can use according to different liquid chromatographies and carry out functionalization.Functionalization is grain porous silica microspherulite diameter homogeneous all, can guarantee consistence and the circulation ratio of chromatographic column on performances such as target compound separation efficiency, stage number, retention time, pressure.
The present invention all equal grain of a grain functionalization porous silica microspherulite diameter can be used for solid phase extraction filler.
The term explanation:
Normal-phase chromatography: the stationary phase that normal-phase chromatography is used is generally silica gel (Silica) and other have the polar functional group amine groups, as (NH
2
, APS) with cyano group group (CN, bonded phase packings CPS).
Because silicon hydroxyl (SiOH) or other polar group polarity on silica gel surface are stronger, therefore, isolating order is the polarity size according to each component in the sample, and promptly the more weak component of polarity is rinsed out chromatographic column at first.The moving phase polar phase contrast stationary phase that normal-phase chromatography uses is low, as normal hexane (Hexane), and chloroform (Chloroform), methylene dichloride (Methylene Chloride) etc.
Reverse chromatograms: the filler that reverse chromatograms is used often is to be matrix with silica gel, and surface bond has the bonding phase of polar phase to more weak functional group.The employed moving phase polarity of reverse chromatograms is stronger, is generally the mixture of water, damping fluid and methyl alcohol, acetonitrile etc.The order that sample flow goes out chromatographic column is that the stronger component of polarity is rinsed out at first, and the weak component of polarity can have stronger reservation on chromatographic column.
(coefficient of variability, CV): the statistic of the particle diameter degree of variation size of the porous silica microballoon for preparing of expression is the percentage ratio of the ratio of standard deviation and mean number to the variation coefficient.The particle size distribution range of representing the porous silica microballoon when the variation coefficient is big is wide, the particle diameter heterogeneity; When the particle size distribution range of the variation coefficient hour expression porous silica microballoon narrow, uniform particle diameter.The variation coefficient of the particle diameter of porous silica microballoon is greater than 10% in the prior art, even reaches about 30%, so need sieve operation; The variation coefficient of the particle diameter of porous silica microballoon of the present invention generally need not screening and promptly can be used as column packing or extraction stuffing use less than 5%.
With respect to scheme of the prior art, advantage of the present invention is:
The equal grain porous silica microballoon aperture structure of the method preparation that technical solution of the present invention openly provides is corresponding with structure guiding material polymer microballoon, so, select for use suitable porous polymer microsphere as the structure guiding material, just can access the equal grain porous silica microballoon in designation hole footpath.Again it is carried out functionalization, just can satisfy the demand of different application.
Another advantage that the present invention is better than prior art is particle diameter and the size distribution and the structure guiding material polymer microballoon correspondence of resulting equal grain porous silica microballoon.The phenomenon that does not have size to dwindle is easy to control the particle diameter of microballoon.The equal grain porous silica microballoon of disclosure preparation is particularly suitable for those quantitative analyses that need stable result to be separated.And the method for technical solution of the present invention is fit to scale operation, and the preparation microballoon is easy to be dispersed in the different liquid, does not have aggregation phenomenon.
Description of drawings
Below in conjunction with drawings and Examples the present invention is further described:
Fig. 1 is the electronic scanning Electronic Speculum figure of the equal grain silicon dioxide microsphere of the present invention's acquisition; Wherein particle diameter is at 10 μ m(embodiment 21);
Fig. 2 is the electronic scanning Electronic Speculum figure of the equal grain silicon dioxide microsphere of the present invention's acquisition; Wherein particle diameter is at 35 μ m(embodiment 23);
Fig. 3 is the electronic scanning Electronic Speculum figure (comparative example) of 10 microns (CV=10%) silicon dioxide microspheres commonly used on the market;
Fig. 4 is the separation and purification color atlas that positive silicon dioxide microsphere (10 microns) is used for taxol;
Fig. 5 is used for Regular Insulin separate colors spectrogram for the anti-phase silicon dioxide microsphere of C18 bonding (10 microns);
Fig. 6 is used for the separate colors spectrogram of benzene ring compound (as aniline, methyl-phenoxide and toluene) for the anti-phase silicon dioxide microsphere of C18 bonding (5 microns).
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are used to the present invention is described and are not limited to limit the scope of the invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.Below by various embodiment specific implementation process of the present invention is described, wherein embodiment 1～7 is equal preparation process of grain porous polymer microsphere.Embodiment 8～18 is the reaction kinetic process of equal grain porous polymer microsphere.Embodiment 19-23 is the building-up process of equal grain porous silica microballoon; Embodiment 24～26 is the reaction kinetic process of equal grain porous silica microballoon.Comparative Examples provides the preparation method of conventional porous silica microballoon in the prior art, and application examples 1～2 is two typically used of technical scheme of the present invention on liquid chromatography.
Embodiment 1 synthetic all grains expanded polystyrene/divinylbenzene polymer microballoon
Get 30g vinylbenzene, 60g divinylbenzene (80%) and 100g hexalin join in three mouthfuls of round-bottomed flasks of 2000mL, and to wherein adding initiator 1.5g Diisopropyl azodicarboxylate, mechanical stirring makes it to dissolve fully.Add 800g in the above in the solution and contain 0.04% octadecyl sulfonic acid and receive the aqueous solution, add 25g 2.5 μ m polystyrene seed after the ultrasonic emulsification, in ℃ reaction of room temperature swelling 24h post-heating to 80.Isolate equal grain porous crosslinked polystyrene microballoon after the cooling, particle diameter 5 μ m, variation coefficient CV=3.5%.
Get 30g vinylbenzene, 60g divinylbenzene (80%) and 100g hexalin join in three mouthfuls of round-bottomed flasks of 2000mL, and to wherein adding initiator 1.5g Diisopropyl azodicarboxylate, mechanical stirring makes it to dissolve fully.Add 800g in the above in the solution and contain 0.04% octadecyl sulfonic acid and receive the aqueous solution, add 25g 5 μ m polystyrene seed after the ultrasonic emulsification, in ℃ reaction of room temperature swelling 24h post-heating to 80.Isolate equal grain porous crosslinked polystyrene microballoon after the cooling, particle diameter is 10 μ m, variation coefficient CV=3.5%.
Embodiment 3 synthetic all grains expanded polystyrene/divinylbenzene polymer microballoons
In 5 liters of reactors, as seed, its granularity is 13.5 μ m with the single granules of polystyrene that disperses swellable of the 60g of pre-preparation, and CV=3.8 adds and contains in the 1300g deionized water of 1g hydroxypropylcellulose; Under 150 rev/mins speed, stir and be heated to 85 ℃.
With 800g vinylbenzene with after the 10g dibenzoyl peroxide mixes; add and contain in the 1500g water of 0.5g KI, 0.5g hydroxypropylcellulose and 4.0g Triton X-405; mixed back emulsification; under 85 ℃, join in the described aqueous solution with the speed that increases progressively; for example original speed is 1ml/min, and final velocity is 10ml/min, drips 6 hours altogether; carry out first step reaction, control its level of response and be about 80%.
With 800g vinylbenzene and 10g dibenzoyl peroxide, add and contain in the 1500g water of 0.5g hydroxypropylcellulose and 4.0gTritonX-405, mixed back emulsification, conditioned reaction still temperature to 50 ℃, be added dropwise to the total overall reaction thing in 2 hours, continue swelling afterwards again 0.5 hour, and then add 0.4% hydroxypropyl cellulose aqueous solution 500g.
Be heated to 85 ℃, carried out polyreaction 10 hours, or up to reacting completely.
Adopt ordinary method at last, comprise filtration, wash, refilter, drying and other steps, reclaim polystyrene microsphere.Measure its particle diameter and size distribution with Beckman Coulter Counter, particle diameter is 50 μ m, variation coefficient CV=4.0%.
Embodiment 4 synthetic all grains expanded polystyrene/divinylbenzene polymer microballoons
In 5 liters of reactors, as seed, its granularity is 50 μ m with the single granules of polystyrene that disperses swellable of the 200g of pre-preparation, and CV=4.2 adds and contains in the 1300g deionized water of 1g hydroxypropylcellulose; Under 150 rev/mins speed, stir and be heated to 85 ℃.
With 800g vinylbenzene with after the 10g dibenzoyl peroxide mixes; add and contain in the 1500g water of 0.5g KI, 0.5g hydroxypropylcellulose and 4.0g Triton X-405; mixed back emulsification; under 85 ℃, join in the described aqueous solution with the speed that increases progressively; for example original speed is 1ml/min, and final velocity is 10ml/min, drips 6 hours altogether; carry out first step reaction, control its level of response and be about 90%.
With 800g vinylbenzene and 10g dibenzoyl peroxide, add and contain in the 1500g water of 0.5g hydroxypropylcellulose and 4.0g Triton X-405, mixed back emulsification, conditioned reaction still temperature to 60 ℃, be added dropwise to the total overall reaction thing in 2 hours, continue swelling afterwards again 0.5 hour, and then add 0.4% hydroxypropyl cellulose aqueous solution 500g.
Be heated to 85 ℃, carried out polyreaction 10 hours, or up to reacting completely.
Adopt ordinary method at last, comprise filtration, wash, refilter, drying and other steps, reclaim polystyrene microsphere.Measure its particle diameter and size distribution with Beckman Coulter Counter, particle diameter is 100 μ m, variation coefficient CV=4.0%.
Get 30g glycidyl methacrylate monomer, 60g Ethylene glycol dimethacrylate and 100g hexalin join in three mouthfuls of round-bottomed flasks of 2000mL, and to wherein adding initiator 1.5g Diisopropyl azodicarboxylate, mechanical stirring makes it to dissolve fully.Add 800g in the above in the solution and contain 0.04% octadecyl sulfonic acid and receive the aqueous solution, add 25g 2.5 μ m polystyrene seed, post-heating to 75 ℃ reaction when room temperature swelling 24h after the ultrasonic emulsification.Isolate equal grain porous glycidyl methacrylate/Ethylene glycol dimethacrylate copolymerization microsphere after the cooling, particle diameter 5 μ m, variation coefficient CV=4.0 %.
Embodiment 6
Get 30g glycidyl methacrylate monomer, 60g Ethylene glycol dimethacrylate and 100g hexalin join in three mouthfuls of round-bottomed flasks of 2000mL, and to wherein adding initiator 1.5g Diisopropyl azodicarboxylate, mechanical stirring makes it to dissolve fully.Add 800g in the above in the solution and contain 0.04% octadecyl sulfonic acid and receive the aqueous solution, add 25g 5 μ m polystyrene seed after the ultrasonic emulsification, in ℃ reaction of room temperature swelling 24h post-heating to 75.Isolate equal grain porous glycidyl methacrylate/Ethylene glycol dimethacrylate copolymerization microsphere after the cooling, particle diameter 10 μ m, variation coefficient CV=4.0%.
7 equal porous propylene acid of embodiment methyl esters/divinylbenzene copolymerization microsphere
Get the 80g methacrylate monomer, 20g divinylbenzene and 100g hexalin join in three mouthfuls of round-bottomed flasks of 2000mL, and to wherein adding initiator 1.5g Diisopropyl azodicarboxylate, mechanical stirring makes it to dissolve fully.Add 800g in the above in the solution and contain 0.04% octadecyl sulfonic acid and receive the aqueous solution, add 25g 10 μ m polystyrene seed after the ultrasonic emulsification, in ℃ reaction of room temperature swelling 24h post-heating to 70.Isolate equal grain porous propylene acid methyl esters/divinylbenzene copolymerization microsphere after the cooling, particle diameter 35 μ m, variation coefficient CV=3.2%.
Embodiment 8 polystyrene/divinylbenzene microsphere surface chloromethylations
Chloromethylation: 50g exsiccant polystyrene/divinylbenzene (PS/DVB) microballoon is joined in the there-necked flask of 1000mL, add 500mL trichloromethane dispersion microsphere, system is at 0 ℃ of following mechanical stirring 1h, and keeps 0 ℃ of condition, adds anhydrous stannic chloride (SnCl then
4
) 8.5ml, stir after 5 minutes, dropwise add chloromethyl ether (CH
3
OCH
2
Cl) 50mL.Chloromethyl ether dropwises, and system stirs 30min, continues to stir 3h then under room temperature.
After reaction finishes, the product vacuum filtration, and use deionized water (100mL), 5% hydrochloric acid (100mL), deionized water (100mL), tetrahydrofuran (THF) (100mL), ethanol (100mL), acetone (100mL) to clean successively, microballoon after the cleaning obtains the polystyrene/divinylbenzene microballoon of chloromethylation in 60 ℃ of following vacuum-drying 12h.
The polystyrene/divinylbenzene microballoon that embodiment 9 synthesis of ethylenediamine are surface-functionalized
Quadrol functionalization: get equal grain chloromethylated polystyrene/Vinylstyrene copolymerization microsphere (10 microns variation coefficient CV=4%) of 80.0g, join in three mouthfuls of round-bottomed flasks of 1000mL, to wherein adding 200 mL ethanol, ultra-sonic dispersion 30min.Under the 100rpm mechanical stirring, add the 200mL quadrol, be warming up to 80 ℃, suction filtration behind the back flow reaction 6h, and it is inferior alternately to give a baby a bath on the third day after its birth with ethanol and distilled water, 50 ℃ of dry 12h obtain 10 microns variation coefficient CV=4% of polystyrene/divinylbenzene microballoon of quadrol functionalization.
The polystyrene/divinylbenzene microballoon that embodiment 10 synthesization of dimethyl quadrols are surface-functionalized
Dimethyl-ethylenediamine functionalization: get equal grain chloromethylated polystyrene/Vinylstyrene copolymerization microsphere of 80.0g, join in three mouthfuls of round-bottomed flasks of 1000mL, to wherein adding 200 mL ethanol, ultra-sonic dispersion 30min.Under the 100rpm mechanical stirring, add the 200mL dimethyl-ethylenediamine, be warming up to 80 ℃, suction filtration behind the back flow reaction 6h, and it is inferior alternately to give a baby a bath on the third day after its birth with ethanol and distilled water, 50 ℃ of dry 12h obtain the polystyrene/divinylbenzene microballoon of dimethyl-ethylenediamine functionalization.
The embodiment 11 synthetic surface-functionalized polystyrene/divinylbenzene microballoons of Trimethylamine
Trimethylamine functionalization: get equal grain chloromethylated polystyrene/Vinylstyrene copolymerization microsphere of 80.0g, join in three mouthfuls of round-bottomed flasks of 1000mL, to wherein adding 200 mL water, ultra-sonic dispersion 30min.Under the 100rpm mechanical stirring, add 200mL Trimethylamine hydrochloride, be warming up to 80 ℃, suction filtration behind the back flow reaction 12h, and it is inferior alternately to give a baby a bath on the third day after its birth with distilled water, 50 ℃ of dry 12h obtain the polystyrene/divinylbenzene microballoon of Trimethylamine amino-functionalizations.
Polymethacrylate/Ethylene glycol dimethacrylate the copolymerization microsphere of embodiment 12 quadrol functionalization
Quadrol functionalization: get all grain porous polymethyl glycidyl acrylate/Ethylene glycol dimethacrylate copolymerization microspheres of 80.0g, join in three mouthfuls of round-bottomed flasks of 1000mL, to wherein adding 200 mL ethanol, ultra-sonic dispersion 30min.Under the 100rpm mechanical stirring, add the 200mL quadrol, be warming up to 80 ℃, suction filtration behind the back flow reaction 6h, and it is inferior alternately to give a baby a bath on the third day after its birth with ethanol and distilled water, 50 ℃ of dry 12h obtain the polymethacrylate/Ethylene glycol dimethacrylate copolymerization microsphere of quadrol functionalization
Embodiment 13 polypropylene amine microsphere surface functionalization
Get 20.0g chloromethylated polystyrene/divinylbenzene microspheres copolymerization microsphere, join in three mouthfuls of round-bottomed flasks of 100mL, to wherein adding 50mL ethanol, ultra-sonic dispersion 30min.Under the 100rpm mechanical stirring, add the 10g polypropylene amine, be warming up to 80 ℃, suction filtration behind the back flow reaction 6h, and it is inferior alternately to give a baby a bath on the third day after its birth with ethanol and distilled water, 50 ℃ of dry 12h obtain the amine functional polyacrylate copolymerization microspheres.
Embodiment 14 polyethyene diamine microsphere surface functionalization
Get 20.0g chloromethylated polystyrene/divinylbenzene microspheres copolymerization microsphere 10 μ m, CV=4% joins in three mouthfuls of round-bottomed flasks of 100mL, to wherein adding 50mL ethanol, ultra-sonic dispersion 30min.Under the 100rpm mechanical stirring, add the poly-ethamine of 10g, be warming up to 80 ℃, suction filtration behind the back flow reaction 6h, and it is inferior alternately to give a baby a bath on the third day after its birth with ethanol and distilled water, 50 ℃ of dry 12h obtain the amine functional polyacrylate copolymerization microspheres.
Get 20.0g 5 μ m, porous polymethyl glycidyl acrylate/Ethylene glycol dimethacrylate copolymerization microsphere of CV=4% joins in three mouthfuls of round-bottomed flasks of 100mL, to wherein adding 50mL ethanol, ultra-sonic dispersion 30min.Under the 100rpm mechanical stirring, add the 10g polypropylene amine, be warming up to 80 ℃, suction filtration behind the back flow reaction 6h, and it is inferior alternately to give a baby a bath on the third day after its birth with ethanol and distilled water, 50 ℃ of dry 12h.
The polyreaction that embodiment 16 adopts atomic migration to cause is introduced the polymers function base at microsphere surface
Get the polystyrene/divinylbenzene copolymerization microsphere (20%) of chloromethylation of 10g particle diameter 7 μ m and 0. 9g cuprous bromide in three mouthfuls of round-bottomed flasks of 100mL.Then in another 100mL single port flask with 1.9g 2,2 '-dipyridyl is dissolved in the 40mL glytidyl methacrylate, and joins in the there-necked flask, with magnetic agitation polymer microsphere is disperseed.System sealing vacuumizes, and uses nitrogen replacement, at last nitrogen is inserted under the liquid level, under nitrogen atmosphere in 100 ℃ of magnetic force splash bar 16h.Resulting microballoon is alternately given a baby a bath on the third day after its birth inferior with deionized water and ethanol, each consumption 50mL is put in the dry polystyrene/divinylbenzene copolymerization microsphere that obtains the poly (glycidylmethacrylate--co-ethylene dimethacrylate) functionalization in 60 ℃ of vacuum drying ovens.
Get the polystyrene/divinylbenzene copolymerization microsphere of above-mentioned equal grain porous polymethyl acrylic acid epoxy propyl ester functionalization, join in three mouthfuls of round-bottomed flasks of 1000mL, to wherein adding 200 mL ethanol, ultra-sonic dispersion 30min.Under the 100rpm mechanical stirring, add the 200mL quadrol, be warming up to 80 ℃, suction filtration behind the back flow reaction 6h, and it is inferior alternately to give a baby a bath on the third day after its birth with ethanol and distilled water, 50 ℃ of dry 12h obtain the copolymerization microsphere of quadrol functionalization
Embodiment 17 adopts the polyreaction of redox initiation to introduce polymers function group at microsphere surface
The polystyrene/divinylbenzene copolymerization microsphere (20%) of getting 10g particle diameter 50 μ m chloromethylations is in three mouthfuls of round-bottomed flasks of 500mL, add 200mL DMF dispersion microsphere, add 19.5g N-methyl D glycosamine and 13.8g salt of wormwood, system is in 80 ℃ of lower magnetic force splash bar 20h, reaction finishes the back microballoon and alternately gives a baby a bath on the third day after its birth inferior with deionized water and ethanol, each consumption 50mL. obtains hydroxylated microballoon, is put in 60 ℃ of vacuum drying ovens dry.
Get above hydroxylated microballoon 10g in three mouthfuls of round-bottomed flasks of 500mL, add 200mL deionized water dispersion microsphere system, system vacuumizes and uses nitrogen replacement, then nitrogen is imported under the liquid level.In the beaker of a 500mL 6g ceric ammonium nitrate is dissolved in the nitric acid of 50mL 1mol/L, this mixture joins in three mouthfuls of round-bottomed flasks.Be warming up to 60 ℃, and keep 0.5h, dropwise add the 50mL glytidyl methacrylate then, dropwise, in 60 ℃ of reaction 4h, alternately give a baby a bath on the third day after its birth inferior with deionized water and ethanol by resulting microballoon under nitrogen atmosphere for system, each consumption 50mL is put in 60 ℃ of vacuum drying ovens dry.
Get above hydroxylated microballoon 10g in three mouthfuls of round-bottomed flasks of 500mL, add 200mL deionized water dispersion microsphere system, system vacuumizes and uses nitrogen replacement, then nitrogen is imported under the liquid level.In the beaker of a 500mL 6g ceric ammonium nitrate is dissolved in the nitric acid of 50mL 1mol/L, this mixture joins in three mouthfuls of round-bottomed flasks.Be warming up to 60 ℃, and keep 0.5h, dropwise add the 50mL Methacrylamide then, dropwise, in 60 ℃ of reaction 4h, alternately give a baby a bath on the third day after its birth inferior with deionized water and ethanol by resulting microballoon under nitrogen atmosphere for system, each consumption 50mL is put in 60 ℃ of vacuum drying ovens dry.
The embodiment 18 polymethyl acrylates/divinylbenzene copolymerization microsphere aminated reaction in surface
5 gram polymethyl acrylate/divinylbenzene copolymerization microspheres (35 microns, variation coefficient CV=3.2%) add 100 milliliters of dimethyl formamides, and the back that stirs adds 20 gram dimethyl-ethylenediamines.Be heated to 120 degree 20 hours.Obtain functionalized acrylic methyl esters/divinylbenzene copolymerization microsphere through filtering to clean.
Synthesizing of 19 equal porous silica microballoons of embodiment
The surface-functionalized microballoon of quadrol (embodiment 9) that has of getting 2g particle diameter 10 μ m places three mouthfuls of round-bottomed flasks of 250mL, adds 40mL ethanol and 10mL deionized water, and ultra-sonic dispersion 30min adds ammoniacal liquor under mechanical stirring.In three mouthfuls of round-bottomed flasks, add 10g tetraethoxysilane and 3mL alcoholic acid mixing solutions.After adding, continue stirring reaction 24h.After having reacted, with F molding sand core funnel suction filtration, and it is inferior alternately to give a baby a bath on the third day after its birth with the second alcohol and water, 50 ℃ of dry 12h.Polymkeric substance/SiO 2 composite microsphere that drying is good is warming up to 800 ℃ piecemeal in retort furnace, keep this temperature calcination 6h, obtains the equal grain porous silica microballoon of 10 μ m at last, CV=4%.Microballoon mean pore size 120 dusts, specific surface area 300 square meter/grams.
Synthesizing of 20 equal porous silica microballoons of embodiment
The surface-functionalized microballoon of quadrol (embodiment 15) that has of getting 2g particle diameter 5 μ m places three mouthfuls of round-bottomed flasks of 250mL, adds 40mL ethanol and 10mL deionized water, and ultra-sonic dispersion 30min adds ammoniacal liquor under mechanical stirring.In three mouthfuls of round-bottomed flasks, add 10g tetraethoxysilane and 3mL alcoholic acid mixing solutions.After adding, continue stirring reaction 24h.After having reacted, with F molding sand core funnel suction filtration, and it is inferior alternately to give a baby a bath on the third day after its birth with the second alcohol and water, 50 ℃ of dry 12h.Polymkeric substance/SiO 2 composite microsphere that drying is good is warming up to 800 ℃ piecemeal in retort furnace, keep this temperature calcination 6 h, obtains the equal grain porous silica microballoon of 5 μ m at last, CV=4%.Microballoon mean pore size 150 dusts, specific surface area 280 square meter/grams
Synthesizing of 21 equal porous silica microballoons of embodiment
The surface-functionalized microballoon of polyethyene diamine (embodiment 14) that has of getting 2g particle diameter 10 μ m places three mouthfuls of round-bottomed flasks of 250mL, adds 40mL ethanol and 10mL deionized water, and ultra-sonic dispersion 30min adds ammoniacal liquor under mechanical stirring.In three mouthfuls of round-bottomed flasks, add 10g tetraethoxysilane and 3mL alcoholic acid mixing solutions.After adding, continue stirring reaction 24h.After having reacted, with F molding sand core funnel suction filtration, and it is inferior alternately to give a baby a bath on the third day after its birth with the second alcohol and water, 50 ℃ of dry 12h.Polymkeric substance/SiO 2 composite microsphere that drying is good is warming up to 800 ℃ piecemeal in retort furnace, keep this temperature calcination 6 h, obtains the equal grain porous silica microballoon of 10 μ m at last, variation coefficient CV=4%.Microballoon mean pore size 300 dusts, specific surface area 100 square meter/grams.Be illustrated in figure 1 as the equal grain porous silica microballoon of acquisition, its median size is 10 μ m; Yield is 99.8%.
Synthesizing of 22 equal porous silica microballoons of embodiment
The surface-functionalized microballoon of quadrol (embodiment 17) that has of getting 2g particle diameter 50 μ m places three mouthfuls of round-bottomed flasks of 250mL, adds 40mL ethanol and 10mL deionized water, and ultra-sonic dispersion 30min adds ammoniacal liquor under mechanical stirring.In three mouthfuls of round-bottomed flasks, add 10g tetraethoxysilane and 3mL alcoholic acid mixing solutions.After adding, continue stirring reaction 24h.After having reacted, with F molding sand core funnel suction filtration, and it is inferior alternately to give a baby a bath on the third day after its birth with the second alcohol and water, 50 ℃ of dry 12h.Polymkeric substance/SiO 2 composite microsphere that drying is good is warming up to 800 ℃ piecemeal in retort furnace, keep this temperature calcination 6 h, obtains the equal grain porous silica microballoon of 49 μ m at last.Microballoon mean pore size 200 dusts, specific surface area 250 square meter/grams, variation coefficient CV=4%, yield are 99.7%.
Synthesizing of 23 equal porous silica microballoons of embodiment
Get 2g particle diameter 35 μ m, the surface-functionalized microballoon of amido (embodiment 18) that has of variation coefficient CV=3.2% places three mouthfuls of round-bottomed flasks of 250mL, adds 40mL ethanol and 10mL deionized water, and ultra-sonic dispersion 30min adds ammoniacal liquor under mechanical stirring.In three mouthfuls of round-bottomed flasks, add 10g tetraethoxysilane and 3mL alcoholic acid mixing solutions.After adding, continue stirring reaction 24h.After having reacted, with F molding sand core funnel suction filtration, and it is inferior alternately to give a baby a bath on the third day after its birth with the second alcohol and water, 50 ℃ of dry 12h.Polymkeric substance/SiO 2 composite microsphere that drying is good is warming up to 800 ℃ piecemeal in retort furnace, keep this temperature calcination 6 h, obtains the equal grain porous silica microballoon of 35 μ m at last.Microballoon mean pore size 50 dusts, specific surface area 600 square meter/grams, variation coefficient CV=3.2%.Be illustrated in figure 2 as the equal grain porous silica microballoon of acquisition, its median size is 35 μ m, and yield is 99.8%.
Polydispersion silicon dioxide microsphere commonly used on the Comparative Examples market is synthetic
In three mouthfuls of round-bottomed flasks of 250mL, add 40mL ethanol and 10mL deionized water, the 10g tetraethoxysilane adds ammoniacal liquor under mechanical stirring.Reaction 24h, after having reacted, with F molding sand core funnel suction filtration, and it is inferior alternately to give a baby a bath on the third day after its birth with the second alcohol and water, 50 ℃ of dry 12h.The silicon dioxide microsphere that drying is good is warming up to 800 ℃ piecemeal in retort furnace, keep this temperature calcination 6h.Obtain the uneven silicon dioxide microsphere of size, CV=12%.The polydispersion silicon dioxide microsphere that Fig. 3 obtains for Comparative Examples, from figure as can be seen, the size of polydispersion silicon dioxide microsphere differs.When carrying out the separation and purification analytical applications, need the polydispersion silicon dioxide microsphere that obtain be sieved, obtain the comparatively silicon dioxide microsphere of homogeneous of particle diameter, last yield is the highest 40%.
Embodiment 24 silicon dioxide microspheres surface alkylated reaction
Octadecyl Trimethoxy silane 200 g are dissolved in the 800 ml toluene, add all grain porous silica microballoon 120 g, are heated to 110 ℃ of backflow 24h, clean after filtration after the cooling, and the dry octadecyl silane that obtains can be made the reverse chromatograms filler.
Embodiment 25 silicon dioxide microspheres surface alkylated reaction
Eight alkyl trimethoxysilanes, 200 g are dissolved in the 800 ml toluene, add all grain porous silica microballoon 120 g, are heated to 110 ℃ of backflow 24h, and cooled and filtered is cleaned, and the dry eight alkyl linked silane that obtain are done the reverse chromatograms filler.
Embodiment 26 silicon dioxide microspheres are surface-functionalized
Amine oxypropyl trimethyl silane 100 g are dissolved in the 800 ml toluene, add all grain porous silica microballoon 120 g, be heated to 110 ℃ of backflow 24h, the cooled and filtered cleaning, the dry silicon dioxide microsphere that obtains surface band amido can be used for sugared post separation and analyzes filler.
Fig. 4 obtains the separation and purification color atlas that equal positive silicon dioxide microspheres (particle diameter is 10 microns) of grain is used for taxol for the present invention; The anti-phase silicon dioxide microsphere of C18 bonding (particle diameter is 10 microns) of grain is used for Regular Insulin separate colors spectrogram to Fig. 5 for the present invention obtains all; Fig. 6 obtains the separate colors spectrogram that equal anti-phase silicon dioxide microspheres of C18 bonding (particle diameter is 5 microns) of grain is used for benzene ring compound (aniline, methyl-phenoxide and toluene) for the present invention.Below be typical analytical applications example and condition thereof.
Application examples 1 is utilized all, and grain porous silica microballoon carries out the analysis of benzene-like compounds as the chromatographic column of high performance liquid chromatography
The 4.6*250mm chromatographic column of equal grain porous silica microballoon of the octadecyl bonding of 10 μ m is equipped with in employing, moving phase is 45% acetonitrile solution that contains 0.1% trifluoroacetic acid, flow velocity 1ml/min, the detection wavelength is 210nm, last sample concentration is the aniline of volume ratio 0.1%, 0.2% methyl-phenoxide, 0.5% toluene, applied sample amount 2 μ L, appearance time aniline is 4.34min, methyl-phenoxide is 7.52min, toluene is 11.51min, calculate post with aniline and imitate 20150 pieces/meter, calculate post with methyl-phenoxide and imitate 44070 pieces/meter, calculate post with toluene and imitate 95679 pieces/meter.
Application examples 2 is utilized all, and grain porous silica microballoon carries out the analysis of Regular Insulin as the chromatographic column of high performance liquid chromatography
The 4.6*150mm chromatographic column of equal grain porous silica microballoon of the octadecyl bonding of 5 μ m is equipped with in employing, and mobile phase A is pH=2.3 0.2mol/L Na
2
CO
3
Solution: acetonitrile=82:18, Mobile phase B is pH=2.3 0.2mol/L Na
2
CO
3
Solution: acetonitrile=50:50, gradient is: 10%B wash-out 10min, in 50 minutes, the concentration of B brings up to 50%, flow velocity 1ml/min from 10% then, the detection wavelength is 210nm, last sample concentration is 20mg/ml, applied sample amount 5 μ L, appearance time 24.44 minutes, post is imitated 186938 pieces/meter, realizes baseline separation with impurity.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (11)
1. the equal grain porous silica microballoon of a functionalization is characterized in that described microballoon prepares by the following method:
(1) prepares composition, particle diameter, the definite equal grain porous polymer microsphere in aperture in advance, and equal grain porous polymer microsphere is carried out surface-functionalized processing, obtain all grain porous polymer microspheres of functionalization;
(2) the equal grain of a functionalization porous polymer microsphere is dispersed in the solution, adds the preparation of silicon-dioxide presoma then and form the middle complex microsphere of silicon-dioxide/polymkeric substance;
(3) complex microsphere was removed the organic polymer material in the middle of heating made silicon-dioxide/polymkeric substance, obtained all grain porous silica microballoons;
(4) use chemical reagent that equal grain porous silica microballoon is carried out finishing and form functional group, the functionalization that makes is grain porous silica microballoon all;
The particle diameter of the equal grain of described functionalization porous silica microballoon is in 1.7 μ m～100 mu m ranges; The mesoporous aperture of the equal grain of described functionalization porous silica microballoon is in 20～1000 scopes.
2. one kind prepares all methods of grain porous silica microballoon of functionalization, it is characterized in that said method comprising the steps of:
(1) prepares composition, particle diameter, the definite equal grain porous polymer microsphere in aperture in advance, and porous polymer microsphere is carried out surface-functionalized processing, obtain all grain porous polymer microspheres of functionalization;
(2) the equal grain of a functionalization porous polymer microsphere is dispersed in the solution, adds the preparation of silicon-dioxide presoma then and form the middle complex microsphere of silicon-dioxide/polymkeric substance;
(3) complex microsphere was removed the organic polymer material in the middle of heating made silicon-dioxide/polymkeric substance, obtained all grain porous silica microballoons;
(4) use chemical reagent that equal grain porous silica microballoon is carried out finishing and form functional group, the functionalization that makes is grain porous silica microballoon all.
3. method according to claim 2 is characterized in that in the described method steps (1) that equal grain porous polymer microspheres is selected from the single polymers or the copolymer microsphere of methacrylic ester, vinylbenzene and derivative thereof.
4. method according to claim 2, the particle diameter that it is characterized in that equal grain porous polymer microsphere in the described method steps (1) is in 1.7 μ m～100 mu m ranges.
5. method according to claim 2, the particle diameter that it is characterized in that the equal grain porous silica microballoon in the described method steps (3) is in 1.7 μ m～100 mu m ranges; The mesoporous aperture of described equal grain porous silica microballoon is in 20～1000 scopes.
6. method according to claim 2, it is characterized in that the surface-functionalized processing of polymer microballoon in the described method steps (1) is to adopt the polymerisation process that atomic migration causes (atom transfer radical polymerization ATRP) finishes.
7. method according to claim 2, the surface-functionalized processing that it is characterized in that polymer microballoon in the described method steps (1) are to adopt the polyreaction (redox polymerization) of redox initiation to finish.
8. method according to claim 2 is characterized in that the surface-functionalized group of polymer microballoon in the described method steps (1) is an amido, and described amido is selected from primary amine, secondary amine and tertiary amine.
9. all application of grain porous silica microballoon aspect analysis or separation organic compound or biomacromolecule of the described functionalization of claim 1.
10. application according to claim 9 is characterized in that the equal grain of described functionalization porous silica microballoon is as chromatographic column filler or solid phase extraction column stuffing.
11. application according to claim 9 is characterized in that described application comprises that the principle of utilizing liquid chromatography separates chromatographic column or analyze the method for the organic and biomolecules of one or more solubilities as stationary phase.
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