CN113019343B - Organic-inorganic hybrid microsphere with ordered pore canal structure and preparation method and application thereof - Google Patents
Organic-inorganic hybrid microsphere with ordered pore canal structure and preparation method and application thereof Download PDFInfo
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- CN113019343B CN113019343B CN202110277665.7A CN202110277665A CN113019343B CN 113019343 B CN113019343 B CN 113019343B CN 202110277665 A CN202110277665 A CN 202110277665A CN 113019343 B CN113019343 B CN 113019343B
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Abstract
The invention provides an organic-inorganic hybrid microsphere with an ordered pore canal structure, a preparation method and application thereof, wherein the organic-inorganic hybrid microsphere comprises a large-aperture polymer matrix and a silica framework filled in the aperture of the large-aperture polymer matrix; the silicon dioxide framework is an ordered mesoporous material. The organic-inorganic hybrid microsphere provided by the invention adopts the large-aperture polymer matrix to coat the silica framework with the ordered pore canal structure, so that the alkali resistance of the organic-inorganic hybrid microsphere can be improved, the organic-inorganic hybrid microsphere is prepared by a chemical method, the aperture size can be accurately regulated and controlled according to the size of a target molecule, the uniformity of the aperture is controlled, and the separation efficiency can be effectively improved when the organic-inorganic hybrid microsphere is used as a chromatographic packing.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to an organic-inorganic hybrid microsphere with an ordered pore canal structure, and a preparation method and application thereof.
Background
The high performance liquid chromatography technology is widely used for separation and purification of biopharmaceuticals, extraction of natural products, food safety detection, environmental protection monitoring, quality monitoring of petrochemical products and the like, and a core component for determining separation efficiency of the chromatography technology is chromatographic packing. As the porous microsphere of the chromatographic packing, the characteristics of high mechanical strength, good chemical stability, uniform particle size, small mass transfer resistance and the like are required to be satisfied. Although the chromatographic packing has a plurality of types, including organic polymer and inorganic porous material, the porous silica gel becomes the most widely used chromatographic packing at present due to the characteristics of stable physical and chemical properties, controllable pore structure parameters, higher mechanical strength, easy surface modification and modification, etc.
Silica gel-based fillers have found widespread use in High Performance Liquid Chromatography (HPLC), solid phase extraction. The surface of silica gel can be chemically modified to prepare bonding phases with various functional groups, water and an organic solvent can be used as mobile phases, and when the solvent is changed, the volume of the silica gel filler cannot be changed. Thus, the packed bed remains stable during the different solvents encountered and the gradient elution.
CN103601198A discloses a mesoporous silica chromatographic packing and a preparation method thereof, which belong to the technical field of inorganic mesoporous material preparation, and comprise the following steps: adding the triblock copolymer into water, adding an acidic solution, stirring for reaction, adding tetraethoxysilane, and continuing stirring for reaction to obtain a reaction solution; carrying out hydrothermal reaction on the reaction liquid, carrying out suction filtration, and washing and drying a filter cake to obtain a hybrid; adding the heterozygote and ammonium perchlorate into nitric acid, performing hydrothermal oxidation reaction, cooling, filtering, washing filter residues with water to neutrality, and drying to obtain the mesoporous silica chromatographic packing. The mesoporous silica material prepared by the method not only perfectly maintains the structure and the surface property of an inorganic framework, but also has the removal rate of the structure directing agent reaching more than 98 percent, the product has good order, and the surface of the product has a large amount of silicon hydroxyl groups, is suitable for being used as chromatographic packing, has good separation effect on organic micromolecular mixture, but has good spherical structure as the chromatographic packing, but has poor sphericity as the chromatographic packing prepared by the method
CN102133513a discloses a method for preparing monodisperse porous inorganic microspheres. The functionalized porous polymer microsphere is used as a template, the hydrolytic condensation reaction of the inorganic precursor is controlled to be carried out in the pores of the microsphere, so that the polymer/inorganic composite microsphere is generated, and the template is removed to obtain the porous inorganic microsphere. The porous inorganic microspheres and the template microspheres provided by the invention have the same size, no size reduction phenomenon is seen, the yield reaches more than 98%, the inorganic microspheres have stable chemical properties and high mechanical strength, and the porous inorganic microspheres and the template microspheres have potential application values in the fields of chromatographic analysis, biological separation, wastewater treatment, catalyst carriers, immobilized enzymes and the like.
CN110508222a discloses a monodisperse core-shell microsphere with mesoporous silica shell layer and a preparation method thereof. The method comprises the following steps: one-pot method for efficiently preparing micron-sized and uniform-sized silane microspheres; then taking the nonporous silane microsphere as a core, preparing a controllable mesoporous silica shell layer, and obtaining a core-shell microsphere; and removing the template agent in the pore canal to obtain the monodisperse core-shell microsphere with the mesoporous silica shell layer. The mesoporous core-shell microsphere prepared by the method has the particle size of 0.22-10.6 mu m, the mesoporous pore diameter of the mesoporous silica core-shell microsphere is 2-40 nm, the thickness of the mesoporous shell layer is 20-600 nm, and the open pore channels perpendicular to the surface of the core can effectively increase the specific surface area of the microsphere, so that the mesoporous core-shell microsphere has excellent application prospects in the fields of chromatographic packing, molecular adsorption and reaction catalysis.
However, the biggest disadvantage of silica gel is its poor alkali resistance and its dissolution at high pH. This is because silica gel surface contains various silanol groups, is acidic, and combines with alkaline solute when separating alkaline compounds (such as amines), so that the alkaline compounds remain increased, widened and tailing, and the application of the silica gel in the field of separating alkaline compounds is limited.
Therefore, developing an organic-inorganic hybrid microsphere with excellent alkali resistance, good mechanical property and ordered pore canal structure is a technical problem which needs to be solved in the field at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an organic-inorganic hybrid microsphere with an ordered pore canal structure, and a preparation method and application thereof; the organic-inorganic hybrid microsphere comprises a large-aperture polymer matrix and a silica framework filled in the aperture of the large-aperture polymer matrix; the silicon dioxide framework is an ordered mesoporous material. The silica framework with the ordered pore canal structure is coated by the large-aperture polymer matrix, so that the alkali resistance of the organic-inorganic hybrid microsphere can be improved at the same time, the particle size of the microsphere can be accurately selected, the aperture size and the uniformity of the pores (ordered pore canal structure) can be accurately regulated and controlled, the utilization rate of the organic-inorganic hybrid microsphere as a chromatographic filler can be effectively improved, and the organic-inorganic hybrid microsphere has important research significance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an organic-inorganic hybrid microsphere having an ordered pore structure, the organic-inorganic hybrid microsphere comprising a large pore polymer matrix and a silica skeleton filled in pores of the large pore polymer matrix; the silicon dioxide framework is an ordered mesoporous material.
At present, silica gel structures with ordered pore channels are directly synthesized by a chemical method, basically are block structures or integral materials, cannot be directly used as chromatographic packing, are poor in direct synthesis sphericity and are very nonuniform in particle size. The preparation method of the (monodisperse) polymer microsphere with uniform particle size distribution is simple, and the polymer microsphere with different particle sizes and different pore diameters can be easily obtained through the market. The invention selects the polymer microsphere with large aperture as the basic skeleton of the target chromatographic packing, has wide grain size selectivity and uniform grain size. Based on Van Deemter theory, compared with the chromatographic packing with non-uniform particle size (polydisperse), the chromatographic packing with uniform particle size has the advantages of small eddy current diffusion coefficient, small radial diffusion, low mass transfer resistance, smaller band broadening effect of a sample, higher column efficiency, and stronger resolution and separation and purification capability of substances.
Meanwhile, for chromatographic separation, the structure and the size of the pore diameter are important factors influencing the separation effect, and the size of the effective specific surface area is determined to a large extent. If the size of the pore diameter can be accurately regulated according to the size of the target molecule, the uniformity of the pore (such as an ordered pore structure) can be controlled, the utilization rate of the chromatographic packing can be effectively improved, and the method is another breakthrough in the development history of the chromatographic packing. Besides the precise selection and control of the particle size, the invention can precisely control the pore size and the uniformity of pores, and the ordered pore channel structure of the silicon dioxide introduced into the pore size has more obvious mass transfer advantage compared with the current disordered and disordered pore channel structure.
The organic-inorganic hybrid microsphere provided by the invention comprises a large-aperture polymer matrix and a silica framework filled in the aperture of the large-aperture polymer matrix; the theoretical principle schematic diagram is shown in figure 1, wherein 1 represents a large-aperture polymer matrix, and 2 represents a silica framework with an ordered aperture structure; the silicon dioxide framework with a mesoporous structure is coated by a large-aperture polymer matrix, so that on one hand, the alkali resistance of the organic-inorganic hybrid microsphere is improved by the large-aperture polymer matrix; on the other hand, the silica framework with the ordered pore canal structure can effectively improve the separation effect.
Preferably, the mass ratio of the large pore size polymer matrix to the silica backbone is 1 (0.5-4), such as 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, or 1:4, etc.
As the preferable technical scheme of the invention, when the mass ratio of the large-aperture polymer matrix to the silicon dioxide skeleton is 1 (0.5-4), the prepared organic-inorganic hybrid microsphere can have excellent alkali resistance and mechanical property, on one hand, if the content of the large-aperture polymer matrix is too low, the addition amount of silicon dioxide is too large, excessive silicon dioxide cannot enter the large-aperture polymer, and excessive silicon dioxide directly enters the final product, so that the alkali resistance of the prepared organic-inorganic hybrid microsphere is reduced; on the other hand, if the content of the large-aperture polymer matrix is too high, the introduced amount of silicon dioxide is low, the framework is insufficiently filled, and the mechanical properties of the prepared organic-inorganic hybrid microsphere are reduced; whichever content is too high, it ultimately affects the separation effect when used as a chromatographic packing.
Preferably, the pore size of the large pore polymer matrix is 100 to 400nm, such as 140nm, 180nm, 220nm, 260nm, 300nm, 340nm or 380nm, and specific point values between the above point values, are for brevity and for brevity the present invention is not exhaustive of the specific point values encompassed by the described ranges.
Preferably, the particle size of the large pore size polymer matrix is 5 to 40 μm, e.g. 10 μm, 15 μm, 20 μm, 25 μm, 30 μm or 35 μm, and specific point values between the above point values, are for the sake of brevity and for the sake of brevity the invention is not exhaustive of the specific point values comprised by the stated range.
Preferably, the silica skeleton has a pore size of 6 to 20nm, for example 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 22nm or 24nm, and specific point values between the above point values, the present invention is not exhaustive of the specific point values included in the range for the sake of brevity and conciseness.
Preferably, the large pore size polymer matrix comprises any one or a combination of at least two of polystyrene-divinylbenzene, polystyrene-pyrrolidone copolymer, polystyrene or polystyrene and derivatives thereof.
The large pore size polymer matrix used in the present invention may be obtained commercially or synthesized by itself.
In a second aspect, the present invention provides a method for preparing the organic-inorganic hybrid microsphere according to the first aspect, the method comprising the steps of:
(1) Performing functionalization treatment on the large-aperture polymer matrix to obtain a functionalized large-aperture polymer matrix;
(2) Mixing the functionalized large-aperture polymer matrix obtained in the step (1), a template agent and a silicon source precursor in a solvent for reaction to obtain an intermediate product;
(3) And (3) removing the template agent in the intermediate product obtained in the step (2) to obtain the organic-inorganic hybrid microsphere.
The invention provides a preparation method of organic-inorganic hybrid microspheres, which comprises the steps of firstly, carrying out surface functionalization treatment on a large-aperture polymer matrix; then, directly reacting the large-aperture polymer matrix subjected to surface functionalization treatment, a silicon source precursor and a template agent in a solvent to obtain an intermediate product; finally removing the template agent in the intermediate product to obtain the organic-inorganic hybrid microsphere.
The organic-inorganic hybrid microsphere provided by the invention can directly synthesize the silica gel structure with ordered pore canals by a chemical method, can precisely regulate and control the pore size according to the size of target molecules, can control the uniformity of pores (the ordered pore canal structure) and can effectively improve the utilization rate of chromatographic packing.
Preferably, the functionalization processing in step (1) includes the steps of:
(A1) Chloromethylation reaction is carried out on the large-aperture polymer matrix to obtain chloromethylation large-aperture polymer matrix;
(A2) And (3) carrying out amination treatment on the chloromethylated large-aperture polymer matrix obtained in the step (1) by adopting amino groups to obtain the functionalized large-aperture polymer matrix.
Preferably, the amine group of step (A2) comprises any one or a combination of at least two of a primary amine, a secondary amine or a tertiary amine.
Preferably, the secondary amine comprises ethylenediamine.
The functionalization processing method provided by the invention specifically comprises the following steps: adding the dried macroporous polymer microspheres into a three-mouth bottle, adding chloroform dispersion microspheres, mechanically stirring at 0 ℃ for 1h, keeping the temperature at 0 ℃, then adding anhydrous tin tetrachloride, stirring for 5min, and dropwise adding chloromethyl ether; after the chloromethyl ether is added, stirring the system for 30min, and then continuing stirring for 3h at room temperature; after the reaction is finished, the product is filtered in vacuum, deionized water, 5% hydrochloric acid, deionized water, tetrahydrofuran, ethanol and acetone are sequentially used (the cleaned macroporous polymer microsphere is dried in vacuum at 60 ℃ for 12 hours to obtain chloromethylated macroporous polymer microsphere, the chloromethylated macroporous polymer microsphere prepared in the process is added into a three-port round bottom flask, ethanol is added into the three-port round bottom flask, ultrasonic dispersion is carried out for 30 minutes, ethylenediamine is added under mechanical stirring at 100rpm, the temperature is raised to 80 ℃, reflux reaction is carried out for 6 hours, then the filtration is carried out, ethanol and distilled water are used for three times alternately, and the ethylenediamine functionalized macroporous polymer microsphere is obtained after drying at 50 ℃ for 12 hours.
Preferably, the mass ratio of the silicon source precursor and the template agent in the step (2) is 1 (1.5-3.5), such as 1:1.7, 1:1.9, 1:2.1, 1:2.3, 1:2.5, 1:2.7, 1:2.9, 1:3.1 or 1:3.3, etc.
Preferably, the templating agent comprises a polyether templating agent.
Preferably, the mass ratio of the functionalized large pore polymer matrix and the silicon source precursor in step (2) is 1 (0.8-6), such as 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or 1:5, etc.
Preferably, the silicon source precursor comprises ethyl orthosilicate and/or ethyl orthosilicate methyl ester.
Preferably, the solvent comprises a combination of deionized water and hydrochloric acid.
Preferably, the mixing in step (2) is performed under stirring, more preferably under stirring at a rotational speed of 400 to 600rpm (e.g., 420rpm, 440rpm, 460rpm, 480rpm, 500rpm, 520rpm, 540rpm, 560rpm, 580rpm, etc.).
Preferably, the mixing time in step (2) is from 0.5 to 24 hours, such as 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours or 20 hours, and the specific point values between the above point values, are limited in space and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values comprised in the range.
Preferably, the temperature of the reaction in step (2) is 90 to 160 ℃, such as 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ or 155 ℃, and the specific values between the above values, are limited in space and for the sake of brevity, the invention is not exhaustive of the specific values comprised in the range.
Preferably, the reaction in step (2) is carried out for a period of time ranging from 20 to 30 hours, for example 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, or 29 hours, and specific point values between the above point values, which are limited in space and for the sake of brevity, the invention is not intended to be exhaustive.
Preferably, the method for removing the template agent in the intermediate product obtained in the step (2) in the step (3) comprises the following steps: washing the intermediate product with deionized water, drying, repeatedly extracting the intermediate product for 6-12 h (such as 7h, 8h, 9h, 10h or 11 h) under the conditions of absolute ethyl alcohol and 50-70 ℃ (such as 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 66 ℃ or 68 ℃) for 2-3 times, and drying to obtain the organic-inorganic hybrid microsphere.
Preferably, the step (3) further comprises a step of functional modification after the template agent is removed.
As a preferable technical scheme, the preparation method comprises the following steps:
(1) Chloromethylation reaction is carried out on the large-aperture polymer matrix to obtain chloromethylation large-aperture polymer matrix; carrying out amination treatment on the obtained chloromethylated macroporous polymer matrix by adopting amino groups to obtain the functionalized macroporous polymer matrix;
(2) Mixing the functionalized large-aperture polymer matrix obtained in the step (1), a template agent, a silicon source precursor and a solvent under the stirring condition of 400-600 rpm for 0.5-2 h and reacting at 90-120 ℃ for 20-30 h to obtain an intermediate product;
(3) Washing the intermediate product obtained in the step (2) by deionized water, drying, extracting the intermediate product in absolute ethyl alcohol at 50-70 ℃ for 6-12 h through Soxhlet extraction, repeatedly extracting for 2-3 times, drying, and functionally modifying to obtain the organic-inorganic hybrid microsphere.
In a third aspect, the present invention provides the use of an organic-inorganic hybrid microsphere according to the first aspect for material separation.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides an organic-inorganic hybrid microsphere with an ordered pore canal structure, which comprises a large-aperture polymer matrix and a silica framework filled in the aperture of the large-aperture polymer matrix; compared with a simple silica gel structure, the silica gel structure has better acid and alkali resistance by adopting a large-aperture polymer matrix to coat the silica framework, can greatly widen the application range of the silica gel structure, remarkably prolongs the service life under acidic and alkaline conditions, and can widen the pH application range to 1-11.
(2) Compared with the common polymer microsphere, the organic-inorganic hybrid microsphere with the ordered pore canal structure has the advantages that the silicon dioxide framework material is adopted to fill the inside of the organic-inorganic hybrid microsphere, so that the organic-inorganic hybrid microsphere has better mechanical strength, compared with the common polymer microsphere, the hybrid structure has the silicon dioxide microsphere support in the framework, the mechanical strength of the hybrid structure is greatly improved, and the mechanical strength of the hybrid microsphere is similar to that of a pure silicon dioxide microsphere through testing, and the hybrid microsphere has good mechanical strength.
(3) The organic-inorganic hybrid microsphere provided by the invention is used for directly synthesizing a silica gel structure with ordered pore canals by a chemical method, is different from a block structure or an integral material, can be directly used as chromatographic packing, can accurately regulate and control the size of the pore diameter according to the size of a target molecule, can control the uniformity of the pore (the ordered pore canal structure), can effectively improve the utilization rate of the chromatographic packing, and has important research value.
Drawings
FIG. 1 is a schematic diagram of the theoretical principle of the organic-inorganic hybrid microsphere provided by the invention, wherein the polymer matrix with 1-large pore diameter and the silica framework with ordered pore canal structure are 2-arranged;
FIG. 2 is an N-type hybrid organic-inorganic microsphere provided in example 1 and ordered mesoporous material provided in comparative example 1 2 Adsorption-desorption isotherms, wherein 1-example 1, 2-comparative example 1;
FIG. 3 is a graph showing theoretical plate number versus time under alkaline conditions for the organic-inorganic hybrid microspheres provided in example 1 and the conventional silica gel provided in comparative example 3, wherein 1-example 1, 2-comparative example 3;
FIG. 4 is a graph showing retention time versus time under alkaline conditions for the organic-inorganic hybrid microspheres provided in example 1 and comparative example 3, wherein 1 is example 1,2 is comparative example 3;
FIG. 5 is a graph of theoretical plate number versus time for the organic-inorganic hybrid microspheres provided in example 1 and comparative example 3 under acidic conditions for conventional silica gel, wherein 1 is from example 1,2 is from comparative example 3;
FIG. 6 is a graph showing retention time versus time under acidic conditions for the organic-inorganic hybrid microspheres provided in example 1 and comparative example 3, wherein 1 is example 1,2 is comparative example 3;
FIG. 7 is a graph showing the pressure change of a chromatographic column in which the organic-inorganic hybrid microspheres provided in example 1 were repeatedly packed 20 times as a chromatographic packing.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
An organic-inorganic hybrid microsphere with an ordered pore structure, comprising a polystyrene-divinylbenzene matrix (available from sodium microtech, inc. In su, uniPS, particle diameter 10 μm, pore diameter 200 nm) and a silica skeleton filled in the pore diameter of the polystyrene-divinylbenzene matrix; the silicon dioxide framework is an ordered mesoporous material, and the aperture is 10nm;
the preparation method comprises the following steps:
(1) 50g of the dried polystyrene-divinylbenzene matrix was added to a 1000mL three-necked flask, 500mL of chloroform dispersion microspheres were added, the system was mechanically stirred at 0deg.C for 1h, and maintained at 0deg.C, then anhydrous tin tetrachloride (SnCl) 4 ) 8.5mL, stirring for 5min, dropwise adding 50mL of chloromethyl ether, and stirring the system for 30min after the chloromethyl ether is completely added; then stirring continuously at room temperature for 3 hours, after the reaction is finished, vacuum filtering the product, and cleaning the product with deionized water (100 mL), 5% hydrochloric acid (100 mL), deionized water (100 mL), tetrahydrofuran (100 mL), ethanol (100 mL) and acetone (100 mL) in sequence, and vacuum drying the product at 60 ℃ for 12 hours after cleaning to obtain chloromethylated polystyrene-divinylbenzene matrix; taking 80g of chloromethylated polystyrene-divinylbenzene matrix prepared by the process, adding 80g of chloromethylated polystyrene-divinylbenzene matrix into a 1000mL three-necked round bottom flask, adding 200mL of ethanol into the flask, performing ultrasonic dispersion for 30min, adding 200mL of ethylenediamine under mechanical stirring at 100rpm, heating to 80 ℃, performing reflux reaction for 6h, performing suction filtration, alternately washing with ethanol and distilled water for three times, and drying at 50 ℃ for 12h to obtain the functionalized polystyrene-divinylbenzene matrix;
(2) 3g of P123 template agent is dissolved in a mixed solution of 90g of hydrochloric acid aqueous solution (2 mol/L) and 22.5g of deionized water, the system temperature is regulated to 40 ℃ after P123 is completely dissolved, 2g of the functionalized polystyrene-divinylbenzene matrix obtained in the step (1) is added, stirring is continued, and then 6.38g of tetraethyl orthosilicate (TEOS) is added, and constant-temperature stirring is kept for 24 hours. Taking out a sample, putting the sample into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 24 hours at 100 ℃ to obtain an intermediate product;
(3) Washing the intermediate product obtained in the step (2) by deionized water, drying, stirring in absolute ethyl alcohol at 60 ℃ for 6 hours, and drying to obtain the organic-inorganic hybrid microsphere.
Example 2
An organic-inorganic hybrid microsphere with an ordered pore structure, comprising a polystyrene-pyrrolidone microsphere polymer (UniPSA, suzhou sodium micro-tech Co., ltd.), a particle size of 15 μm, a pore size of 100nm and a silica skeleton filled in the pore size of the large pore size polymer matrix; the silicon dioxide framework is an ordered mesoporous material, and the aperture is 6nm;
the preparation method comprises the following steps:
(1) Adding 50g of dry polyvinylpyrrolidone-divinylbenzene into a 1000mL three-mouth bottle, adding 500mL of chloroform dispersion microspheres, mechanically stirring the system at 0 ℃ for 1h, keeping the temperature at 0 ℃, then adding 8.5mL of anhydrous tin tetrachloride, stirring for 5min, dropwise adding 50mL of chloromethyl ether, and stirring the system for 30min after the dropwise adding of chloromethyl ether is completed; then stirring continuously at room temperature for 3 hours, after the reaction is finished, vacuum filtering the product, and cleaning the product with deionized water (100 mL), 5% hydrochloric acid (100 mL), deionized water (100 mL), tetrahydrofuran (100 mL), ethanol (100 mL) and acetone (100 mL) in sequence, and vacuum drying the product at 60 ℃ for 12 hours after cleaning to obtain chloromethylated polyvinylpyrrolidone-divinylbenzene microspheres; taking 80g of chloromethylated polyvinylpyrrolidone-divinylbenzene microspheres prepared by the process, adding the 80g into a 1000mL three-necked round bottom flask, adding 200mL of ethanol into the flask, performing ultrasonic dispersion for 30min, adding 200mL of ethylenediamine under mechanical stirring at 100rpm, heating to 80 ℃, performing reflux reaction for 6h, performing suction filtration, alternately washing with ethanol and distilled water for three times, and drying at 50 ℃ for 12h to obtain functionalized polyvinylpyrrolidone-divinylbenzene microspheres;
(2) 2g of P123 template agent is dissolved in a mixed solution of 80g of HCl (2 mol/L) and 12.5g of deionized water, the temperature of the system is regulated to 40 ℃ after P123 is completely dissolved, 2g of the functionalized polyvinylpyrrolidone-divinylbenzene microspheres obtained in the step (1) are added, stirring is continued, 5g of TEOS is added, and constant-temperature stirring is kept for 12h; taking out a sample, putting the sample into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 24 hours at 100 ℃ to obtain an intermediate product;
(3) Washing the intermediate product obtained in the step (2) by deionized water, drying, stirring the intermediate product in absolute ethyl alcohol at 60 ℃ for 6 hours, and drying; 200g of octadecyltrimethoxy silane is dissolved in 800mL of toluene, 120g of dried organic-inorganic hybrid microsphere is added, the mixture is heated to 110 ℃ for refluxing for 24 hours, and after cooling, the mixture is filtered, washed and dried to obtain the C18 functionalized organic-inorganic hybrid microsphere.
Example 3
An organic-inorganic hybrid microsphere having an ordered pore structure, which is different from example 1 only in that the reaction temperature of step (2) is 160℃and other conditions and steps are the same as those of example 1.
The pore diameter of the silica skeleton of the organic-inorganic hybrid microsphere with the ordered pore canal structure obtained in the embodiment is 15.6nm.
Comparative example 1
An ordered mesoporous material with the aperture of 10nm;
the preparation method comprises the following steps: 3g of P123 template agent is dissolved in a mixed solution of 90g of hydrochloric acid aqueous solution (2 mol/L) and 22.5g of deionized water, the system temperature is regulated to 40 ℃ after P123 is completely dissolved, 2g of the functionalized polystyrene-divinylbenzene matrix obtained in the step (1) is added, stirring is continued, and then 6.38g of tetraethyl orthosilicate (TEOS) is added, and constant-temperature stirring is kept for 24 hours. And then taking out the sample, putting the sample into a reaction kettle with a polytetrafluoroethylene lining, and aging the sample at 100 ℃ for 24 hours to obtain the ordered mesoporous material SBA-15.
Specific procedures of this comparative example can be referred to in the literature: zhao D Y, feng J L, huo Q S, et al, triblock copolymer syntheses of mesoporous silica with periodic 50to 300angstrom pores[J, science,1998,279 (5350):548-552.
Comparative example 2
An organic-inorganic hybrid microsphere comprising a polystyrene-divinylbenzene matrix (available from UniPS, molecular weight 10 μm, pore size 200nm, available from nanotechnology, inc.) and a silica skeleton filled in the pore size of the polystyrene-divinylbenzene matrix;
the preparation method is different from example 1 only in that no template agent is added in step (2), other conditions and steps are the same as those in example 1, and the obtained organic-inorganic hybrid microsphere basically has no pore structure, because no P123 template agent is added, and no pore can be formed.
Comparative example 3
A common silica gel is available from Soy micro technology Co., ltd., product model UniSil10-100 (substrate: high purity silica, particle size 10 μm, pore size 10 nm).
Performance test:
(1)N 2 adsorption-desorption isotherms:
vacuum activating the organic-inorganic hybrid microsphere obtained in example 1 and the ordered mesoporous material obtained in comparative example 1 for 3h at a certain temperature on a Belsorp II specific surface and pore analyzer, and carrying out N at-196 DEG C 2 Adsorption-desorption experiments. The Brunauer-Emmett-Teller (BET) specific surface of the sample was measured in terms of specific pressure (p/p 0 ) Adsorption data in the range of 0.04 to 0.20.
The organic-inorganic hybrid microspheres obtained in example 1 and the comparative examples gave N as the chromatographic packing material 2 The adsorption-desorption isotherms are shown in fig. 2, wherein 1 represents example 1, and 2 represents comparative example 1; as can be seen from FIG. 2, the organic-inorganic hybrid microspheres obtained in example 1 and the N of the ordered mesoporous material obtained in comparative example 1 2 The adsorption-desorption isotherms have similar IV-type isotherms and H1-type hysteresis loops, which indicates that the mesoporous structure of the organic-inorganic hybrid microspheres obtained in example 1 is well maintained.
(2) Alkali resistance test:
test conditions: alkaline washing conditions: meOH/NaOH (ph=13) =40:60; mobile phase: ACN/H 2 O=60:40; column temperature: 35 ℃; sample: toluene.
The organic-inorganic hybrid microspheres obtained in example 1 and the silica gel of comparative example 3 were tested according to the above test method, and theoretical plate number-time spectra of example 1 obtained by the test under alkaline conditions are shown in fig. 3, wherein 1 represents example 1 and 2 represents comparative example 3; as can be seen from FIG. 3, the theoretical plate number of the organic-inorganic hybrid microspheres obtained in example 1 can still reach 11000 or more at 100h, while the theoretical plate number of the silica gel obtained in comparative example 3 is reduced to 3000 within 20h, which proves that the organic-inorganic hybrid microspheres provided in example 1 have better separation efficiency and alkali resistance as chromatographic packing.
The retention time-time spectra of the organic-inorganic hybrid microspheres obtained in example 1 and the silica gel of comparative example 3, in which 1 represents example 1 and 2 represents comparative example 3, were tested according to the above test method, are shown in fig. 4; as can be seen from fig. 3, the retention time of the organic-inorganic hybrid microspheres obtained in example 1 as a chromatographic packing was reduced little within 100h, while the retention time of the silica gel obtained in comparative example 3 as a chromatographic packing was reduced to about 2h within 20h, demonstrating that the alkali resistance of the organic-inorganic hybrid microspheres provided in example 1 as a chromatographic packing was better.
(3) Acid resistance test:
test conditions: acid washing conditions: meOH/HCl (ph=1.0) =40:60; mobile phase: ACN/H 2 O=60:40; column temperature: 35 ℃; sample: toluene.
The organic-inorganic hybrid microspheres obtained in example 1 and the silica gel obtained in comparative example 3 were tested according to the above test method, and theoretical plate number-time spectra of the test obtained in example 1 and comparative example 3 under acidic conditions are shown in fig. 5, wherein 1 represents example 1 and 2 represents comparative example 3; as can be seen from FIG. 5, the theoretical plate number of the organic-inorganic hybrid microspheres obtained in example 1 is not significantly reduced in 100 hours, while the theoretical plate number of the silica gel obtained in comparative example 3 is significantly reduced in 20 hours, which proves that the organic-inorganic hybrid microspheres provided in example 1 have better separation efficiency and acid resistance as chromatographic packing.
The retention time-time spectra of example 1 and comparative example 3 obtained by the test under acidic conditions are shown in fig. 6, wherein 1 represents example 1 and 2 represents comparative example 3; as can be seen from fig. 6, the retention time of the organic-inorganic hybrid microspheres obtained in example 1 as a chromatographic packing was reduced little within 100 hours, while the retention time of the silica gel obtained in comparative example 3 as a chromatographic packing was reduced much within 100 hours, demonstrating that the organic-inorganic hybrid microspheres provided in example 1 were better acid resistance as a chromatographic packing.
(3) Mechanical strength:
the testing method comprises the following steps: the organic-inorganic hybrid filler obtained in example 1 was repeatedly packed 20 times to obtain a column pressure change of 20 times for the repeated packing.
The pressure change chart of the chromatographic column of the organic-inorganic hybrid microsphere obtained in example 1 as the chromatographic packing material repeatedly packed 20 times is shown in fig. 7, and it can be seen from fig. 7 that the pressure change of the chromatographic column of the organic-inorganic hybrid microsphere obtained in example 1 as the chromatographic packing material repeatedly packed 20 times is small, which indicates that the organic-inorganic hybrid microsphere obtained in example has better mechanical strength.
The applicant states that the present invention is illustrated by the above examples as an organic-inorganic hybrid microsphere having an ordered pore structure, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must be carried out by relying on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (22)
1. An organic-inorganic hybrid microsphere having an ordered pore structure as a chromatographic packing, characterized in that the organic-inorganic hybrid microsphere comprises a large pore polymer matrix and a silica skeleton filled in the pore diameter of the large pore polymer matrix;
the silicon dioxide framework is an ordered mesoporous material;
the mass ratio of the large-aperture polymer matrix to the silicon dioxide skeleton is 1 (0.5-4);
the large pore size polymer matrix comprises any one or a combination of at least two of polystyrene-divinylbenzene, polystyrene-pyrrolidone copolymer or polystyrene.
2. The organic-inorganic hybrid microsphere according to claim 1, wherein the pore size of the large pore size polymer matrix is 100-400 nm.
3. The organic-inorganic hybrid microsphere according to claim 1, wherein the particle size of the large pore size polymer matrix is 5-40 μm.
4. The organic-inorganic hybrid microsphere according to claim 1, wherein the pore size of the silica skeleton is 6-20 nm.
5. A method for preparing the organic-inorganic hybrid microsphere according to any one of claims 1 to 4, comprising the steps of:
(1) Performing functionalization treatment on the large-aperture polymer matrix to obtain a functionalized large-aperture polymer matrix;
(2) Mixing the functionalized large-aperture polymer matrix obtained in the step (1), a template agent and a silicon source precursor in a solvent for reaction to obtain an intermediate product;
(3) And (3) removing the template agent in the intermediate product obtained in the step (2) to obtain the organic-inorganic hybrid microsphere.
6. The method of claim 5, wherein the functionalization process of step (1) comprises the steps of:
(A1) Chloromethylation reaction is carried out on the large-aperture polymer matrix to obtain chloromethylation large-aperture polymer matrix;
(A2) And (3) carrying out amination treatment on the chloromethylated large-aperture polymer matrix obtained in the step (1) by adopting amino groups to obtain the functionalized large-aperture polymer matrix.
7. The method of claim 6, wherein the amine group of step (A2) comprises any one or a combination of at least two of a primary amine, a secondary amine, or a tertiary amine.
8. The method of claim 7, wherein the secondary amine comprises ethylenediamine.
9. The preparation method of claim 5, wherein the mass ratio of the silicon source precursor and the template agent in the step (2) is 1 (1.5-3.5).
10. The method of claim 9, wherein the templating agent comprises a polyether templating agent.
11. The preparation method of claim 5, wherein the mass ratio of the functionalized large-pore polymer matrix to the silicon source precursor in the step (2) is 1 (0.8-6).
12. The method of claim 11, wherein the silicon source precursor comprises ethyl orthosilicate and/or methyl orthosilicate.
13. The method of claim 5, wherein the solvent comprises deionized water and hydrochloric acid.
14. The method according to claim 5, wherein the mixing in the step (2) is performed under stirring.
15. The method according to claim 14, wherein the mixing in the step (2) is performed under stirring at a rotation speed of 400 to 600 rpm.
16. The method according to claim 5, wherein the mixing time in the step (2) is 0.5 to 24 hours.
17. The method according to claim 5, wherein the reaction temperature in step (2) is 90 to 160 ℃.
18. The method according to claim 5, wherein the reaction time in the step (2) is 20 to 30 hours.
19. The method according to claim 5, wherein the step (3) of removing the template agent from the intermediate product obtained in the step (2) comprises: washing the intermediate product with deionized water, drying, extracting the intermediate product by Soxhlet at 50-70 ℃ for 6-12 hours, repeatedly extracting for 2-3 times, and drying to obtain the organic-inorganic hybrid microsphere.
20. The method according to claim 5, wherein the step (3) further comprises a step of functional modification after the template is removed.
21. The preparation method according to claim 5, characterized in that the preparation method comprises the steps of:
(1) Chloromethylation reaction is carried out on the large-aperture polymer matrix to obtain chloromethylation large-aperture polymer matrix; carrying out amination treatment on the obtained chloromethylated macroporous polymer matrix by adopting amino groups to obtain the functionalized macroporous polymer matrix;
(2) Mixing the functionalized large-aperture polymer matrix, the template agent, the silicon source precursor and the solvent obtained in the step (1) for 0.5-24 hours under the stirring condition of the rotating speed of 400-600 rpm, and carrying out hydrothermal reaction for 20-30 hours at the temperature of 90-120 ℃ to obtain an intermediate product;
(3) Washing the intermediate product obtained in the step (2) with deionized water, drying, extracting the intermediate product in absolute ethyl alcohol at 50-70 ℃ for 6-12 h through Soxhlet extraction, repeatedly extracting for 2-3 times, and drying to obtain the organic-inorganic hybrid microsphere.
22. Use of the organic-inorganic hybrid microsphere according to any one of claims 1 to 4 in material separation.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070152A (en) * | 2010-12-01 | 2011-05-25 | 苏州纳微生物科技有限公司 | Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof |
| CN102643398A (en) * | 2012-05-10 | 2012-08-22 | 河北工业大学 | Method for preparing monodisperse three-dimensional ordered macroporous (3DOM) organic/inorganic hybrid material |
| CN102942921A (en) * | 2012-11-30 | 2013-02-27 | 上海理工大学 | Preparation method of polymer functional rare-earth/organic/inorganic mesoporous fluorescent material |
| CN104437437A (en) * | 2014-12-14 | 2015-03-25 | 苏州大学 | Hyperbranched polymer functionalized mesoporous material and application thereof |
| CN105329904A (en) * | 2015-11-29 | 2016-02-17 | 北京工业大学 | Preparation method of organic-inorganic hybrid silicon oxide microsphere bonded by octadecyl and bridged by ethylidene through HPLC (High Performance Liquid Chromatography) |
| WO2016026464A1 (en) * | 2014-08-22 | 2016-02-25 | 中国科学院化学研究所 | Organic/inorganic hybrid janus particle and preparation method and modification method, and modified janus particle and use thereof |
-
2021
- 2021-03-15 CN CN202110277665.7A patent/CN113019343B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070152A (en) * | 2010-12-01 | 2011-05-25 | 苏州纳微生物科技有限公司 | Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof |
| CN102643398A (en) * | 2012-05-10 | 2012-08-22 | 河北工业大学 | Method for preparing monodisperse three-dimensional ordered macroporous (3DOM) organic/inorganic hybrid material |
| CN102942921A (en) * | 2012-11-30 | 2013-02-27 | 上海理工大学 | Preparation method of polymer functional rare-earth/organic/inorganic mesoporous fluorescent material |
| WO2016026464A1 (en) * | 2014-08-22 | 2016-02-25 | 中国科学院化学研究所 | Organic/inorganic hybrid janus particle and preparation method and modification method, and modified janus particle and use thereof |
| CN104437437A (en) * | 2014-12-14 | 2015-03-25 | 苏州大学 | Hyperbranched polymer functionalized mesoporous material and application thereof |
| CN105329904A (en) * | 2015-11-29 | 2016-02-17 | 北京工业大学 | Preparation method of organic-inorganic hybrid silicon oxide microsphere bonded by octadecyl and bridged by ethylidene through HPLC (High Performance Liquid Chromatography) |
Non-Patent Citations (4)
| Title |
|---|
| "Controlled Polymerization in Mesoporous Silica toward the Design of Organic-Inorganic Composite Nanoporous Materials";Minkee Choi等;《JACS》;20050119;第127卷;第1924-1932页 * |
| "Studies on a poly(styrene-divinylbenzene)-encapsulated sub-micrometer sized organic–inorganic hybrid silica packing, its synthesis, some of its characteristics and applications";Y.S. Li等;《Journal of Chromatography A》;20030930;第1021卷;第183-189页 * |
| "一种制备聚苯乙烯/二氧化硅纳米杂化空球的新方法";冷文光等;《2010中国材料研讨会论文集》;20121216;第1-6页 * |
| "聚苯乙烯-SiO2杂化材料的合成与表征";裘小宁;《涂料工业》;20090609;第39卷(第5期);第31-34页 * |
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