CN112850724B - Preparation method of monodisperse pore-size-adjustable full-porous silica chromatographic microspheres - Google Patents
Preparation method of monodisperse pore-size-adjustable full-porous silica chromatographic microspheres Download PDFInfo
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Abstract
A preparation method of monodisperse pore-size-adjustable full-porous silica chromatographic microspheres relates to a preparation process of silica gel fixing phase in chromatographic separation. The method separates the two aspects of the appearance and the particle size of the microsphere and the control of the pore size and the pore size distribution, regulates and controls one by one, overcomes the defects of seeking a one-pot method in the traditional mode and simultaneously solves the two problems, and provides a preparation method of the monodisperse pore size adjustable full-porous silica chromatographic microsphere which is full-porous, adjustable in pore size and free of metal. The method mainly comprises the steps of template-guided seed synthesis, seed growth, pore expansion of a template agent, calcination and solidification, pore expansion of alkali liquor and the like. The prepared silicon dioxide microsphere has excellent sphericity and monodispersity, controllable particle size, simple pore size regulating method, narrow pore size distribution range, no metal element residue, expansibility and replicability. As the used reagents do not contain inorganic salt, the purity of the microsphere is high, and the method is particularly suitable for high performance liquid chromatography separation and analysis.
Description
Technical Field
The invention relates to a preparation process of silica gel fixing phase in chromatographic separation, in particular to a preparation method of monodisperse pore-size-adjustable full-porous silica chromatographic microspheres.
Background
As an important separation and analysis tool, the chromatography technology has been widely applied to various fields such as food, biology, medicine, and environment, and is one of the indispensable tools. And the chromatographic separation is shortened from the first one or more hours to several minutes or even one minute nowadays, the separation time is remarkably shortened, and the separation efficiency is rapidly improved, so that the chromatographic instrument technology is benefited from development, and the chromatographic packing is mainly promoted by the development of chromatographic packing.
An ideal chromatographic packing generally meets the following requirements: 1. the filler is spherical and has uniform particle size distribution; 2. the filler has larger specific surface area and pore volume, larger mesoporous diameter and narrower pore diameter distribution; 3. the filler has better mechanical strength and pressure resistance; 4. enough modification sites on the surface of the filler are available for chemical modification bonding; 5. the filler matrix has no interaction with the separating substance and the eluent as far as possible, and has good chemical stability under the condition of the eluent. Silica is the most widely used stationary phase material due to its advantages such as excellent chemical inertness, high mechanical strength and many modifiable sites.
However, the silica gel filler used at present has wide particle size distribution due to the characteristics of sol-gel, and even if a time-consuming and labor-consuming screening technology is adopted in the later stage, a monodisperse spherical silica gel stationary phase is difficult to obtain; secondly, the size of the pore channel is difficult to control, and the required pore channel size is difficult to control flexibly; the filler prepared in large scale usually adopts silicate as a silicon source, so that the filler is inevitably carried with metal ions, and the final separation effect is influenced. The occurrence of these problems limits the further development of chromatography packing and ultimately limits the separation performance of chromatography.
Disclosure of Invention
The invention aims to separate the two aspects of the appearance and the particle size of the microsphere and the control of the pore size and the pore size distribution, regulate and control one by one, get rid of the defects of seeking a one-pot method in the traditional mode and simultaneously solving the two problems, and provide a preparation method of a monodisperse pore size-adjustable full-porous silica chromatographic microsphere which is full-porous, adjustable in pore size and free of metal.
The invention comprises the following steps:
1) Adding a template agent into a solvent system of water and ethanol, adding ammonia water, and uniformly stirring at a high stirring speed to form a template agent solution; dispersing tetraethoxysilane in ethanol, uniformly mixing to form a TEOS solution, injecting the TEOS solution into the template solution once again, stirring for reaction, washing with water, washing with alcohol and drying to obtain silicon dioxide seed microspheres with uniform particle size distribution;
2) Adding ammonia water, a template agent and the silicon dioxide seed microspheres prepared in the step 1) into a solvent of ethanol and water, stirring and uniformly mixing at a high speed to form a seed-template agent solution, slowly adding a TEOS solution, stirring and reacting, washing with water, washing with alcohol, and drying to obtain microspheres with a target size;
3) Placing the microspheres prepared in the step 2) into a hydrothermal reaction kettle, adding a hydrochloric acid solution, carrying out hydrothermal reaming at a high temperature, filtering the reaction solution after the reaction is finished, washing the filter cake with deionized water until the filtrate is neutral, and drying;
4) Placing the microspheres dried in the step 3) in a muffle furnace, removing the template agent by temperature programming and calcining in a certain atmosphere, crosslinking and curing the microspheres, improving the crosslinking degree and mechanical strength of the microspheres, and then naturally cooling to room temperature;
5) And (3) placing the microspheres calcined in the step 4) in a hydrothermal reaction kettle, adding ammonia water, carrying out alkali liquor reaming, filtering the reaction solution after the reaction is finished to obtain target microspheres, repeatedly cleaning the target microspheres with deionized water until the cleaning solution is neutral, and drying to obtain the monodisperse pore-size-adjustable full-porous silica chromatographic microspheres.
In the step 1), the volume ratio of ethanol to water in the solvent system of water and ethanol can be (1-4): 1, the ammonia water can be 25-28% of commercially available ammonia water, and the particle size of the generated seed microspheres can be controlled by controlling the amount of the added ammonia water and adjusting the ratio of ethanol to water; the volume ratio of the TEOS solution to the seed-template agent solution is 1: 1-2, wherein the TEOS solvent is ethanol; the template agent can adopt dodecylamine, dodecylamine polyoxyethylene ether, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer or polyethylene glycol dodecyl ether, wherein the mass ratio of the dodecylamine to the dodecylamine polyoxyethylene ether can be 1: 1; the stirring reaction can be carried out at the speed of 1000-1500 rpm for 1-2 min, the rotating speed is reduced to 360-400 rpm, and the stirring reaction is carried out at room temperature for 1.5-2.5 h.
In the step 2), the TEOS concentration in the TEOS solution can be 0.03-0.24 mol/L, the concentration of ammonia water can be 1-4 mol/L, and the volume ratio of ethanol to water is (1-4): 1; the stirring speed of the high-speed stirring can be 1500-1800 rpm; the time for slowly adding the TEOS solution can be 5-6 h.
In the step 3), the concentration of the hydrochloric acid can be 1M-4M HCl; the temperature of the hydrothermal reaming can be 100-130 ℃, the time of the hydrothermal reaming can be 6-96 h, the higher the temperature is, the larger the aperture is in the same time.
In the step 4), the temperature can be raised to 500-700 ℃ at the rate of 1 ℃/min through temperature programming and calcination in a certain atmosphere at the constant temperature of 500-700 ℃ for 5-7 h, wherein the atmosphere is air or oxygen.
In the step 5), the concentration of the ammonia water can be 0.01-0.1M; the temperature of the alkali liquor hole expanding can be 90-120 ℃, and the time of the alkali liquor hole expanding can be 6-72 hours; the concentration of the alkali liquor is increased, the pore diameter is larger under the same temperature and time, other conditions are kept unchanged, the pore diameter can be enlarged by increasing the hydrothermal temperature, the hydrothermal treatment time is correspondingly prolonged, and the pore channel size is enlarged; however, excessive hole expansion causes a decrease in the mechanical strength of the microspheres, and may lead to breakage of the microspheres.
The invention aims to separate the control of the appearance and the particle size of the microsphere and the control of the aperture size and the aperture distribution, regulate and control the microspheres one by one, and get rid of the idea that the traditional mode seeks a one-pot method to solve the two problems at the same time. Therefore, the method is more expandable and reproducible for preparing other silica chromatographic microspheres with uniform particle size and target pore size. The silicon dioxide microspheres prepared by the invention have excellent sphericity and monodispersity, controllable particle size, simple method for regulating and controlling pore size and narrow pore size distribution range. As the used reagents do not contain inorganic salt, no metal element impurity is doped in the microspheres, and the microspheres have high purity and are particularly suitable for high performance liquid chromatography separation and analysis.
Drawings
FIG. 1 is a schematic view of a preparation process of an embodiment of the present invention.
Fig. 2 is an SEM image of the seed microspheres obtained in example 1.
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
Referring to fig. 1, an embodiment of the present invention includes the steps of:
1) Template-guided seed synthesis: adding a template agent into a solvent system of water and ethanol, then adding ammonia water, and uniformly stirring at a high stirring speed to form a template agent solution; dispersing tetraethoxysilane in ethanol, uniformly mixing to form a TEOS solution, injecting the TEOS solution into the template agent solution once again, stirring for reaction, washing with water, washing with alcohol and drying to obtain silicon dioxide seed microspheres with uniform particle size distribution; the volume ratio of ethanol to water in the solvent system of water and ethanol can be (1-4): 1, the ammonia water can be 25-28% of commercial ammonia water, and the particle size of the generated seed microspheres can be controlled by controlling the amount of the added ammonia water and adjusting the ratio of ethanol to water; the volume ratio of the TEOS solution to the seed-template agent solution is 1: 1-2, wherein the TEOS solvent is ethanol; the template agent can adopt dodecylamine, dodecylamine polyoxyethylene ether, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer or polyethylene glycol dodecyl ether, wherein the mass ratio of the dodecylamine to the dodecylamine polyoxyethylene ether can be 1: 1; the stirring reaction can be carried out at the speed of 1000-1500 rpm for 1-2 min, the rotating speed is reduced to 360-400 rpm, and the stirring reaction is carried out for 2h at room temperature.
2) Seed growth: adding the silicon dioxide seed microspheres prepared in the step 1) into a solvent of ethanol and water, adding a certain amount of dodecylamine, dodecylamine polyoxyethylene ether and ammonia water, adjusting the rotation speed to 1500rpm, and stirring the reaction substances uniformly to obtain a seed-template agent solution; dispersing a certain amount of tetraethoxysilane solvent in an ethanol solution, slowly injecting the mixture into a seed-template agent solution after uniformly mixing, and continuously maintaining the rotating speed for reaction for 2 hours at room temperature after the injection is finished; after the reaction is finished, obtaining the silicon dioxide microspheres with uniform particle size through water system, alcohol washing and drying; repeating the steps until microspheres with target particle sizes are obtained; the TEOS concentration in the TEOS solution can be 0.03-0.24 mol/L, the concentration of ammonia water can be 1-4 mol/L, and the volume ratio of ethanol to water is (1-4): 1; the stirring speed of the high-speed stirring can be 1500rpm; the time for slowly adding the TEOS solution can be 5-6 h.
3) Reaming by using a template agent: placing the microspheres prepared in the step 2) into a hydrothermal reaction kettle, adding a hydrochloric acid solution with a certain concentration, carrying out hydrothermal reaming at a high temperature, filtering the reaction solution after the reaction is finished, washing the filter cake with deionized water until the filtrate is neutral, and drying; the concentration of the hydrochloric acid can be 1M-4M HCl; the temperature of the hydrothermal reaming can be 100-130 ℃, the time of the hydrothermal reaming can be 6-96 h, the higher the temperature is, the larger the aperture is in the same time.
4) Calcining and curing: placing the dried microspheres in the step 3) in a muffle furnace, raising the temperature to 600 ℃ at a slow heating rate, calcining at the constant temperature of 600 ℃ for 6 hours, removing the template agent, further improving the crosslinking degree and the mechanical strength of the microspheres, and naturally cooling to room temperature; the temperature can be raised to 600 ℃ at the rate of 1 ℃/min through temperature programming calcination in a certain atmosphere, and the constant-temperature calcination is carried out for 6h at the temperature of 600 ℃, wherein the atmosphere is air or oxygen.
5) Expanding pores with alkali liquor: and (3) placing the calcined microspheres in a hydrothermal reaction kettle, adding ammonia water with a certain concentration, carrying out high-temperature hydrothermal reaming, after the reaction is finished, filtering the reaction solution to obtain target microspheres, repeatedly cleaning the target microspheres with deionized water until the cleaning solution is neutral, and drying to obtain the final monodisperse pore-size-adjustable full-porous silica chromatographic microspheres. The concentration of the ammonia water can be 0.01-0.1M; the temperature of the alkali liquor reaming can be 90-120 ℃, and the time of the alkali liquor reaming can be 6-72 hours; the concentration of the alkali liquor is increased, the pore diameter is larger under the same temperature and time, other conditions are kept unchanged, the pore diameter can be enlarged by increasing the hydrothermal temperature, the hydrothermal treatment time is correspondingly prolonged, and the pore channel size is enlarged along with the increase; however, excessive pore expansion causes a decrease in the mechanical strength of the microspheres, and may cause breakage of the microspheres.
Specific examples are given below.
Example 1:
in a 25mL single-neck flask, 1.8mL of ammonia water, 3.25mL of EtOH,4.95mL of water, 0.153g of dodecylamine and 0.153g of dodecylamine polyoxyethylene ether were added, and after stirring and mixing at a stirring speed of 1100rpm, 0.9mL of TEOS and 9.1mL of EtOH which had been previously mixed were added, and the mixture was quickly poured into a reaction flask. Stirring and reacting for 1min at the stirring speed of 1100rpm, then regulating the rotating speed to 360rpm, and stirring and reacting for 2h at room temperature; filtering the reaction solution, washing with water, washing with alcohol, drying, taking 50mg of cleaned seed microspheres, adding the seeds microspheres into 330mL of the reaction solution, wherein the concentration of ammonia water is 3.5mol/L, the concentration of water is 10mol/L, the balance is ethanol, adding 3.212g of dodecylamine and 3.212g of dodecylamine polyoxyethylene ether into the reaction solution, uniformly mixing the reactants at the stirring speed of 1500rpm, slowly injecting 100mL of 0.03mol/L TEOS solution (the solvent is ethanol) into the reaction system, lasting for 450min, after the injection is finished, keeping the rotation speed at room temperature, and reacting for 2h. And filtering the reaction solution, washing with water, washing with alcohol, drying, transferring to a hydrothermal reaction kettle, adding 1M hydrochloric acid as a solvent, and carrying out hydrothermal reaction for 48 hours at 120 ℃. And after the reaction is finished, filtering to obtain microspheres, washing with deionized water, drying, transferring to a muffle furnace, calcining for 6 hours at 600 ℃, then placing the microspheres in a hydrothermal reaction kettle, adding 0.01M ammonia water, carrying out hydrothermal reaction for 48 hours at 120 ℃, after the reaction is finished, washing with deionized water, and drying. Finally obtaining the uniform silicon dioxide microspheres with the particle size of 650nm and the pore diameter of 12.5 nm.
SEM image of the obtained seed microsphere in example 1 is shown in fig. 2.
Example 2:
1.8mL of ammonia, 1.00mL of EtOH,7.10mL of water, 0.153g of dodecylamine and 0.153g of dodecylamine polyoxyethylene ether are added to a 25mL single-neck flask, and after stirring and mixing at a stirring speed of 1100rpm, 0.9mL of TEOS and 9.1mL of EtOH which are mixed in advance are added and quickly poured into a reaction flask. Stirring and reacting for 1min at the stirring speed of 1100rpm, reducing the rotation speed to 360rpm, stirring and reacting for 2h at room temperature, filtering the reaction solution, washing with water, washing with alcohol, drying, adding 50mg of cleaned seed microspheres into 330mL of the reaction solution, wherein the concentration of ammonia water is 3.5mol/L, the concentration of water is 10mol/L, and the balance is ethanol, adding 3.212g of dodecylamine and 3.212g of dodecylamine polyoxyethylene ether, mixing the reactants uniformly at the stirring speed of 1500rpm, slowly injecting 100mL of 0.03mol/L TEOS solution (the solvent is ethanol) into the reaction system for 450min, after the injection is finished, keeping the rotation speed at room temperature and reacting for 2h. And filtering the reaction solution, washing with water, washing with alcohol, drying, taking the grown silicon dioxide microspheres, repeating the step of seed ball growth again, transferring to a hydrothermal reaction kettle, adding 1M hydrochloric acid as a solvent, and carrying out hydrothermal reaction at 120 ℃ for 48 hours. After the reaction is finished, washing with deionized water, drying, transferring to a muffle furnace, calcining for 6h at 600 ℃ to obtain microspheres, putting the microspheres into a hydrothermal reaction kettle again, adding 0.01M ammonia water, carrying out hydrothermal reaction for 48h at 120 ℃, after the reaction is finished, washing with deionized water, and drying. Finally obtaining the uniform silicon dioxide microspheres with the particle size of 1.65 mu m and the pore diameter of 12.5 nm.
Example 3
Similar to example 1, except that in the template-directed seed growth step, the volume ratio of ethanol/water in a solvent system of water and ethanol is 1: 1, and a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is used as the template agent. In the seed growing step, the TEOS concentration in the TEOS solution is 0.03mol/L, and the ammonia water concentration is 1mol/L; the stirring speed of the high-speed stirring was 1800rpm. The temperature of the hydrothermal hole expanding is 100 ℃, and the time of the hydrothermal hole expanding can be 96h. The temperature of constant temperature calcination is 500 ℃ for 7h, and the atmosphere is oxygen. The temperature of the alkali liquor for reaming is 90 ℃, and the time of the alkali liquor for reaming can be 60 hours.
Example 4
Similar to example 1, except that in the template-directed seed growth step, the volume ratio of ethanol/water in a solvent system of water and ethanol is 4: 1, and a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is used as the template agent. In the seed growth step, the TEOS concentration in the TEOS solution is 0.24mol/L, and the concentration of the ammonia water is 2mol/L; the stirring speed of the high-speed stirring was 1600rpm. The temperature of the hydrothermal hole expanding is 130 ℃, and the time of the hydrothermal hole expanding can be 6 hours. The temperature of constant temperature calcination is 650 ℃, the time is 6h, and the atmosphere is air. The temperature of the alkali liquor hole expanding is 120 ℃, and the time of the alkali liquor hole expanding can be 25 hours.
Example 5
Similar to example 2, except that in the template-directed seed growth step, the volume ratio of ethanol to water in a solvent system of water and ethanol is 3: 1, and polyethylene glycol dodecyl ether is used as a template agent. In the seed growing step, the TEOS concentration in the TEOS solution is 0.18mol/L, and the ammonia water concentration is 3mol/L; the stirring speed of the high-speed stirring was 1700rpm. The temperature of the hydrothermal hole expanding is 120 ℃, and the time of the hydrothermal hole expanding can be 50h. The temperature of constant temperature calcination is 700 ℃, the time is 6h, the temperature of alkali liquor reaming is 110 ℃, and the time of alkali liquor reaming can be 12h.
Claims (6)
1. A preparation method of monodisperse pore-size-adjustable full-porous silica chromatographic microspheres is characterized by comprising the following steps:
1) Adding a template agent into a solvent system of water and ethanol, adding ammonia water, and uniformly stirring at a high stirring speed to form a template agent solution; dispersing tetraethoxysilane in ethanol, uniformly mixing to form a TEOS solution, injecting the TEOS solution into the template solution once again, stirring for reaction, washing with water, washing with alcohol and drying to obtain silicon dioxide seed microspheres with uniform particle size distribution; the volume ratio of ethanol to water in the solvent system of water and ethanol is (1-4): 1, and the ammonia water is 25-28% of commercially available ammonia water; the template agent adopts dodecylamine, dodecylamine polyoxyethylene ether, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer or polyethylene glycol dodecyl ether, wherein the mass ratio of the dodecylamine to the dodecylamine polyoxyethylene ether is 1: 1; the volume ratio of the TEOS solution to the template solution is 1: 1-2, wherein the TEOS solvent is ethanol;
2) Adding ammonia water, a template and the silicon dioxide seed microspheres prepared in the step 1) into a solvent of ethanol and water, stirring and uniformly mixing at a high speed to form a seed-template solution, slowly adding a TEOS solution, stirring and reacting, and then washing, washing with alcohol and drying to obtain microspheres with a target size; the TEOS solution contains 0.03-0.24 mol/L TEOS, 1-4 mol/L ammonia water and ethanol/water in a volume ratio of (1-4): 1;
3) Placing the microspheres prepared in the step 2) into a hydrothermal reaction kettle, adding a hydrochloric acid solution, carrying out hydrothermal reaming at high temperature, filtering the reaction solution after the reaction is finished, washing the filter cake with deionized water until the filtrate is neutral, and drying;
4) Placing the microspheres dried in the step 3) in a muffle furnace, removing the template agent by temperature programming and calcining in a certain atmosphere, crosslinking and curing the microspheres, improving the crosslinking degree and mechanical strength of the microspheres, and then naturally cooling to room temperature;
5) And (3) placing the microspheres calcined in the step 4) in a hydrothermal reaction kettle, adding ammonia water, carrying out alkali liquor reaming, filtering the reaction solution after the reaction is finished to obtain target microspheres, repeatedly cleaning the target microspheres with deionized water until the cleaning solution is neutral, and drying to obtain the monodisperse pore-size-adjustable full-porous silica chromatographic microspheres.
2. The method for preparing monodisperse pore-size-adjustable porous silica chromatographic microspheres according to claim 1, wherein in step 1), after stirring at a speed of 1000-1500 rpm for 1-2 min, the rotation speed is reduced to 360-400 rpm, and stirring is performed at room temperature for 1.5-2.5 h.
3. The method for preparing monodisperse pore-size-adjustable full-porous silica chromatographic microspheres according to claim 1, wherein in the step 2), the stirring speed of the high-speed stirring is 1500-1800 rpm; the time for slowly adding the TEOS solution is 5-6 h.
4. The method for preparing monodisperse pore-size-adjustable full-porous silica chromatographic microspheres according to claim 1, wherein in step 3), the concentration of the hydrochloric acid is 1M to 4M HCl; the temperature of the hydrothermal reaming is 100-130 ℃, the time of the hydrothermal reaming is 6-96 h, the higher the temperature is, the larger the aperture is in the same time.
5. The method for preparing monodisperse pore-size-adjustable full-porous silica chromatographic microspheres according to claim 1, wherein in the step 4), the calcination under programmed temperature is performed at a temperature rise rate of 1 ℃/min to 500-700 ℃ for 5-7 h at a constant temperature of 500-700 ℃, and the atmosphere is air or oxygen.
6. The method for preparing monodisperse pore-size-adjustable full-porous silica chromatographic microspheres according to claim 1, wherein in the step 5), the concentration of the ammonia water is 0.01-0.1M; the temperature of the alkali liquor reaming is 90-120 ℃, and the time of the alkali liquor reaming is 6-72 hours.
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