CN106215908A - Porous spherical silica gel chromatographic column filling material and preparation method - Google Patents
Porous spherical silica gel chromatographic column filling material and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of porous spherical silica gel chromatographic column filling material and preparation method, method is: dehydrated alcohol and component 1 are mixed by (1), obtain mixed solution；(2) aqueous hydrochloric acid solution is joined in mixed solution, stirring, remove solvent, obtain polysiloxane prepolymers；(3) dehydrated alcohol and viscosity modifier are made continuous phase；Polysiloxane prepolymers is distributed in continuous phase, obtains emulsion dispersion system；(4) strong aqua ammonia is added in emulsion dispersion system, stirring reaction, stands aging, microsphere is collected by filtration, washing, it is dried, obtains spherical silica gel microsphere；(5) spherical silica gel microsphere is disperseed in deionized water；(6) strong aqua ammonia is added in spherical silica gel microsphere dispersion liquid, stirring；Collect solid, washing, be dried, calcining, obtain porous spherical silica gel chromatographic column filling material.The spherical rounding of filler of the present invention, narrow diameter distribution.Can be used for the clastotypes such as normal-phase chromatography, preparation method is simple, and condition is easily-controllable, and yield rate is high.
Description
Technical field
The present invention relates to a kind of porous spherical silica gel chromatographic column filling material and preparation method, belong to porous spherical silica gel chromatographic column filling material
Technology of preparing.
Background technology
High performance liquid chromatography is one of most important laboratory separate analytical technique, at food, medicine, environment, chemical industry
Have a wide range of applications Deng in field.Chromatograph of liquid is by critical components such as high pressure pump, injection valve, chromatographic column and detectors
Composition.Infusion pump is used for driving liquid flowing to pass through chromatographic column mutually.After sample enters chromatographic column by injection valve, flowed
Chromatographic column is passed through in carrying of phase.Due to the difference of different compounds partition coefficient between chromatographic stationary phases and flowing mutually,
They arrive the detector being positioned at column outlet at different rates, thus are separated and detect.And sample is by detection
Spectral bandwidth during device, represents the separation efficiency of this technology, mainly by the chromatographic stationary phases filled in the chromatography column
Character is determined.And chromatographic stationary phases is made typically by the surface bond selectivity functional group at chromatograph packing material or carrier
?.Therefore, the core component of decision chromatographic technique separation efficiency is chromatograph packing material.Porous microsphere as chromatograph packing material, it is necessary to
Meet mechanical strength high, indeformable under high pressure；Uniform particle diameter, interstitital texture is uniform；Mesopore pore size, resistance to mass tranfer is little；Chemistry is steady
Qualitative good, not with the requirement such as analyzed compound reacts.Although the kind of chromatograph packing material is many, including organic polymer and
Inorganic porous material, Bio-sil is due to its stable physicochemical properties, controlled pore structure parameter, higher machinery by force
Spend, be prone to the features such as surface modification and modification and become current most widely used chromatograph packing material.
Due to silica matrix chromatogram packing for improve chromatographic technique separation efficiency significance, develop spherical rounding,
The preparation method of size tunable, pore structure adjustable Bio-sil microsphere is the research heat in chemistry and material science all the time
Point.Traditional spray drying method is the mature industry technology of batch production spheroidal particle, but there is particle diameter distribution width, easily generates
The shortcomings such as hollow ball and pore structure defect；Silica gel uniform particle diameter prepared by polymerisation induced colloidal agglomerates method, but the microsphere generated
Pore structure not easy-regulating, be also not suitable for the preparation of big particle diameter microsphere.Base catalysis sol-gal process with alkoxyl silicone as raw material
Preparation-obtained silica gel microball monodispersity is good, but, particle diameter is less and mostly is microcellular structure, should not be used as chromatograph packing material.
Unger and working together first proposed the two-stage catalysis sol-gal process combining emulsion polymerization in 1973, is used for preparing particle diameter
Narrowly distributing, pore structure adjustable porous silica microsphere.In this process, silester (TEOS) or polysilicon acid second
Ester-40 (TES-40) is after acid-catalyzed hydrolysis, and obtaining molecular weight is the prepolymer between 700-2000.Then prepolymer is disperseed
Emulsion droplet is formed to aqueous phase.Under the effect of base catalyst, the prepolymer generation condensation reaction in drop, form titanium dioxide
Silicone-hydrogel.After suitable post processing such as aging dry grade, obtain porous silica gel microball.But, this method there is also seriously
Not enough.Owing to the viscosity of dispersion phase is much higher than the viscosity of continuous phase, viscosity resistance is big, and needing vigorous mechanical agitation could will be pre-
Polymers is emulsified into droplet, easily forms the emulsion structure of water/oil/water, cause in prepared microsphere and be mingled with in emulsion process
Substantial amounts of hollow ball and bar, particle size distribution is the widest.Although these hollow balls and bar can be by follow-up
Gradation method is eliminated, and they will have a strong impact on the yield of target grain size microsphere, increases production cost.Obviously, development
Narrow diameter distribution, the preparation method of morphology controllable can receive energy-saving and cost-reducing effect, have important economic benefit and society
Meaning.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that the preparation of a kind of porous spherical silica gel chromatographic column filling material
Method.
Second object of the present invention is to provide a kind of porous spherical silica gel chromatographic column filling material prepared by said method.
Technical scheme is summarized as follows:
The preparation method of a kind of porous spherical silica gel chromatographic column filling material, comprises the steps:
(1) 1-6, by dehydrated alcohol and component 1 mix homogeneously, obtains mixed solution in molar ratio；
Described component 1 be tetraethyl orthosilicate, silester-40, mol ratio be tetraethyl orthosilicate and the tri-alkoxy of 2-10
The mixture of silane or silester-40 that mol ratio is 2-4 and the mixture of trisiloxanes；
(2) joining in mixed solution by the aqueous hydrochloric acid solution of 0.1M, 25-30 DEG C of stirring 0.5-4h, decompression is distilled off
Solvent, obtains polysiloxane prepolymers；Water in described aqueous hydrochloric acid solution is 0.5-2 with the mol ratio of component 1；
(3) dehydrated alcohol is mixed homogeneously with viscosity adjustment agent solution and is made continuous phase by 0-0.5 by volume；By volume
Dispersion phase polysiloxane prepolymers is distributed in described continuous phase by 0.2-0.5, stirs, and obtains emulsion dispersion system；
Described viscosity adjustment agent solution is that mass concentration is the Aqueous Solutions of Polyethylene Glycol of 10%-30% or water or mass ratio is
The surfactant of 0.5-5% and mass concentration are the solution of the Aqueous Solutions of Polyethylene Glycol of 0%-30%；
(4), during strong aqua ammonia is joined described emulsion dispersion system by 0.01-0.2 by volume, stir under 500-1000rpm
Mix reaction 20min-60min, obtain soft gel micro-ball；At room temperature stand aging 2-5d, microsphere is collected by filtration, use volumetric concentration
Be 95% ethanol water and water alternately washing to filtrate be neutrality, vacuum drying, i.e. obtain spherical silica gel microsphere；
(5) spherical silica gel microsphere is disperseed in deionized water by 0.05-0.3 in mass ratio, mix homogeneously；
(6) during strong aqua ammonia is joined the spherical silica gel microsphere dispersion liquid that step (5) obtains by 0-0.5 by volume, 70 DEG C-
At 200 DEG C, stir 0-24h；Solid is collected by filtration, alternately washs to filtrate with the ethanol water that volumetric concentration is 95% and water
For neutrality, obtain porous spherical silica gel microball；It is dried, calcines 6-10h, obtain porous spherical silica gel chromatographic column filling material.
Described trialkoxy silane is MTMS, 1,2-ethidene bridged linkage triethoxysilane or methyl three
Ethoxysilane.
Described Polyethylene Glycol is polyethylene glycol 200, Macrogol 2000, Macrogol 4000, polyethylene glycol 6000, poly-second
Glycol 8000 or PEG20000.
Described surfactant includes triton x-100, polysorbas20, Tween 80 or OP-10.
A kind of porous spherical silica gel chromatographic column filling material prepared by said method.
Advantages of the present invention:
Porous spherical silica gel chromatographic column filling material of the present invention, its particle diameter is in 0.5-150 μm, and pore volume is at 0.4-2.0mL/g, specific surface
Amass at 215.0-500.3m2/ g, aperture is at 3.0-30.1nm.The method of the present invention is prepared spherical rounding, narrow diameter distribution, is not contained
Special-shaped object and the adjustable spherical silica gel of pore structure.This silica gel can be directly used in normal-phase chromatography splitting die as chromatograph packing material
Formula, it is also possible to react through chemical bonding, make the chemistry containing groups such as amino, carboxyl, glycol-based, cyano group, octyl group, octadecyls
Bonded Phase, for different chromatographic isolation patterns, the method preparation process of the present invention is simple, and condition is easily-controllable, and yield rate is high.
Accompanying drawing explanation
Fig. 1, with tetraethyl orthosilicate for silicon source, uses the mol ratio institute of the water in different aqueous hydrochloric acid solution and tetraethyl orthosilicate
Prepare porous spherical silica gel chromatographic column filling material microphotograph (prepared by embodiment 1).
Fig. 2, with silester-40 for silicon source, uses the porous spherical silica gel chromatography prepared by different types of Polyethylene Glycol
The microphotograph (prepared by embodiment 2) of filler.
Fig. 3, with silester-40 for silicon source, uses the porous spherical silica gel color prepared by different types of surfactant
The microphotograph (prepared by embodiment 3) of spectrum filler.
Fig. 4 with mol ratio be 2 silester and MTMS for silicon source, use the poly-second of different quality concentration
The microphotograph of the glycol 10000 methyl prepared by continuous phase hybridization porous spherical silica gel chromatograph packing material (make by embodiment 6
Standby).
Fig. 5, with mol ratio 4 ethyl polysilicate-40 and ethylene bridging trimethoxy silicon for silicon source, uses not homogeneity
The PEG20000 of amount concentration is that the microscope of the porous spherical silica gel chromatographic column filling material of the bridging hydridization prepared by continuous phase shines
Sheet (prepared by embodiment 8).
(embodiment 9, by embodiment 4 step 6 for the pattern microphotograph of Fig. 6 porous spherical silica filler after screening
Middle ammonia is gained after microsphere prepared by 0.01 sieves with the volume ratio of spherical silica gel microsphere dispersion liquid).
Adsorption-desorption isothermal curve (Fig. 7 a) and the BJH aperture of Fig. 7 porous spherical silica gel chromatographic column filling material after screening are divided
(ammonia in embodiment 4 step 6 and the volume ratio of spherical silica gel microsphere dispersion liquid are 0.01 made to Butut (Fig. 7 b) by embodiment 9
Gained after standby microsphere screening).
Fig. 8 uracil, toluene, ethylbenzene, 1,4-dihydroxyanthraquinone and amitriptyline are made with silester-40 for silicon source
Standby porous spherical silica gel chromatographic column filling material is that (embodiment 9, by ammonia and ball in embodiment 4 step 6 for the separation on chromatographic stationary phases
The volume ratio of shape silica gel microball dispersion liquid is gained after microsphere screening prepared by 0.01).
Detailed description of the invention
The present invention is realized by following proposal.
Use two-stage catalysis emulsion gel polymerization process, in the emulsion system that siloxane prepolymer is formed, add suitably
Viscosity modifier, to reduce the differences in viscosity between dispersion phase and continuous phase.Then by the condensation under base catalyst effect
Reaction, is converted into porous spherical silica gel chromatographic column filling material by the polysiloxane prepolymers in emulsion droplet.Prepared by the method many
The narrow diameter distribution of hole silica gel microball, without hollow ball and special-shaped object, the particle diameter of microsphere and pore structure parameter are within the specific limits
Adjustable.Therefore, the yield rate of target grain size granule is improved.
Below by specific embodiment, the present invention is further illustrated.The following examples are in order to make this area
Technical staff better understood when the present invention, but does not impose any restrictions the present invention.
Embodiment 1
The preparation method of porous spherical silica gel chromatographic column filling material, comprises the steps:
(1) 1 dehydrated alcohol and tetraethyl orthosilicate (TEOS, 104g) being added there-necked flask in molar ratio, 500rpm stirring is mixed
Close uniformly, obtain mixed solution；
(2) aqueous hydrochloric acid solution of 0.1M is joined in mixed solution, 30 DEG C of stirring 0.5h, decompression is distilled off solvent,
Obtain polysiloxane prepolymers；The mol ratio of the water in described aqueous hydrochloric acid solution and tetraethyl orthosilicate is respectively 0.5,1.0,1.5,
2.0；
(3) viscosity adjustment agent solution is continuous phase；The ratio of 0.2 by volume, divides dispersion phase polysiloxane prepolymers
It is scattered in described continuous phase, stirs, obtain emulsion dispersion system；
Viscosity adjustment agent solution be mass ratio be surfactant triton x-100 and the mass concentration of 0.5% be 20%
The solution of PEG20000 aqueous solution,
(4) 0.01 strong aqua ammonia is joined in described emulsion dispersion system by volume, stirring reaction under 1000rpm
20min, obtains soft gel micro-ball；At room temperature stand aging 2d, microsphere is collected by filtration, with the ethanol water that volumetric concentration is 95%
Solution and water alternately washing to filtrate is neutral, and vacuum drying i.e. obtains spherical silica gel microsphere；
(5) spherical silica gel microsphere is disperseed in deionized water by mass ratio 0.05, mix homogeneously；
(6) 0.05 strong aqua ammonia is joined in the spherical silica gel microsphere dispersion liquid that step (5) obtains by volume, 70 DEG C
Under, stir 24h；Solid is collected by filtration, is neutral with the ethanol water that volumetric concentration is 95% and water alternately washing to filtrate,
Obtain porous spherical silica gel microball；It is dried, Muffle furnace 600 DEG C calcining 6h, obtains porous spherical silica gel chromatographic column filling material.
The sign data characterization data of porous spherical silica gel chromatographic column filling material include specific surface area, pore volume, and aperture is listed in table 1
In, microphotograph is shown in Fig. 1, is different mol ratio a:0.5 in figure, b:1.0, c:1.5, d:2.0.
Table 1
Embodiment 2
The preparation method of porous spherical silica gel chromatographic column filling material, comprises the steps:
(1) 4 dehydrated alcohol and silester-40 (TES-40,48g) being added there-necked flask in molar ratio, 500rpm stirs
Mix homogeneously, obtains mixed solution；
(2) aqueous hydrochloric acid solution of 0.1M is joined in mixed solution, 30 DEG C of stirring 1h, decompression is distilled off solvent,
To polysiloxane prepolymers；Water in described aqueous hydrochloric acid solution is 1.2 with the mol ratio of silester-40；
(3) 0.5 dehydrated alcohol mixed homogeneously with viscosity adjustment agent solution make continuous phase by volume；By volume
Dispersion phase polysiloxane prepolymers is distributed in described continuous phase by 0.2, stirs, obtains emulsion dispersion system；
Described viscosity adjustment agent solution respectively mass concentration is polyethylene glycol 200 aqueous solution, the Polyethylene Glycol of 30%
2000 aqueous solutions, Macrogol 4000 aqueous solution, polyethylene glycol 6000 aqueous solution, PEG 8000 aqueous solution, Polyethylene Glycol
10000 aqueous solutions；
(4) 0.01 strong aqua ammonia is joined in described emulsion dispersion system by volume, stirring reaction under 1000rpm
20min, obtains soft gel micro-ball；At room temperature stand aging 3d, microsphere is collected by filtration, with the ethanol water that volumetric concentration is 95%
Solution and water alternately washing to filtrate is neutral, and vacuum drying i.e. obtains spherical silica gel microsphere；
(5) spherical silica gel microsphere is disperseed in deionized water by mass ratio 0.1, mix homogeneously；
(6) 0.05 strong aqua ammonia is joined in the spherical silica gel microsphere dispersion liquid that step (5) obtains by volume, 70 DEG C
Under, stir 24h；Solid is collected by filtration, is neutral with the ethanol water that volumetric concentration is 95% and water alternately washing to filtrate,
Obtain porous spherical silica gel microball；It is dried, Muffle furnace 600 DEG C calcining 10h, obtains porous spherical silica gel chromatographic column filling material.
Porous spherical silica gel chromatographic column filling material be characterized as microphotograph, see Fig. 2.Different Polyethylene Glycol a: poly-second two in figure
Alcohol 200, b: Macrogol 2000, c: Macrogol 4000, d: polyethylene glycol 6000, e: PEG 8000, f: Polyethylene Glycol
10000。
Embodiment 3
The preparation method of porous spherical silica gel chromatographic column filling material, comprises the steps:
(1) 4 dehydrated alcohol and silester-40 (TES-40,48g) being added there-necked flask in molar ratio, 500rpm stirs
Mix homogeneously, obtains mixed solution；
(2) aqueous hydrochloric acid solution of 0.1M is joined in mixed solution, 30 DEG C of stirring 1h, decompression is distilled off solvent,
To polysiloxane prepolymers；Water in described aqueous hydrochloric acid solution is 1.2 with the mol ratio of silester-40；
(3) 0.5 dehydrated alcohol mixed homogeneously with viscosity adjustment agent solution make continuous phase by volume；By volume
Dispersion phase polysiloxane prepolymers is distributed in described continuous phase by 0.2, stirs, obtains emulsion dispersion system；
Described viscosity adjustment agent solution be mass ratio be surfactant and the mass concentration of 5% be the Polyethylene Glycol of 10%
The solution of 10000 aqueous solutions,
Described surfactant is respectively triton x-100, polysorbas20, Tween 80, OP-10；
(4) 0.01 strong aqua ammonia is joined in described emulsion dispersion system by volume, stirring reaction under 1000rpm
20min, obtains soft gel micro-ball；At room temperature stand aging 3d, microsphere is collected by filtration, with the ethanol water that volumetric concentration is 95%
Solution and water alternately washing to filtrate is neutral, and vacuum drying i.e. obtains spherical silica gel microsphere；
(5) spherical silica gel microsphere is disperseed in deionized water by mass ratio 0.2, mix homogeneously；
(6) 0.05 strong aqua ammonia is joined in the spherical silica gel microsphere dispersion liquid that step (5) obtains by volume, 110 DEG C
Under, stir 8h；Solid is collected by filtration, is neutral with the ethanol water that volumetric concentration is 95% and water alternately washing to filtrate,
Obtain porous spherical silica gel microball；It is dried, Muffle furnace 600 DEG C calcining 10h, obtains porous spherical silica gel chromatographic column filling material.
Porous spherical silica gel chromatographic column filling material be characterized as microphotograph, see Fig. 3.Different surfaces activating agent in figure: a: tell
Temperature-20, b: tween 80, c:OP-1, d: triton x-100.
Embodiment 4
The preparation method of porous spherical silica gel chromatographic column filling material, comprises the steps:
(1) 1 dehydrated alcohol and silester-40 (TES-40,48g) being added there-necked flask in molar ratio, 500rpm stirs
Mix homogeneously, obtains mixed solution；
(2) aqueous hydrochloric acid solution of 0.1M is joined in mixed solution, 28 DEG C of stirring 3h, decompression is distilled off solvent,
To polysiloxane prepolymers；Water in described aqueous hydrochloric acid solution is 1.2 with the mol ratio of silester-40；
(3) 0.3 dehydrated alcohol mixed homogeneously with viscosity adjustment agent solution make continuous phase by volume；By volume
Dispersion phase polysiloxane prepolymers is distributed in described continuous phase by 0.5, stirs, obtains emulsion dispersion system；
Described viscosity adjustment agent solution be mass concentration be the PEG20000 aqueous solution of 20%；
(4) 0.1 strong aqua ammonia is joined in described emulsion dispersion system by volume, stir reaction at 500 rpm
30min, obtains soft gel micro-ball；At room temperature stand aging 2d, microsphere is collected by filtration, with the ethanol water that volumetric concentration is 95%
Solution and water alternately washing to filtrate is neutral, and vacuum drying i.e. obtains spherical silica gel microsphere；
(5) spherical silica gel microsphere is disperseed in deionized water by mass ratio 0.1, mix homogeneously；
(6) it is respectively 0,0.01,0.05,0.1 by volume and strong aqua ammonia is added separately to the spherical silicon that step (5) obtains
In glue microsphere dispersion liquid, at 110 DEG C, stir 8h；Solid is collected by filtration, hands over the ethanol water that volumetric concentration is 95% and water
It is neutral for washing to filtrate, obtains porous spherical silica gel microball；It is dried, Muffle furnace 600 DEG C calcining 10h, obtains porous spherical
Silica gel chromatographic column filling material.
The sign data characterization data of porous spherical silica gel microball chromatograph packing material include specific surface area, pore volume, and aperture arranges
In table 2.
Table 2
Embodiment 5
The preparation method of porous spherical silica gel chromatographic column filling material, comprises the steps:
(1) 1 dehydrated alcohol and tetraethyl orthosilicate (TEOS, 104g) being added there-necked flask in molar ratio, 500rpm stirring is mixed
Close uniformly, obtain mixed solution；
(2) aqueous hydrochloric acid solution of 0.1M is joined in mixed solution, 25 DEG C of stirring 4h, decompression is distilled off solvent,
To polysiloxane prepolymers；Water in described aqueous hydrochloric acid solution is 1.2 with the mol ratio of tetraethyl orthosilicate；
(3) 0.3 dehydrated alcohol mixed homogeneously with viscosity adjustment agent solution make continuous phase by volume；By volume
Dispersion phase polysiloxane prepolymers is distributed in described continuous phase by 0.2, stirs, obtains emulsion dispersion system；
Described viscosity adjustment agent solution be mass concentration be the PEG20000 aqueous solution of 20%；
(4) 0.05 strong aqua ammonia is joined in described emulsion dispersion system by volume, stir reaction at 800 rpm
60min, obtains soft gel micro-ball；At room temperature stand aging 3d, microsphere is collected by filtration, with the ethanol water that volumetric concentration is 95%
Solution and water alternately washing to filtrate is neutral, and vacuum drying i.e. obtains spherical silica gel microsphere；
(5) spherical silica gel microsphere is disperseed in deionized water by mass ratio 0.1, mix homogeneously；
(6) 0.1 strong aqua ammonia is joined in the spherical silica gel microsphere dispersion liquid that step (5) obtains by volume, at 70 DEG C,
Stir 0 respectively, 4,8,24h；Solid is collected by filtration, alternately washs to filtrate with the ethanol water that volumetric concentration is 95% and water
For neutrality, obtain porous spherical silica gel microball；It is dried, Muffle furnace 600 DEG C calcining 10h, obtains porous spherical silica gel chromatographic column filling material.
The sign data characterization data of porous spherical silica gel chromatographic column filling material include specific surface area, pore volume, and aperture is listed in table 3
In.
Table 3
Embodiment 6
The synthesis of porous methyl hybridisation silica gel chromatograph packing material, comprises the steps:
(1) in molar ratio 1 by dehydrated alcohol and component 1 mix homogeneously, mixed solution is obtained；Component 1 is 2 for mol ratio
Silester-40 and the mixture of MTMS；
(2) aqueous hydrochloric acid solution of 0.1M is joined in mixed solution, 25 DEG C of stirring 4h, decompression is distilled off solvent,
To polysiloxane prepolymers；Water in described aqueous hydrochloric acid solution and the mol ratio 1.2 of component 1；
(3) viscosity adjustment agent solution mix homogeneously makes continuous phase；0.25 by dispersion phase polysiloxane pre polymers by volume
Thing is distributed in described continuous phase, stirs, and obtains emulsion dispersion system；
Described viscosity adjustment agent solution be mass ratio be 1.5% surfactant triton x-100 respectively with not homogeneity
The mixed solution of the PEG20000 aqueous solution of amount concentration 0%, 10%, 20%, 30%；
(4) 0.1 strong aqua ammonia is joined in above-mentioned emulsion dispersion by volume, stir reaction at 500 rpm
60min, obtains soft gel micro-ball；At room temperature stand aging 3d, microsphere be collected by filtration, volumetric concentration be 95% ethanol water-soluble
Liquid and water alternately washing to filtrate is neutral, and vacuum drying i.e. obtains spherical methyl hybridisation silica gel microsphere；
(5) spherical silica gel microsphere is disperseed in deionized water by mass ratio 0.3, mix homogeneously；
(6) 0.2 strong aqua ammonia is joined in the spherical silica gel microsphere dispersion liquid that step (5) obtains by volume, 200 DEG C
Under, stir 12h；Solid is collected by filtration, volumetric concentration be 95% ethanol water and water alternately washing to filtrate be neutrality,
Obtain porous spherical silica gel microball；After drying, 300 DEG C of calcining 10h, obtain porous spherical silica gel chromatographic column filling material.
The sign data of porous methyl hybridisation silica gel chromatograph packing material include specific surface area, pore volume, and aperture is shown in Table 4,
Microphotograph is shown in Fig. 4.In figure with silester-and MTMS for silicon source, the poly-second two of different quality concentration
Alcohol is the microphotograph of methyl hybridisation silica gel microsphere prepared by continuous phase, a:0%, b:10%, c:20%, d:30%.
Table 4
Embodiment 7
The synthesis of porous methyl hybridisation silica gel chromatograph packing material, comprises the steps:
(1) in molar ratio 6 by dehydrated alcohol and component 1 mix homogeneously, mixed solution is obtained；Component 1 is respectively mol ratio
10,5,2 tetraethyl orthosilicate and the mixture of MTES；
(2) aqueous hydrochloric acid solution of 0.1M is joined in mixed solution, 30 DEG C of stirring 4h, decompression is distilled off solvent,
To polysiloxane prepolymers；Water in described aqueous hydrochloric acid solution and the mol ratio 1.2 of component 1；
(3) 0.2 dehydrated alcohol mixed homogeneously with viscosity adjustment agent solution make continuous phase by volume；By volume
Dispersion phase polysiloxane prepolymers is distributed in described continuous phase by 0.25, stirs, obtains emulsion dispersion system；
Described viscosity adjustment agent solution be mass ratio be that the surfactant triton x-100 of 2.5% is with mass concentration
The solution of the PEG20000 aqueous solution of 20%；
(4) 0.1 strong aqua ammonia is joined in above-mentioned emulsion dispersion by volume, stir reaction at 500 rpm
60min, obtains soft gel micro-ball；At room temperature stand aging 5d, microsphere be collected by filtration, volumetric concentration be 95% ethanol water-soluble
Liquid and water alternately washing to filtrate is neutral, and vacuum drying i.e. obtains spherical methyl hybridisation silica gel microsphere；
(5) spherical silica gel microsphere is disperseed in deionized water by mass ratio 0.3, mix homogeneously；
(6) 0.5 strong aqua ammonia is joined in the spherical silica gel microsphere dispersion liquid that step (5) obtains by volume, 200 DEG C
Under, stir 12h；Solid is collected by filtration, volumetric concentration be 95% ethanol water and water alternately washing to filtrate be neutrality,
Obtain porous spherical silica gel microball；After drying, 300 DEG C of calcining 10h obtain porous spherical silica gel chromatographic column filling material.
The sign data of porous methyl hybridisation silica gel chromatograph packing material include specific surface area, pore volume, and aperture is listed in Table 5 below.
Table 5
Embodiment 8
The synthesis of porous methyl hybridisation silica gel chromatograph packing material, comprises the steps:
(1) in molar ratio 6 by dehydrated alcohol and component 1 mix homogeneously, obtain closing solution；Wherein component 1 is respectively mole
Than the silester-40 and the mixture of 1,2-ethidene bridged linkage triethoxysilane that are 4；
(2) joining in siloxanes mixed solution by the aqueous hydrochloric acid solution of 0.1M, 30 DEG C of stirring 4h, decompression is distilled off molten
Agent, obtains polysiloxane prepolymers；Water in described aqueous hydrochloric acid solution and the mol ratio 1.5 of component 1；
(3) 0.2 dehydrated alcohol mixed homogeneously with viscosity adjustment agent solution make continuous phase by volume；By volume
Dispersion phase polysiloxane prepolymers is distributed in described continuous phase by 0.25, stirs, obtains emulsion dispersion system；
The PEG20000 that described viscosity adjustment agent solution is respectively mass concentration 0%, 10%, 20%, 30% is water-soluble
Liquid,
(4) 0.2 strong aqua ammonia is joined in above-mentioned emulsion dispersion by volume, stirring reaction under 1000rpm
30min, obtains soft gel micro-ball；At room temperature stand aging 3d, microsphere be collected by filtration, volumetric concentration be 95% ethanol water-soluble
Liquid and water alternately washing to filtrate is neutral, and vacuum drying i.e. obtains spherical overseas Chinese federation hybridisation silica gel microsphere；
(5) spherical silica gel microsphere is disperseed in deionized water by mass ratio 0.3, mix homogeneously；
(6) 0.2 strong aqua ammonia is joined in the spherical silica gel microsphere dispersion liquid that step (5) obtains by volume, 200 DEG C
Under, stir 24h；Solid is collected by filtration, volumetric concentration be 95% ethanol water and water alternately washing to filtrate be neutrality,
Obtain porous spherical silica gel microball；After drying, 300 DEG C of calcining 10h, obtain porous spherical silica gel chromatographic column filling material.
Characterizing data and include specific surface area, pore volume, aperture is shown in Table 6, and microphotograph is shown in Fig. 5.With poly-silicon in figure
Acetoacetic ester-40 and ethylene bridging trimethoxy silicon are silicon source, and the Polyethylene Glycol of different quality concentration is that continuous phase is made
The microphotograph of standby bridging hybridisation silica gel microsphere, a:0%, b:10%, c:20%, d:30%
What table 5 was listed is, and to use the PEG20000 of different quality concentration be that the porous bridging prepared by continuous phase is miscellaneous
Change the particle diameter distribution of silica gel microball.
Table 6
Embodiment 9: reverse-phase HPLC chromatography evaluation
(1) classification of porous spherical silica gel chromatographic column filling material
It is the porous prepared by 0.01 by the volume ratio of ammonia in embodiment 4 step (6) Yu spherical silica gel microsphere dispersion liquid
Spherical silica gel filler is screened, obtains the porous spherical silica gel chromatographic column filling material of 10 μm, and the pattern of filler is shown in Fig. 6 microphotograph；
Pore structure parameter is shown in nitrogen adsorption curve (Fig. 7 a) and pore size distribution curve (Fig. 7 b).
(2) silica gel activating
In there-necked flask, porous spherical silica gel chromatographic column filling material and 100mL mass fraction that addition 10g is sieving through are 10%
Hydrochloric acid, 250rpm mechanical agitation mix homogeneously, in 105 DEG C of oil baths, it is heated to reflux 8.0h.Reaction is washed to neutrality, nothing after terminating
Water-ethanol washs rear 90 DEG C of vacuum drying, the porous spherical silica gel microball after being acidified；
(3) bonding reaction
In another there-necked flask, add the porous spherical silica gel microball after 10g acidifying and 80mL dry toluene, add
1.0mL triethylamine, under nitrogen protection, 110 DEG C, adds 4mL octadecyl trichlorosilane alkane after 250rpm stirring mixing 30min, continues
Continuous back flow reaction 8h.After reaction uses toluene, ethanol, water, washing with alcohol after terminating successively, 90 DEG C of vacuum drying, C18 must be bonded
Bio-sil chromatograph packing material.
(4) post effect measures
Take the appropriate Bio-sil chromatograph packing material being bonded C18, be uniformly dispersed in acetone, with methanol as displacement fluid,
Under 400bar pressure, load rustless steel chromatographic column.It is made up of uracil, toluene, ethylbenzene, 1,4-dihydroxyanthraquinone and amitriptyline
Test mixing thing, for the chromatographic performance evaluation of chromatograph packing material.Uracil is used for measuring chromatographic column dead time, toluene and ethylbenzene
For measuring hydrophobicity and methane selectivity, Isosorbide-5-Nitrae-dihydroxyanthraquinone is used for measuring metal ion activity and amitriptyline for surveying
Determine silanol base activity.Gained chromatographic data is listed in Table 7 below, and chromatogram is shown in Fig. 8.Uracil, toluene, ethylbenzene, 1,4-dihydroxy in figure
Base anthraquinone and amitriptyline with silester-40 for the silica gel microball prepared by silicon source as chromatographic stationary phases on separation.
The chromatographic isolation result of table 7 uracil, toluene, ethylbenzene, 1,4-dihydroxyanthraquinone and amitriptyline
The test mixing thing being made up of uracil, toluene, ethylbenzene, Isosorbide-5-Nitrae-dihydroxyanthraquinone and amitriptyline, is used for implementing
The chromatographic performance evaluation of the porous spherical silica gel microball chromatograph packing material of example 1,2,3,5,6,7,8 preparation.Its effect and embodiment 4 phase
Seemingly.
The porous spherical silica gel chromatographic column filling material rich surface that the method for the present invention prepares contain silicone hydroxyl, can by with contain
Chlorosilane reagent or the reaction of alkoxysilane reagent, be bonded the functional groups such as octadecyl, obtain chemical bonding chromatograph packing material.
During above-mentioned preparation method, preparing of emulsion dispersion system is most important.The viscosity modifiers such as Polyethylene Glycol
Addition, improve the viscosity of continuous phase, can be that emulsion droplet drop provides intensity higher interfacial film, simultaneously because continuous phase
Viscosity resistance effect reduces emulsion droplet movement rate, reduces the probability of emulsion droplet coalescence, and emulsion droplet is able to stably deposit in continuous phase
, it is to avoid the generation of bar.It addition, use with the close aqueous solution of dispersed phase viscosity as continuous phase, reduce biphase it
Between energy transfer resistance, under relatively low mixing speed, can be obtained by the small particle microsphere of narrow diameter distribution.Mixing speed
Decline so that air is difficult to be mixed in whipping process and inclusion is inside emulsion droplet, it is to avoid the formation of hollow-core construction.Cause
This, the viscosity using viscosity modifier to improve continuous phase is conducive to obtaining the microsphere of spherical rounding and narrow diameter distribution.
Claims (5)
1. a preparation method for porous spherical silica gel chromatographic column filling material, is characterized in that comprising the steps:
(1) 1-6, by dehydrated alcohol and component 1 mix homogeneously, obtains mixed solution in molar ratio；
Described component 1 be tetraethyl orthosilicate, silester-40, mol ratio be tetraethyl orthosilicate and the trialkoxy silane of 2-10
Mixture or silester-40 that mol ratio is 2-4 and the mixture of trisiloxanes；
(2) aqueous hydrochloric acid solution of 0.1M is joined in mixed solution, 25-30 DEG C of stirring 0.5-4h, decompression is distilled off solvent,
Obtain polysiloxane prepolymers；Water in described aqueous hydrochloric acid solution is 0.5-2 with the mol ratio of component 1；
(3) dehydrated alcohol is mixed homogeneously with viscosity adjustment agent solution and is made continuous phase by 0-0.5 by volume；0.2-by volume
Dispersion phase polysiloxane prepolymers is distributed in described continuous phase by 0.5, stirs, obtains emulsion dispersion system；
Described viscosity adjustment agent solution is that mass concentration is the Aqueous Solutions of Polyethylene Glycol of 10%-30% or water or mass ratio is 0.5-
The surfactant of 5% and mass concentration are the solution of the Aqueous Solutions of Polyethylene Glycol of 0%-30%；
(4), during strong aqua ammonia is joined described emulsion dispersion system by 0.01-0.2 by volume, under 500-1000rpm, stirring is anti-
Answer 20min-60min, obtain soft gel micro-ball；At room temperature stand aging 2-5d, microsphere is collected by filtration, by volumetric concentration be
The ethanol water of 95% and water alternately washing to filtrate is neutral, and vacuum drying i.e. obtains spherical silica gel microsphere；
(5) spherical silica gel microsphere is disperseed in deionized water by 0.05-0.3 in mass ratio, mix homogeneously；
(6) during strong aqua ammonia is joined the spherical silica gel microsphere dispersion liquid that step (5) obtains by 0-0.5 by volume, 70 DEG C-200
At DEG C, stir 0-24h；Solid is collected by filtration, with the ethanol water that volumetric concentration is 95% and water alternately washing to filtrate is
Neutrality, obtains porous spherical silica gel microball；It is dried, calcines 6-10h, obtain porous spherical silica gel chromatographic column filling material.
The preparation method of porous spherical silica gel chromatographic column filling material the most according to claim 1, is characterized in that described tri-alkoxy
Silane is MTMS, 1,2-ethidene bridged linkage triethoxysilane or MTES.
The preparation method of porous spherical silica gel chromatographic column filling material the most according to claim 1, is characterized in that described Polyethylene Glycol
For polyethylene glycol 200, Macrogol 2000, Macrogol 4000, polyethylene glycol 6000, PEG 8000 or Polyethylene Glycol
10000。
The preparation method of porous spherical silica gel chromatographic column filling material the most according to claim 1, is characterized in that described surface activity
Agent includes triton x-100, polysorbas20, Tween 80 or OP-10.
5. a kind of porous spherical silica gel chromatographic column filling material that prepared by the method for one of claim 1-4.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110064382A (en) * | 2019-05-20 | 2019-07-30 | 中谱科技(福州)有限公司 | A kind of porous silica microballoon and the preparation method and application thereof |
| CN112221474A (en) * | 2020-09-23 | 2021-01-15 | 重庆天外天生物技术有限公司 | Bilirubin adsorbent with high mechanical strength and good biocompatibility and preparation method thereof |
| CN112675809A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Silicon-containing material with adsorption function, preparation method thereof and method for removing polar compounds in material |
| CN115178245A (en) * | 2022-06-21 | 2022-10-14 | 南通裕弘分析仪器有限公司 | Preparation method and application of organic-inorganic hybrid silica gel particles |
| CN117563558A (en) * | 2024-01-17 | 2024-02-20 | 广州研创生物技术发展有限公司 | Modified porous spherical silica gel and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110064382A (en) * | 2019-05-20 | 2019-07-30 | 中谱科技(福州)有限公司 | A kind of porous silica microballoon and the preparation method and application thereof |
| CN112675809A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Silicon-containing material with adsorption function, preparation method thereof and method for removing polar compounds in material |
| CN112221474A (en) * | 2020-09-23 | 2021-01-15 | 重庆天外天生物技术有限公司 | Bilirubin adsorbent with high mechanical strength and good biocompatibility and preparation method thereof |
| CN112221474B (en) * | 2020-09-23 | 2023-04-07 | 重庆天外天生物技术有限公司 | Bilirubin adsorbent with high mechanical strength and good biocompatibility and preparation method thereof |
| CN115178245A (en) * | 2022-06-21 | 2022-10-14 | 南通裕弘分析仪器有限公司 | Preparation method and application of organic-inorganic hybrid silica gel particles |
| CN117563558A (en) * | 2024-01-17 | 2024-02-20 | 广州研创生物技术发展有限公司 | Modified porous spherical silica gel and preparation method thereof |
| CN117563558B (en) * | 2024-01-17 | 2024-04-16 | 广州研创生物技术发展有限公司 | Modified porous spherical silica gel and preparation method thereof |
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