CN102070152B - 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
- Publication number
- CN102070152B CN102070152B CN 201010567428 CN201010567428A CN102070152B CN 102070152 B CN102070152 B CN 102070152B CN 201010567428 CN201010567428 CN 201010567428 CN 201010567428 A CN201010567428 A CN 201010567428A CN 102070152 B CN102070152 B CN 102070152B
- Authority
- CN
- China
- Prior art keywords
- microballoon
- microsphere
- functionalization
- porous silica
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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 liquid chromatography technology, be specifically related to all preparation method and application of grain porous silica microballoon of a kind of micron-sized functionalization.
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.Due to 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 to accurately control size and the aperture structure of porous silica microballoon, and size requires to be controlled between 3 to 10 microns, hole surface need to have certain hydrophobicity.With regard to chromatographic property, all grain porous silica microballoon due to the physical property of its uniform particle diameter, is much better than the wider silicon dioxide microsphere of those size distribution in application process.Therefore, the controlled equal grain porous silica microballoon of size and aperture structure is the first-selected column packing in liquid chromatography technology.At present, adopt traditional sol-gel method can prepare the equal grain silicon dioxide microsphere of tens nanometers to the hundreds of nanometer, but be difficult to over 1 micron.Therefore, the equal grain porous silica microballoon of synthesizing micron-grade is the emphasis problem of current research always.
a kind of method that Chinese patent application 200810019069.3 discloses preparing mesoporous silicon dioxide micro-sphere by combined template on July 9th, 2008; the steps include: the ammonia soln that compound concentration is 1.8～3.0MOL/L; add template and co-template, stirring and dissolving in ammonia soln; Upper step gained mixing solutions is heated to 30～80 ℃, then to the tetraethyl orthosilicate of mixed solution and dripping calculated amount, finishes after reacting 5～6H under constant agitation speed; To after upper step gained mixture drying, obtain the former powder of mesoporous silicon oxide; By 5～6 hours removed template methods of the former powder roasting of silicon-dioxide of drying, obtain the silicon dioxide microsphere that can obtain the meso-hole structure that particle diameter is 80-500 nanometer left and right, particle diameter is less than 1 micron.
chinese patent application 200810202772.8 discloses the preparation method of the controlled mesoporous silicon dioxide micro-sphere in a kind of aperture on April 22nd, 2009, the novel four-head quaternary cationics of take is structure directing agent, under alkaline condition, pass through the sol-gel method synthesizing mesoporous silicon dioxide microsphere in alcohol-water system.The particle diameter of the porous silica microballoon obtained is approximately 1 micron.
deng (Chem. Master., 1995,10,1623-1626) announced a kind of method for preparing mesoporous microsphere in quaternary ammonium salt and ether, the microspherulite diameter obtained is distributed between 2 to 6 microns.(the J. Chromatography A such as Shi, 2009,1216,7388-7393) announced a kind of method for preparing the porous silica microballoon in polyethylene oxide, because the microspherulite diameter distribution of gained is very wide, must sieve before being applied to high performance liquid chromatography and remove macrobead and small-particle.
the method of the polymer microsphere template synthesis porous microsphere relevant to the disclosure (referring to Adv.Mater:2002,14,1768-1772; U.S. Pat 2006088470A1) be to take the expanded polystyrene microballoon as template, with spending the night after the salt acid soak, add the inorganics presoma, hydrolysis-condensation reaction, remove the polymer template and obtain the porous, inorganic microballoon.But the size of the porous, inorganic microballoon that adopts the method to obtain has been dwindled 20-50% than original template microsphere, nearly 40% left and right of its productive rate.
therefore inquire into a kind of preparation method micron-sized, equal grain porous silica microballoon that the particle diameter aperture is controlled and be urgently firm key issue of liquid chromatography stuffing field.
Summary of the invention
the object of the invention is to provide all grain porous silica microballoons of a kind of functionalization, solved that the microspherulite diameter that in the prior art, the porous silica method for preparing microsphere obtains is inhomogeneous or particle diameter is too small or the problem such as can not be controlled in mesoporous aperture, the present invention, when guaranteeing porous silica microballoon homogeneous sphere diameter, can effectively control aperture, structure and the pattern of microballoon.
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 prepared by the following method by described microballoon:
(1) the equal grain porous polymer microsphere that previously prepared composition, particle diameter, aperture are determined, and equal grain porous polymer microsphere is carried out to surface-functionalized processing, obtain all grain porous polymer microspheres of functionalization;
(2) the equal grain of a functionalization porous polymer microsphere is dispersed in solution, then adds the preparation of silicon-dioxide presoma to form the middle complex microsphere of silicon-dioxide/polymkeric substance;
(3) heating makes the middle complex microsphere of silicon-dioxide/polymkeric substance remove the organic polymer material, obtains all grain porous silica microballoons;
(4) use chemical reagent to carry out finishing to equal grain porous silica microballoon, at an equal grain porous silica microsphere surface, form the functionalization group, form all grain porous silica microballoons of functionalization;
the particle diameter of the equal grain of described functionalization porous silica microballoon is in 1.7 μ m～100 μ m scopes; 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) the equal grain porous polymer microsphere that previously prepared composition, particle diameter, aperture are determined, and equal grain porous polymer microsphere is carried out to 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, then adds the preparation of silicon-dioxide presoma to form the middle complex microsphere of silicon-dioxide/polymkeric substance;
(3) heating makes the middle complex microsphere of silicon-dioxide/polymkeric substance remove the organic polymer material, obtains all grain porous silica microballoons;
(4) use chemical reagent to carry out finishing to equal grain porous silica microballoon, at an equal grain porous silica microsphere surface, form the functionalization group, form all grain porous silica microballoons of functionalization.
preferably, in described method steps (1) all the grain porous polymer microsphere be selected from single polymers or the copolymer microsphere of methacrylic ester, Styrene and its derivatives.
preferably, in described method steps (1) all the particle diameter of grain porous polymer microsphere in 1.7 μ m～100 μ m scopes.
preferably, the particle diameter of the equal grain porous silica microballoon in described method steps (3) is in 1.7 μ m～100 μ m scopes; The mesoporous aperture of described equal grain porous silica microballoon is in 20～1000 scopes.
preferably, in described method steps (1), the surface-functionalized processing of polymer microballoon is that the polymerisation process (atom transfer radical polymerization, ATRP) that adopts atomic migration to cause completes.
preferably, in described method steps (1), the surface-functionalized processing of polymer microballoon is to adopt the polyreaction (redox polymerization) of redox initiation to complete.
preferably, in described method steps (1), the surface-functionalized group of polymer microballoon is amido, and described amido is selected from primary amine, secondary amine and tertiary amine.
on the other hand, the present invention provides again all application of grain porous silica microballoon aspect the isolated or purified compound of a kind of functionalization, 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 separated or analyze the method for one or more soluble compounds using chromatographic column as stationary phase.
preferably, described application comprises flows through chromatographic column to the liquor that contains to be separated or analysis of compounds, then being adsorbed on to be separated on stationary phase or step that compound that analyze elutes.
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 separated or analyze the method for the organic and biomolecules of one or more solubilities using chromatographic column as stationary phase.
technical solution of the present invention is used for obtaining a kind of applicable liquid chromatography, there is accurate size and aperture structure, and the monodisperse silica microspheres of functionalization, adopt the functionalized polymer microsphere of a kind of known size and the equal grain with vesicular structure as the structure guiding material, allow the presoma of silicon-dioxide be penetrated in functionalized polymer microsphere, form silicon-dioxide/polymer composite microsphere under ammonia-catalyzed, remove the structure guiding material, obtain the equal grain porous silica microballoon that productive rate is high, its structure is corresponding with structure guiding material polymer microballoon, its particle diameter is consistent with the porous polymer microsphere of structure guiding, then the equal grain porous silica microballoon of gained carried out to finishing.
method of the present invention, when guaranteeing silicon dioxide microsphere homogeneous sphere diameter, can effectively be controlled aperture, structure and the pattern of microballoon.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 aperture; At first the method 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, then adds the silicon-dioxide precursor, form under suitable condition silicon-dioxide, generate the middle complex microsphere of silicon-dioxide/polymkeric substance.Again, from middle mixture, remove functionalized polymer, obtain porous silica spheres, the size of porous silica spheres is corresponding with the equal particle/polymer microballoon of functionalization.Finally porous silica spheres is carried out to finishing, introduce the functionalization group.
spheroidal microsphere polymer microballoon with vesicular structure comprises single polymers and the copolymer microsphere of methacrylic ester, Styrene and its derivatives.There is the particle diameter of spheroidal microsphere polymer microballoon of vesicular structure from 1.7 μ m to 100 μ m.All the particle diameter of grain silicon dioxide microsphere is 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) complete, also can be formed 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, intermediate are porous material.
preparation method's the first step, be the spherical polymer microballoon that preparation has vesicular structure, then this polymer microballoon carried out to finishing, obtains the polymer microballoon of functionalization.
as the polymer microballoon of structure guiding material, it is porous, crosslinked or without crosslinked.The diameter of polymer microballoon is in the 1.7-100 micrometer range.
above-mentioned polymer microballoon refers to 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 step (1) refers to using chemical reagent to introduce the functionalization group by chemical reaction, chemical reagent used 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.Applicable chemical reagent 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 the oxyethyl group in oligopolymer or polyethylene oxide, and the amino in oligopolymer or polyvinylamine, the hydroxyl in oligopolymer or polyvinyl alcohol etc.Vinyl polymer based on, but be not limited to polystyrene, polyacrylic ester, and can be connected to by atomic migration initiated polymerization or redox reaction the derivative that comprises the functionalization group on polymer microballoon surface.The atomic migration initiated polymerization has a detailed description and relevant references in U.S. Pat 6071980.Redox initiation refers to that the polymerization of monomer is by oxidising agent and goes back the transfer of electronics between original reagent and cause such process.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, there is nanometer and may contain the halogen atom group before the polymer microballoon polymerization of micrometer structure.For the redox initiate polymerization reaction, there is nanometer and may contain before the polymer microballoon polymerization of micrometer structure, but be not limited to hydroxyl, thiol group, aldehyde radical, thiohydroxy, amino etc.Before 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 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, alcohol used 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 containing 1-24 carbon atom chain length), phenyltrimethoxysila,e, phenyl triethoxysilane, the 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) 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.
during the finishing of step (4), by chemical process, various functional group graftings are comprised to these functional groups of silicon dioxide microsphere surface, 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 utilizes the difference of the affinities such as the partition ratio of various materials to be separated in the solid-liquid two-phase, adsorptive power to be separated.The liquid-flow that uses external force will contain sample is mutually by stationary phase, and the mixture flow of carrying in moving phase is when stationary phase, and each component and stationary phase hole surface in mixture interact.Due to each component in mixture in character and structural difference, different from size, the power of the reactive force produced between the stationary phase hole surface, movement along with moving phase, mixture is in the repeated multiple times partition equilibrium of two alternate processes, the asynchronism(-nization) that makes each component be fixed mutually to retain and being separated, particle diameter and the aperture structure of the equal grain porous silica microballoon that present method stationary phase is used can accurately be controlled by the polymer microballoon of structure guiding material, and can carry out functionalization according to different liquid chromatography application.Functionalization is grain porous silica microspherulite diameter homogeneous all, can guarantee consistence and the circulation ratio of chromatographic column on the 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) and the bonded phase packings of cyano group group (CN, CPS).
because silicon hydroxyl (SiOH) or other polar group polarity of Silica Surface are stronger, therefore, the order of separation is the polarity size according to each component in sample, and weak component of polarity is rinsed out chromatographic column at first.The moving phase polar phase contrast stationary phase that normal-phase chromatography is used is low, as normal hexane (Hexane), and chloroform (Chloroform), methylene dichloride (Methylene Chloride) etc.
reverse chromatograms: the filler that reverse chromatograms is used is often to take silica gel as matrix, and surface bond has the Bonded Phase of the relatively weak functional group of polarity.The moving phase polarity that reverse chromatograms is used 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 component that polarity is stronger is rinsed out at first, and the weak component of polarity can have stronger reservation on chromatographic column.
the variation coefficient (coefficient of variability, CV): meaning the statistic of the particle diameter degree of variation size of the porous silica microballoon prepare, is the percentage ratio of the ratio of standard deviation and mean number.The particle size distribution range that means the porous silica microballoon when the variation coefficient is large is wide, the particle diameter heterogeneity; When the variation coefficient hour, meaning that the particle size distribution range of porous silica microballoon is narrow, uniform particle diameter.In prior art, the variation coefficient of the particle diameter of porous silica microballoon is greater than 10%, even reaches 30% left and right, so need to be sieved operation; The variation coefficient of the particle diameter of porous silica microballoon of the present invention is less than 5%, generally without screening, can be used as column packing or extraction stuffing use.
with respect to scheme of the prior art, advantage of the present invention is:
equal grain porous silica microballoon aperture structure prepared by the method that technical solution of the present invention openly provides is corresponding with structure guiding material polymer microballoon, so, select 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 to functionalization, just can meet the demand of different application.
another advantage that the present invention is better than prior art is particle diameter and 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, be easy to control the particle diameter of microballoon.The quantitative analysis that equal grain porous silica microballoon prepared by the disclosure is particularly suitable for the stable result of those needs separates.And the method for technical solution of the present invention is applicable to scale operation, prepare microballoon and be easy to be dispersed in different liquid, do not have the phenomenon of reunion.
The accompanying drawing explanation
below in conjunction with drawings and Examples, the invention will be further described:
the electronic scanning Electronic Speculum figure that Fig. 1 is the equal grain silicon dioxide microsphere that obtains of the present invention; Wherein particle diameter is at 10 μ m(embodiment 21);
the electronic scanning Electronic Speculum figure that Fig. 2 is the equal grain silicon dioxide microsphere that obtains of the present invention; Wherein particle diameter is at 35 μ m(embodiment 23);
the electronic scanning Electronic Speculum figure (comparative example) that Fig. 3 is 10 microns (CV=10%) silicon dioxide microspheres commonly used on market;
fig. 4 is the separation and purification color atlas of positive silicon dioxide microsphere (10 microns) for taxol;
fig. 5 is that the anti-phase silicon dioxide microsphere of C18 bonding (10 microns) is for Regular Insulin separate colors spectrogram;
fig. 6 is the separate colors spectrogram of the anti-phase silicon dioxide microsphere of C18 bonding (5 microns) for benzene ring compound (as aniline, methyl-phenoxide and toluene).
Embodiment
below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for the present invention is described.The implementation condition adopted in embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.Below by various embodiment, the specific embodiment of the invention process is described, wherein embodiment 1～7 is equal preparation process of grain porous polymer microsphere.The reaction kinetic process that embodiment 8～18 is equal grain porous polymer microsphere.The building-up process that embodiment 19-23 is equal grain porous silica microballoon; The reaction kinetic process that embodiment 24～26 is 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.
the synthetic all grains of embodiment 1 expanded polystyrene/divinylbenzene polymer microballoon
get 30g vinylbenzene, 60g divinylbenzene (80%) and 100g hexalin join in tri-mouthfuls of round-bottomed flasks of 2000mL, add wherein initiator 1.5g Diisopropyl azodicarboxylate, and mechanical stirring makes it to dissolve fully.In solution, add 800g to contain 0.04% octadecyl sulfonic acid in the above and receive the aqueous solution, add 25g 2.5 μ m polystyrene seed after ultrasonic emulsification, in ℃ reaction of room temperature swelling 24h post-heating to 80.Isolate equal grain porous crosslinked polystyrene microballoon after cooling, particle diameter 5 μ m, variation coefficient CV=3.5%.
the synthetic all grains of embodiment 2 expanded polystyrene/divinylbenzene polymer microballoon
get 30g vinylbenzene, 60g divinylbenzene (80%) and 100g hexalin join in tri-mouthfuls of round-bottomed flasks of 2000mL, add wherein initiator 1.5g Diisopropyl azodicarboxylate, and mechanical stirring makes it to dissolve fully.In solution, add 800g to contain 0.04% octadecyl sulfonic acid in the above and receive the aqueous solution, add 25g 5 μ m polystyrene seed after ultrasonic emulsification, in ℃ reaction of room temperature swelling 24h post-heating to 80.Isolate equal grain porous crosslinked polystyrene microballoon after cooling, particle diameter is 10 μ m, variation coefficient CV=3.5%.
the synthetic all grains of embodiment 3 expanded polystyrene/divinylbenzene polymer microballoon
in 5 liters of reactors, using the granules of polystyrene of the mono-dispersion of pre-prepared 60g swellable as seed, its granularity is 13.5 μ m, and CV=3.8 adds in the 1300g deionized water that contains the 1g hydroxypropylcellulose; Under the speed of 150 rev/mins, stir and be heated to 85 ℃.
by 800g vinylbenzene with after the 10g dibenzoyl peroxide mixes; add in the 1500g water that contains 0.5g KI, 0.5g hydroxypropylcellulose and 4.0g Triton X-405; emulsification after mixed; under 85 ℃, with the speed increased progressively, join in the described aqueous solution; 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%.
by 800g vinylbenzene and 10g dibenzoyl peroxide, add in the 1500g water that contains 0.5g hydroxypropylcellulose and 4.0g Triton X-405, emulsification after mixed, conditioned reaction still temperature to 50 ℃, be added dropwise to the total overall reaction thing in 2 hours, continue again afterwards swelling 0.5 hour, and then add 0.4% hydroxypropyl cellulose aqueous solution 500g.
be heated to 85 ℃, carry out polyreaction 10 hours, or until react completely.
finally adopt ordinary method, 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%.
the synthetic all grains of embodiment 4 expanded polystyrene/divinylbenzene polymer microballoon
in 5 liters of reactors, using the granules of polystyrene of the mono-dispersion of pre-prepared 200g swellable as seed, its granularity is 50 μ m, and CV=4.2 adds in the 1300g deionized water that contains the 1g hydroxypropylcellulose; Under the speed of 150 rev/mins, stir and be heated to 85 ℃.
by 800g vinylbenzene with after the 10g dibenzoyl peroxide mixes; add in the 1500g water that contains 0.5g KI, 0.5g hydroxypropylcellulose and 4.0g Triton X-405; emulsification after mixed; under 85 ℃, with the speed increased progressively, join in the described aqueous solution; 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%.
by 800g vinylbenzene and 10g dibenzoyl peroxide, add in the 1500g water that contains 0.5g hydroxypropylcellulose and 4.0g Triton X-405, emulsification after mixed, conditioned reaction still temperature to 60 ℃, be added dropwise to the total overall reaction thing in 2 hours, continue again afterwards swelling 0.5 hour, and then add 0.4% hydroxypropyl cellulose aqueous solution 500g.
be heated to 85 ℃, carry out polyreaction 10 hours, or until react completely.
finally adopt ordinary method, 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%.
the synthetic all grains of embodiment 5 porous glycidyl methacrylate/Ethylene glycol dimethacrylate copolymerization microsphere
get 30g glycidyl methacrylate monomer, 60g Ethylene glycol dimethacrylate and 100g hexalin join in tri-mouthfuls of round-bottomed flasks of 2000mL, add wherein initiator 1.5g Diisopropyl azodicarboxylate, and mechanical stirring makes it to dissolve fully.In solution, add 800g to contain 0.04% octadecyl sulfonic acid in the above and receive the aqueous solution, add 25g 2.5 μ m polystyrene seed after ultrasonic emulsification, post-heating to 75 ℃ reaction when room temperature swelling 24h.Isolate equal grain porous glycidyl methacrylate/Ethylene glycol dimethacrylate copolymerization microsphere after 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 tri-mouthfuls of round-bottomed flasks of 2000mL, add wherein initiator 1.5g Diisopropyl azodicarboxylate, and mechanical stirring makes it to dissolve fully.In solution, add 800g to contain 0.04% octadecyl sulfonic acid in the above and receive the aqueous solution, add 25g 5 μ m polystyrene seed after 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 cooling, particle diameter 10 μ m, variation coefficient CV=4.0%.
7 equal porous propylene acid methyl esters/divinylbenzene copolymerization microspheres of embodiment
get the 80g methacrylate monomer, 20g divinylbenzene and 100g hexalin join in tri-mouthfuls of round-bottomed flasks of 2000mL, add wherein initiator 1.5g Diisopropyl azodicarboxylate, and mechanical stirring makes it to dissolve fully.In solution, add 800g to contain 0.04% octadecyl sulfonic acid in the above and receive the aqueous solution, add 25g 10 μ m polystyrene seed after 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 cooling, particle diameter 35 μ m, variation coefficient CV=3.2%.
embodiment 8 polystyrene/divinylbenzene microsphere surface chloromethylations
chloromethylation: the polystyrene/divinylbenzene of 50g drying (PS/DVB) microballoon is joined in the there-necked flask of 1000mL, add 500mL trichloromethane dispersion microsphere, system is at 0 ℃ of lower mechanical stirring 1h, and keeps 0 ℃ of condition, then adds anhydrous stannic chloride (SnCl
4
) 8.5ml, after stirring 5 minutes, dropwise add chloromethyl ether (CH
3
oCH
2
cl) 50mL.Chloromethyl ether dropwises, and system stirs 30min, then continues to stir 3h under room temperature.
after reaction finishes, the product vacuum filtration, and use successively deionized water (100mL), 5% hydrochloric acid (100mL), deionized water (100mL), tetrahydrofuran (THF) (100mL), ethanol (100mL), acetone (100mL) to clean, microballoon after cleaning, in 60 ℃ of lower vacuum-drying 12h, obtains the polystyrene/divinylbenzene microballoon of chloromethylation.
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 tri-mouthfuls of round-bottomed flasks of 1000mL, add wherein 200 mL ethanol, ultrasonic dispersion 30min.Add the 200mL quadrol under the 100rpm mechanical stirring, be warming up to 80 ℃, suction filtration after back flow reaction 6h, and alternately wash three times 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 tri-mouthfuls of round-bottomed flasks of 1000mL, add wherein 200 mL ethanol, ultrasonic dispersion 30min.Add the 200mL dimethyl-ethylenediamine under the 100rpm mechanical stirring, be warming up to 80 ℃, suction filtration after back flow reaction 6h, and alternately wash three times with ethanol and distilled water, 50 ℃ of dry 12h obtain the polystyrene/divinylbenzene microballoon of dimethyl-ethylenediamine functionalization.
the synthetic surface-functionalized polystyrene/divinylbenzene microballoon of Trimethylamine of embodiment 11
trimethylamine functionalization: get equal grain chloromethylated polystyrene/Vinylstyrene copolymerization microsphere of 80.0g, join in tri-mouthfuls of round-bottomed flasks of 1000mL, add wherein 200 mL water, ultrasonic dispersion 30min.Add 200mL Trimethylamine hydrochloride under the 100rpm mechanical stirring, be warming up to 80 ℃, suction filtration after back flow reaction 12h, and alternately wash three times with distilled water, 50 ℃ of dry 12h obtain the polystyrene/divinylbenzene microballoon of Trimethylamine amino-functionalization.
the polymethacrylate of embodiment 12 quadrol functionalization/Ethylene glycol dimethacrylate copolymerization microsphere
quadrol functionalization: get all grain porous polymethyl glycidyl acrylate/Ethylene glycol dimethacrylate copolymerization microspheres of 80.0g, join in tri-mouthfuls of round-bottomed flasks of 1000mL, add wherein 200 mL ethanol, ultrasonic dispersion 30min.Add the 200mL quadrol under the 100rpm mechanical stirring, be warming up to 80 ℃, suction filtration after back flow reaction 6h, and alternately wash three times the polymethacrylate of 50 ℃ of dry 12h acquisition quadrol functionalization/Ethylene glycol dimethacrylate copolymerization microsphere with ethanol and distilled water
embodiment 13 polypropylene amine microsphere surface functionalization
get 20.0g chloromethylated polystyrene/divinylbenzene microspheres copolymerization microsphere, join in tri-mouthfuls of round-bottomed flasks of 100mL, add wherein 50mL ethanol, ultrasonic dispersion 30min.Add the 10g polypropylene amine under the 100rpm mechanical stirring, be warming up to 80 ℃, suction filtration after back flow reaction 6h, and alternately wash three times with ethanol and distilled water, 50 ℃ of dry 12h obtain the amine functional polyacrylate copolymerization microsphere.
embodiment 14 polyethyene diamine microsphere surface functionalization
get 20.0g chloromethylated polystyrene/divinylbenzene microspheres copolymerization microsphere 10 μ m, CV=4%, join in tri-mouthfuls of round-bottomed flasks of 100mL, adds wherein 50mL ethanol, ultrasonic dispersion 30min.Under the 100rpm mechanical stirring, add 10g to gather ethamine, be warming up to 80 ℃, suction filtration after back flow reaction 6h, and alternately wash three times with ethanol and distilled water, 50 ℃ of dry 12h obtain the amine functional polyacrylate copolymerization microsphere.
get 20.0g 5 μ m, the porous polymethyl glycidyl acrylate of CV=4%/Ethylene glycol dimethacrylate copolymerization microsphere, join in tri-mouthfuls of round-bottomed flasks of 100mL, adds wherein 50mL ethanol, ultrasonic dispersion 30min.Add the 10g polypropylene amine under the 100rpm mechanical stirring, be warming up to 80 ℃, suction filtration after back flow reaction 6h, and alternately wash three times 50 ℃ of dry 12h with ethanol and distilled water.
embodiment 16 adopts the polyreaction that atomic migration causes to introduce 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 tri-mouthfuls of round-bottomed flasks of 100mL.Then in another 100mL single port flask by 1.9g 2,2 '-dipyridyl is dissolved in the 40mL glytidyl methacrylate, and joins in there-necked flask, by magnetic agitation, polymer microsphere is disperseed.System sealing vacuumizes, and uses nitrogen replacement, finally nitrogen is inserted under liquid level, under nitrogen atmosphere in 100 ℃ of magnetic force splash bar 16h.Resulting microballoon is alternately washed three times with deionized water and ethanol, and 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 Glycidyl Acrylate functionalization, join in tri-mouthfuls of round-bottomed flasks of 1000mL, add wherein 200 mL ethanol, ultrasonic dispersion 30min.Add the 200mL quadrol under the 100rpm mechanical stirring, be warming up to 80 ℃, suction filtration after back flow reaction 6h, and alternately wash three times 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
get the polystyrene/divinylbenzene copolymerization microsphere (20%) of 10g particle diameter 50 μ m chloromethylations in tri-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, after reaction finishes, microballoon is alternately washed three times 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 tri-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 liquid level.In the beaker of a 500mL, the 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, then dropwise add the 50mL glytidyl methacrylate, dropwise, system is in 60 ℃ of reaction 4h under nitrogen atmosphere, and resulting microballoon is alternately washed three times with deionized water and ethanol, each consumption 50mL, be put in 60 ℃ of vacuum drying ovens dry.
get above hydroxylated microballoon 10g in tri-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 liquid level.In the beaker of a 500mL, the 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, then dropwise add the 50mL Methacrylamide, dropwise, system is in 60 ℃ of reaction 4h under nitrogen atmosphere, and resulting microballoon is alternately washed three times with deionized water and ethanol, each consumption 50mL, be put in 60 ℃ of vacuum drying ovens dry.
embodiment 18 polymethyl acrylates/divinylbenzene copolymerization microsphere aminated reaction in surface
5 gram polymethyl acrylates/divinylbenzene copolymerization microsphere (35 microns, variation coefficient CV=3.2%) adds 100 milliliters of dimethyl formamides, adds 20 gram dimethyl-ethylenediamines after stirring.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
that gets 2g particle diameter 10 μ m is placed in tri-mouthfuls of round-bottomed flasks of 250mL with the surface-functionalized microballoon of quadrol (embodiment 9), adds 40mL ethanol and 10mL deionized water, and ultrasonic dispersion 30min adds ammoniacal liquor under mechanical stirring.To the mixing solutions that adds 10g tetraethoxysilane and 3mL ethanol in three mouthfuls of round-bottomed flasks.After adding, continue stirring reaction 24h.After having reacted, with F molding sand core funnel suction filtration, and alternately wash three times 50 ℃ of dry 12h with the second alcohol and water.Dried polymkeric substance/SiO 2 composite microsphere, in retort furnace, is warming up to 800 ℃ piecemeal, maintains this temperature calcination 6 h, finally obtain the equal grain porous silica microballoon of 10 μ m, CV=4%.Microballoon mean pore size 120 dusts, specific surface area 300 square meters/gram.
synthesizing of 20 equal porous silica microballoons of embodiment
that gets 2g particle diameter 5 μ m is placed in tri-mouthfuls of round-bottomed flasks of 250mL with the surface-functionalized microballoon of quadrol (embodiment 15), adds 40mL ethanol and 10mL deionized water, and ultrasonic dispersion 30min adds ammoniacal liquor under mechanical stirring.To the mixing solutions that adds 10g tetraethoxysilane and 3mL ethanol in three mouthfuls of round-bottomed flasks.After adding, continue stirring reaction 24h.After having reacted, with F molding sand core funnel suction filtration, and alternately wash three times 50 ℃ of dry 12h with the second alcohol and water.Dried polymkeric substance/SiO 2 composite microsphere, in retort furnace, is warming up to 800 ℃ piecemeal, maintains this temperature calcination 6 h, finally obtain the equal grain porous silica microballoon of 5 μ m, CV=4%.Microballoon mean pore size 150 dusts, specific surface area 280 square meters/gram
synthesizing of 21 equal porous silica microballoons of embodiment
that gets 2g particle diameter 10 μ m is placed in tri-mouthfuls of round-bottomed flasks of 250mL with the surface-functionalized microballoon of polyethyene diamine (embodiment 14), adds 40mL ethanol and 10mL deionized water, and ultrasonic dispersion 30min adds ammoniacal liquor under mechanical stirring.To the mixing solutions that adds 10g tetraethoxysilane and 3mL ethanol in three mouthfuls of round-bottomed flasks.After adding, continue stirring reaction 24h.After having reacted, with F molding sand core funnel suction filtration, and alternately wash three times 50 ℃ of dry 12h with the second alcohol and water.Dried polymkeric substance/SiO 2 composite microsphere, in retort furnace, is warming up to 800 ℃ piecemeal, maintains this temperature calcination 6 h, finally obtain the equal grain porous silica microballoon of 10 μ m, variation coefficient CV=4%.Microballoon mean pore size 300 dusts, specific surface area 100 square meters/gram.Be illustrated in figure 1 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
that gets 2g particle diameter 50 μ m is placed in tri-mouthfuls of round-bottomed flasks of 250mL with the surface-functionalized microballoon of quadrol (embodiment 17), adds 40mL ethanol and 10mL deionized water, and ultrasonic dispersion 30min adds ammoniacal liquor under mechanical stirring.To the mixing solutions that adds 10g tetraethoxysilane and 3mL ethanol in three mouthfuls of round-bottomed flasks.After adding, continue stirring reaction 24h.After having reacted, with F molding sand core funnel suction filtration, and alternately wash three times 50 ℃ of dry 12h with the second alcohol and water.Dried polymkeric substance/SiO 2 composite microsphere, in retort furnace, is warming up to 800 ℃ piecemeal, maintains this temperature calcination 6 h, finally obtain the equal grain porous silica microballoon of 49 μ m.Microballoon mean pore size 200 dusts, specific surface area 250 square meters/gram, variation coefficient CV=4%, yield is 99.7%.
synthesizing of 23 equal porous silica microballoons of embodiment
get 2g particle diameter 35 μ m, variation coefficient CV=3.2% is placed in tri-mouthfuls of round-bottomed flasks of 250mL with the surface-functionalized microballoon of amido (embodiment 18), adds 40mL ethanol and 10mL deionized water, and ultrasonic dispersion 30min adds ammoniacal liquor under mechanical stirring.To the mixing solutions that adds 10g tetraethoxysilane and 3mL ethanol in three mouthfuls of round-bottomed flasks.After adding, continue stirring reaction 24h.After having reacted, with F molding sand core funnel suction filtration, and alternately wash three times 50 ℃ of dry 12h with the second alcohol and water.Dried polymkeric substance/SiO 2 composite microsphere, in retort furnace, is warming up to 800 ℃ piecemeal, maintains this temperature calcination 6 h, finally obtain the equal grain porous silica microballoon of 35 μ m.Microballoon mean pore size 50 dusts, specific surface area 600 square meters/gram, variation coefficient CV=3.2%.Be illustrated in figure 2 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 Comparative Examples market is synthetic
in tri-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 alternately wash three times 50 ℃ of dry 12h with the second alcohol and water.Dried silicon dioxide microsphere, in retort furnace, is warming up to 800 ℃ piecemeal, maintains this temperature calcination 6 h.Obtain the uneven silicon dioxide microsphere of size, CV=12%.Fig. 3 is the polydispersion silicon dioxide microsphere that Comparative Examples obtains, and as can be seen from Fig., the size of polydispersion silicon dioxide microsphere differs.When carrying out the separation and purification analytical applications, need to the polydispersion silicon dioxide microsphere obtained be sieved, obtain the comparatively silicon dioxide microsphere of homogeneous of particle diameter, last yield is the highest 40%.
embodiment 24 silicon dioxide microsphere surface alkylated reactions
octadecyl Trimethoxy silane 200 g are dissolved in 800 ml toluene, add equal grain porous silica microballoon 120 g, are heated to 110 ℃ of backflow 24h, and cooling by filtering cleaning, the dry octadecyl silane that obtains can be made the reverse chromatograms filler.
embodiment 25 silicon dioxide microsphere surface alkylated reactions
eight alkyl trimethoxysilane 200 g are dissolved in 800 ml toluene, add equal 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 800 ml toluene, add equal grain porous silica microballoon 120 g, be heated to 110 ℃ of backflow 24h, cooled and filtered is cleaned, and the dry silicon dioxide microsphere that obtains the surface band amido can be used for sugared post separation and analyzes filler.
fig. 4 is that the present invention obtains the separation and purification color atlas of the positive silicon dioxide microsphere (particle diameter is 10 microns) of equal grain for taxol; Fig. 5 is that the present invention obtains the anti-phase silicon dioxide microsphere of C18 bonding (particle diameter is 10 microns) of equal grain for Regular Insulin separate colors spectrogram; Fig. 6 is that the present invention obtains the separate colors spectrogram of the anti-phase silicon dioxide microsphere of C18 bonding (particle diameter is 5 microns) of equal grain for benzene ring compound (aniline, methyl-phenoxide and toluene).Be below typical analytical applications example and condition thereof.
application examples 1 utilizes all grain porous silica microballoons to carry 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, the aniline that loading concentration is 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 20150 pieces/meter of post effects with aniline, with methyl-phenoxide, calculate 44070 pieces/meter of post effects, with toluene, calculate 95679 pieces/meter of post effects.
application examples 2 utilizes all grain porous silica microballoons to carry 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, then in 50 minutes, the concentration of B brings up to 50%, flow velocity 1ml/min from 10%, the detection wavelength is 210nm, loading concentration is 20mg/ml, applied sample amount 5 μ L, appearance time 24.44 minutes, 186938 pieces/meter of post effects, realize baseline separation with impurity.
above-mentioned example is only explanation technical conceive of the present invention and characteristics, and its purpose is to allow the person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations that spirit is done according to the present invention or modification, within all should being encompassed in protection scope of the present invention.
Claims (11)
1. the equal grain porous silica microballoon of a functionalization is characterized in that prepared by the following method by described microballoon:
(1) the equal grain porous polymer microsphere that previously prepared composition, particle diameter, aperture are determined, and equal grain porous polymer microsphere is carried out to surface-functionalized processing, obtain all grain porous polymer microspheres of functionalization;
(2) the equal grain of a functionalization porous polymer microsphere is dispersed in solution, then adds the preparation of silicon-dioxide presoma to form the middle complex microsphere of silicon-dioxide/polymkeric substance;
(3) heating makes the middle complex microsphere of silicon-dioxide/polymkeric substance remove the organic polymer material, obtains all grain porous silica microballoons;
(4) use chemical reagent to carry out finishing to equal grain porous silica microballoon and form functional group, make all grain porous silica microballoons of functionalization;
The particle diameter of the equal grain of described functionalization porous silica microballoon is in 1.7 μ m～100 μ m scopes; The described functionalization all mesoporous aperture of grain porous silica microballoon exists
in scope.
2. one kind prepares all methods of grain porous silica microballoon of the described functionalization of claim 1, it is characterized in that said method comprising the steps of:
(1) the equal grain porous polymer microsphere that previously prepared composition, particle diameter, aperture are determined, and porous polymer microsphere is carried out to surface-functionalized processing, obtain all grain porous polymer microspheres of functionalization;
(2) the equal grain of a functionalization porous polymer microsphere is dispersed in solution, then adds the preparation of silicon-dioxide presoma to form the middle complex microsphere of silicon-dioxide/polymkeric substance;
(3) heating makes the middle complex microsphere of silicon-dioxide/polymkeric substance remove the organic polymer material, obtains all grain porous silica microballoons;
(4) use chemical reagent to carry out finishing to equal grain porous silica microballoon and form functional group, make all grain porous silica microballoons of functionalization.
3. method according to claim 2, is characterized in that in described method steps (1) that equal grain porous polymer microspheres is selected from single polymers or the copolymer microsphere of methacrylic ester, Styrene and its derivatives.
4. method according to claim 2, is characterized in that the particle diameter of equal grain porous polymer microsphere in described method steps (1) is in 1.7 μ m～100 μ m scopes.
5. method according to claim 2, is characterized in that the particle diameter of the equal grain porous silica microballoon in described method steps (3) is in 1.7 μ m～100 μ m scopes; The mesoporous aperture of described equal grain porous silica microballoon exists
in scope.
6. method according to claim 2, the surface-functionalized processing that it is characterized in that polymer microballoon in described method steps (1) is that the polymerisation process (atom transfer radical polymerization, ATRP) that adopts atomic migration to cause completes.
7. method according to claim 2, the surface-functionalized processing that it is characterized in that polymer microballoon in described method steps (1) is to adopt the polyreaction (redox polymerization) of redox initiation to complete.
8. method according to claim 2, is characterized in that the surface-functionalized group of polymer microballoon in described method steps (1) is 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 functionalization claimed in 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 separated or analyze the method for one or more solubility organic compound or biomacromolecule using chromatographic column as stationary phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010567428 CN102070152B (en) | 2010-12-01 | 2010-12-01 | Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010567428 CN102070152B (en) | 2010-12-01 | 2010-12-01 | Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102070152A CN102070152A (en) | 2011-05-25 |
| CN102070152B true CN102070152B (en) | 2013-06-12 |
Family
ID=44028939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010567428 Active CN102070152B (en) | 2010-12-01 | 2010-12-01 | Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102070152B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557047B (en) * | 2011-10-18 | 2014-08-20 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing mesoporous silica with biomass power plant ash as raw material |
| CN102495120B (en) * | 2011-12-21 | 2014-07-30 | 昆明理工大学 | Preparation method of porous silicon-based voltammetric sensing material sensitive to lead ions |
| CN102814168A (en) * | 2012-09-18 | 2012-12-12 | 济南大学 | Preparation method and application of loofah sponge surface malachite green molecular imprinting adsorbing material |
| CN104689806B (en) * | 2015-03-18 | 2017-03-29 | 南京中医药大学 | Functional mesoporous SiO2/TiO2Composite nano-microsphere solid phase extraction column and preparation method thereof |
| CN106348252B (en) * | 2015-07-15 | 2019-03-08 | 中国科学院大连化学物理研究所 | A kind of monodispersed oxidate microspheres and its microfluidic control Preparation Method |
| CN105056960B (en) * | 2015-07-15 | 2017-04-12 | 西北大学 | Cobalt-based composite oxide catalyst as well as preparation method and application thereof |
| CN106732476A (en) * | 2016-11-17 | 2017-05-31 | 南昌大学 | A kind of preparation method of the amino modified mesoporous silicon oxide for separating and purifying taxol |
| CN106943985A (en) * | 2017-04-11 | 2017-07-14 | 南昌大学 | Preparation method for the amino modified mesoporous silicon oxide of separating and purifying taxol |
| CN107792858B (en) * | 2017-10-30 | 2020-06-30 | 西北工业大学 | Preparation method of large-particle-size porous high-specific-surface-area silicon dioxide microspheres |
| CN108459003A (en) * | 2018-01-17 | 2018-08-28 | 安徽农业大学 | A kind of preparation method of silver nano-grain coating zinc oxide surface enhanced Raman scattering effect substrate |
| CN108892144B (en) * | 2018-06-22 | 2021-09-28 | 南京亘闪生物科技有限公司 | Preparation method of functionalized porous particle size monodisperse silicon dioxide spherical material |
| CN108889285B (en) * | 2018-07-12 | 2021-05-14 | 纳谱分析技术（苏州）有限公司 | Limited-feeding chromatographic packing, preparation method thereof, stationary phase containing limited-feeding chromatographic packing and application of stationary phase |
| CN109675343A (en) * | 2018-12-07 | 2019-04-26 | 天津迪沃特生物电子科技有限公司 | A kind of method and device extracted and/or purify |
| CN111434610B (en) * | 2019-01-11 | 2021-10-01 | 江苏集萃智能液晶科技有限公司 | Porous silicon dioxide microsphere and preparation method and application thereof |
| CN112791674B (en) * | 2020-12-31 | 2022-07-12 | 广州牌牌生物科技有限公司 | Core-shell micron-sized monodisperse silica gel microsphere and preparation method thereof |
| CN113019343B (en) * | 2021-03-15 | 2023-06-16 | 苏州纳微科技股份有限公司 | Organic-inorganic hybrid microsphere with ordered pore canal structure and preparation method and application thereof |
| CN113237969A (en) * | 2021-04-21 | 2021-08-10 | 南京大学 | Preparation of monodisperse mesoporous silicon nano chromatographic packing with center-through and radial aperture and application of packing in chromatographic separation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101181184A (en) * | 2007-11-30 | 2008-05-21 | 华南理工大学 | Multiple efficacy complex microsphere for cosmetics and preparation method thereof |
| CN101225179A (en) * | 2008-02-05 | 2008-07-23 | 复旦大学 | Large-area ordered porous membrane material and preparation method thereof |
| CN101695652A (en) * | 2009-10-29 | 2010-04-21 | 复旦大学 | Gas separation functional material and preparation method and application thereof |
-
2010
- 2010-12-01 CN CN 201010567428 patent/CN102070152B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101181184A (en) * | 2007-11-30 | 2008-05-21 | 华南理工大学 | Multiple efficacy complex microsphere for cosmetics and preparation method thereof |
| CN101225179A (en) * | 2008-02-05 | 2008-07-23 | 复旦大学 | Large-area ordered porous membrane material and preparation method thereof |
| CN101695652A (en) * | 2009-10-29 | 2010-04-21 | 复旦大学 | Gas separation functional material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102070152A (en) | 2011-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102070152B (en) | Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof | |
| CN109261128B (en) | Boric acid type magnetic COFs material, preparation method and application thereof | |
| Gao et al. | Preparation, characterization, and adsorption evaluation of chitosan-functionalized mesoporous composites | |
| CN105555383B (en) | Chromatographic column and separator comprising porous surface material and its for supercritical fluid chromatography and the purposes of other chromatograms | |
| Yuan et al. | Highly efficient removal of uranium from aqueous solution using a magnetic adsorbent bearing phosphine oxide ligand: A combined experimental and density functional theory study | |
| CN102492428B (en) | Uniform fluorescent microball and preparation method | |
| CN110938282B (en) | Composite material with covalent organic framework and core-shell structure and preparation method and application thereof | |
| CN110508249B (en) | Amidoxime modified silicon dioxide nano microsphere composite material and preparation method thereof | |
| CN105233799A (en) | Magnetic metal-organic framework material with core-shell structure and preparation method therefor | |
| CN104312215A (en) | Silicon dioxide surface grafting modification method | |
| CN102513064A (en) | Preparation method and application of ionic liquid bonded silica adsorbent | |
| Chen et al. | Microwave-assisted RAFT polymerization of well-constructed magnetic surface molecularly imprinted polymers for specific recognition of benzimidazole residues | |
| CN104558409A (en) | Surface molecular imprinting polymer made from nanoflower material, and preparation and application of surface molecular imprinting polymer | |
| Yang et al. | A novel morphological ion imprinted polymers for selective solid phase extraction of Cd (II): preparation, adsorption properties and binding mechanism to Cd (II) | |
| CN106582543A (en) | Chiral MOF (Metal-Organic Framework) magnetic graphene functional material, and preparation method and application thereof | |
| CN107189012B (en) | The preparation method and product of phthalate molecularly imprinted polymer and application | |
| CN109970912B (en) | Preparation method of flavonoid magnetic molecularly imprinted polymer | |
| CN107200812A (en) | A kind of preparation method of magnetic molecularly imprinted material | |
| CN106061601A (en) | Multifunctional sorbent materials and uses thereof | |
| Mahmoud et al. | Evaluation of silica/ferrocyanide composite as a dual-function material for simultaneous removal of 137Cs+ and 99TcO4− from aqueous solutions | |
| CN107551987A (en) | A kind of magnetic adsorbent and its production and use | |
| CN107970878A (en) | A kind of preparation method of phosphate group functionalization hollow mesoporous silica microsphere | |
| CN107474060A (en) | It is a kind of have be selectively adsorbing and separating metal-organic framework material of anionic dye performance and its preparation method and application | |
| CN110372737A (en) | A kind of nano silicon-based microballoon preparation method of sulfhydrylation and application | |
| CN110127762A (en) | The method of urania is recycled in a kind of uranium-containing waste water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SUZHOU NANO-MICRO TECHNOLOGY CO., LTD. Free format text: FORMER NAME: SUZHOU NANO-MICRO BIO-TECHNOLOGY CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: Xinghu Street Industrial Park of Suzhou city in Jiangsu province 215123 No. 218 BioBAY building C1 Patentee after: SUZHOU NANOMICRO TECHNOLOGY COMPANY LIMITED Address before: Xinghu Street Industrial Park of Suzhou city in Jiangsu province 215123 No. 218 BioBAY group C building A Patentee before: Suzhou Nano-Micro Bio-technology Co., Ltd. |
|
| CP03 | Change of name, title or address |
Address after: No. 2, Bai Sichuan street, Suzhou Industrial Park, Jiangsu Province Patentee after: Suzhou Nanwei Polytron Technologies Inc Address before: 215123 C1 Biological Park, No. 218 Xing Hu Street, Suzhou Industrial Park, Jiangsu. Patentee before: SUZHOU NANOMICRO TECHNOLOGY COMPANY LIMITED |
|
| CP03 | Change of name, title or address |