CN107413395B - Agglomeration type high-hydrophilicity strong anion exchanger, preparation method and application thereof in liquid chromatography column packing - Google Patents
Agglomeration type high-hydrophilicity strong anion exchanger, preparation method and application thereof in liquid chromatography column packing Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of liquid chromatographic column packing, and particularly relates to an agglomeration type high-hydrophilicity strong anion exchanger, a preparation method and application thereof in liquid chromatographic column packing. The agglomeration type high-hydrophilicity strong anion exchanger is prepared by agglomerating sulfonated polymer microspheres by quaternized polyvinyl alcohol. The quaternized polyvinyl alcohol is prepared by the following steps: dispersing polyvinyl alcohol in water, adding sodium hydroxide solution and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, continuously reacting under stirring, filtering, washing with water, and drying. The invention has the advantages that: the quaternized polyvinyl alcohol agglomerated aromatic olefin organic copolymer base spheres are used for preparing the high-hydrophilicity strong anion exchanger, the preparation speed is high, the operation process is simple and green, the use of highly toxic reagents such as chloromethyl ether or dichloromethyl ether and the like is avoided, and the defect of poor hydrophilicity of the anion exchanger caused by modification of nano particles or carbon nano tubes is also overcome.
Description
Technical Field
The invention belongs to the technical field of preparation of liquid chromatographic column packing, and particularly relates to an agglomeration type high-hydrophilicity strong anion exchanger, a preparation method and application thereof in liquid chromatographic column packing.
Technical Field
Most of high-hydrophilicity strong-anion chromatographic packing is based on an organic polymer matrix, most of functional groups are quaternary ammonium groups, however, quaternary ammonium groups are introduced on the surface of an organic polymer base sphere, the preparation process usually needs to adopt highly toxic reagents such as chloromethyl ether, dichloromethyl ether and the like to perform chloromethylation on organic polymers so as to introduce active chlorine, and then the preparation process reacts with a tertiary amine reagent so as to introduce the quaternary ammonium groups, so that the preparation process has complicated steps, and the chloromethyl ether and the dichloromethyl ether have great toxicity to people and the environment.
In order to solve the problem, a common method in the prior art is to use quaternary ammonium nanoparticles and sulfonated polymer microspheres (with a particle size of micron order) to form core-shell type microspheres (the core is sulfonated polymer microspheres and the shell is quaternary ammonium nanoparticles) with surface rich in quaternary ammonium groups through agglomeration reaction, for example, US patent nos. 4119580, 4376047 and 4351909 adopt the strategy method to prepare the strong anion chromatographic packing. Although the method can obtain the quaternary amine type chromatographic stationary phase filler with high capacity, the method has the defects that: the nanoparticles are difficult to agglomerate uniformly on the surface of the micro-sized polymer microspheres due to electrostatic repulsion between the nanoparticles, resulting in partial exposure of the surface without agglomeration of the nanoparticles. And because the surface of the polymer microsphere is strong hydrophobic, the chromatographic packing obtained by the method has poor hydrophilicity. Another disadvantage is that: it is difficult to accurately control the particle size of the nanoparticles, thus resulting in insufficient batch reproducibility of the type of chromatographic packing preparation.
Chinese patent CN201210426077.6 discloses an anionic chromatographic filler prepared by agglomerating micron-sized polymer microspheres with quaternized carbon nanotubes. This method simply replaces the quaternized carbon nanotubes with quaternized nanoparticles, and the problems of non-uniform agglomeration and lack of hydrophilicity of the nanoparticle agglomerated polymer microsphere method described above still remain.
Chinese patent No. CN 104226283B discloses a polyvinyl alcohol coating type chromatographic stationary phase, a preparation method and an application thereof, and provides a method for modifying the surface of a matrix such as silica gel by physical coating, although the method can obtain a strong hydrophilic polar chromatographic filler, the preparation process is also simple and green. However, this method utilizes the principle that polyvinyl alcohol is copolymerized into a film on the surface of a polar base sphere, and the surface of the base sphere inside is required to contain sufficient polar sites due to the strong hydrophilicity of polyvinyl alcohol. Therefore, the method is difficult to be applied to polymer microspheres represented by chloromethyl styrene-divinylbenzene which has strong hydrophobicity, thereby limiting the kinds and development of the ion exchanger. Even the filler obtained by coating the polymeric microspheres with polyvinyl alcohol several times is still a neutral filler and cannot be used for anion separation.
The invention obtains the high-hydrophilicity strong anion exchanger by innovatively mixing and oscillating the quaternized polyvinyl alcohol solution and the sulfonated organic copolymer microsphere solution, and is applied to the liquid chromatography column packing.
Disclosure of Invention
Aiming at the defects in the preparation method, the invention provides a high-hydrophilicity strong anion exchanger.
The invention also provides a preparation method of the high-hydrophilicity strong anion exchanger, and the preparation method is simple in preparation process and environment-friendly.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: an agglomerated high-hydrophilicity strong anion exchanger is prepared by agglomerating sulfonated polymer microspheres by quaternized polyvinyl alcohol.
Preferably, the quaternized polyvinyl alcohol is prepared by the following steps: dispersing polyvinyl alcohol in water, adding sodium hydroxide and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, continuously reacting under stirring, filtering, washing with water, and drying to obtain the quaternized polyvinyl alcohol.
Preferably, the mass-to-volume ratio of the polyvinyl alcohol to the water is 1 g: 15mL, wherein the mass ratio of the polyvinyl alcohol to the sodium hydroxide to the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 4: 1: 5, the continuous reaction time is 7-9 h.
Further preferably, the agglomeration, a specific reaction step, is: stirring the quaternized polyvinyl alcohol, the sulfonated polymer microspheres and water uniformly at the reaction temperature of 50-70 ℃, filtering, and drying the filter cake.
More preferably, the polymeric microspheres are chloromethylstyrene and divinylbenzene copolymer microspheres.
In order to achieve the other purpose of the invention, the invention adopts the technical scheme that: a preparation method of an agglomeration type high-hydrophilicity strong anion exchanger comprises the preparation steps of:
1) preparing polymer microspheres;
preparing polymer microspheres by a suspension polymerization method, wherein the polymer microspheres are copolymer-based spheres of chloromethyl styrene and divinylbenzene;
2) sulfonating the polymer microspheres;
dispersing the copolymer-based spheres of chloromethyl styrene and divinylbenzene prepared in the step 1) in a sulfuric acid solution under the condition of ice-water bath; then continuously stirring and reacting at room temperature to prepare a suspension, pouring the suspension into an ice-water bath solution to terminate the reaction, and washing a filter cake to be neutral after suction filtration to obtain sulfonated polymer microspheres;
3) preparing quaternized polyvinyl alcohol;
dispersing polyvinyl alcohol in water, adding sodium hydroxide and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride at the temperature of 80-95 ℃, continuously reacting under the condition of magnetic stirring, filtering water, washing and drying to obtain quaternized polyvinyl alcohol;
4) agglomeration;
and (2) under the condition of reaction temperature of 50-70 ℃, uniformly stirring the quaternized polyvinyl alcohol prepared in the step 3), the sulfonated polymer microspheres prepared in the step 2) and water, performing suction filtration, and drying a filter cake to obtain the agglomeration type high-hydrophilicity strong anion exchanger.
Wherein, in the step 1), the particle size of the polymer microsphere is 8 μm; in the step 2), the mass-to-volume ratio of the chloromethyl styrene and divinylbenzene copolymer-based spheres to the sulfuric acid solution is 1 g: 2mL, wherein the mass fraction of the sulfuric acid solution is 60%, and the stirring reaction is carried out for 20-40 min.
In the step 3), the mass-to-volume ratio of the polyvinyl alcohol to the water is 1 g: 15mL, wherein the mass-volume ratio of the polyvinyl alcohol to the sodium hydroxide solution to the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution is 4: 1: 5, the continuous reaction time is 7-9 h; in the step 4), the mass-to-volume ratio of the quaternized polyvinyl alcohol to the sulfonated polymer microspheres to water is 2 g: 4 g: 50 mL.
The invention also provides the application of the agglomeration type high-hydrophilicity strong anion exchanger in the liquid chromatographic column packing, wherein the agglomeration type high-hydrophilicity strong anion exchanger is dispersed in homogenate and is filled into a chromatographic column under a hydraulic condition. Preferably, the hydraulic conditions are 5000 psi.
The technical advantages of the invention are as follows:
1) the present invention utilizes quaternized polyvinyl alcohol solutions to replace the quaternized nanoparticles or carbon nanotubes used in traditional methods to agglomerate sulfonated polymer microspheres. The quaternized polyvinyl alcohol is still a homogeneous solution system, which is beneficial to overcoming the defects of nonuniform agglomeration and poor hydrophilicity of nano particles, and the quaternized polyvinyl alcohol can ensure that the obtained strong anion exchanger has high hydrophilicity.
2) According to the agglomeration type high-hydrophilicity strong anion exchanger, the high-hydrophilicity strong anion exchange filler is obtained by agglomerating quaternized polyvinyl alcohol and sulfonated organic polymer microspheres, so that the use of highly toxic reagents such as chloromethyl ether, dichloromethyl ether and the like is avoided, the preparation speed is high, the operation process is simple and green and environment-friendly, particularly, when the polyvinyl alcohol is quaternized, the quaternizing reagents with different anion exchange group types and structures can be selected, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is preferably adopted to perform quaternization modification on the polyvinyl alcohol under the alkaline condition to obtain the quaternized polyvinyl alcohol, and the method provides a new thought for preparing the high-hydrophilicity anion exchanger.
3) The 3-chloro-2-hydroxypropyl trimethyl ammonium chloride adopted by the invention carries out quaternization modification on polyvinyl alcohol under the alkaline condition, although the preparation method is more conventional, no report that the quaternized polyvinyl alcohol solution and sulfonated polymer microspheres are agglomerated to prepare a high-hydrophilicity strong anion exchanger to be applied to chromatographic column packing exists at present, and the anion exchange chromatographic packing obtained by agglomerating the sulfonated polymer microspheres with the quaternized polyvinyl alcohol provided by the invention has good separation performance on inorganic anions, which is the innovative content of the invention.
Drawings
FIG. 1 is a chromatogram of inorganic anion separated by a chromatographic column filled with the highly hydrophilic strong anion exchanger prepared by the invention.
FIG. 2 is a chromatogram of a comparative experiment of non-quaternized polyvinyl alcohol coated sulfonated polymer microspheres for the separation of inorganic anions.
Wherein the peaks in FIG. 1 are IO in sequence from left to right3 -、BrO3 -、NO2 -、NO3 -、I-、SCN-。
Detailed Description
In order to make the content of the present invention more accurately understood, the following description will be made in detail with reference to the accompanying drawings. However, the practice of the present invention is not limited to the following examples.
The agglomeration type high-hydrophilicity strong anion exchanger is prepared by agglomerating sulfonated polymer microspheres by quaternized polyvinyl alcohol.
The preparation method comprises the following specific steps:
1) preparing polymer microspheres;
preparing polymer microspheres by a suspension polymerization method, wherein the polymer microspheres are copolymer-based spheres of chloromethyl styrene and divinylbenzene;
2) sulfonating the polymer microspheres;
dispersing the copolymer-based spheres of chloromethyl styrene and divinylbenzene prepared in the step 1) in a sulfuric acid solution under the condition of ice-water bath; then continuously stirring and reacting at room temperature to prepare a suspension, pouring the suspension into an ice-water bath solution to terminate the reaction, and washing a filter cake to be neutral after suction filtration to obtain sulfonated polymer microspheres;
3) preparing quaternized polyvinyl alcohol;
dispersing polyvinyl alcohol in water, adding sodium hydroxide and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride at the temperature of 80-95 ℃, continuously reacting under the condition of magnetic stirring, filtering water, washing and drying to obtain quaternized polyvinyl alcohol;
4) agglomeration;
and (2) under the condition of reaction temperature of 50-70 ℃, uniformly stirring the quaternized polyvinyl alcohol prepared in the step 3), the sulfonated polymer microspheres prepared in the step 2) and water, performing suction filtration, and drying a filter cake to obtain the agglomeration type high-hydrophilicity strong anion exchanger.
Example 1
1) Preparation of polymer microspheres: chloromethyl styrene and divinylbenzene copolymer-based spheres having a particle size of about 8 μm were prepared by suspension polymerization.
2) Sulfonation of polymer microspheres: weighing 10g of the prepared chloromethyl styrene and divinylbenzene copolymer base spheres, placing the weighed chloromethyl styrene and divinylbenzene copolymer base spheres in a 50mL round-bottom flask, adding 20 mL of sulfuric acid solution with the mass percentage of 60% into the round-bottom flask under the condition of ice-water bath, completely dispersing the chloromethyl styrene and divinylbenzene copolymer base spheres in the sulfuric acid solution by magnetic stirring, continuously stirring for 30min at the room temperature of 30 ℃ to prepare suspension, pouring the suspension into the ice-water bath solution to terminate the reaction, carrying out suction filtration on the ice-water bath solution, and washing the obtained filter cake to be neutral to obtain the required sulfonated polymer microspheres.
3) Quaternization of polyvinyl alcohol: dispersing 10g of polyvinyl alcohol in a 250mL three-necked flask filled with 150mL of water, adding a proper amount of sodium hydroxide at the temperature of 90 ℃, slowly dropwise adding a proper amount of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, continuously reacting for 8 hours under the condition of magnetic stirring, carrying out suction filtration and washing, and drying at the temperature of 60 ℃ to obtain the quaternized polyvinyl alcohol.
4) Agglomeration: adding 150mL of water into a 250mL round-bottom flask, placing the flask in an oil bath pan at 60 ℃, adding the prepared quaternized polyvinyl alcohol and sulfonated polymer microspheres under the action of magnetic stirring to uniformly disperse the quaternized polyvinyl alcohol and sulfonated polymer microspheres in the oil bath pan, performing suction filtration, and drying the obtained filter cake in an oven at 140 ℃ for 2 hours.
Example 2
Dispersing the highly hydrophilic anion exchanger obtained by agglomerating sulfonated polymer-based spheres with quaternized polyvinyl alcohol in a homogenate, and charging the homogenate under a hydraulic pressure condition of 5000psiA chromatographic column. IO separation under ultraviolet detection mode at flow rate of 1mL/min and mobile phase of 5mM potassium carbonate3 -、BrO3 -、NO2 -、NO3 -、I-And SCN-Ion, spectrogram is shown in figure 1. It is clear that the anion exchange chromatography packing obtained in this example using the sulfonated polymer microspheres agglomerated with the quaternized polyvinyl alcohol proposed by the present invention shows good separation performance for the above ions.
And (3) comparison test: to further highlight the separation effect of the chromatographic packing of the present invention, the same samples as those in the above example 2 were separated from the chromatographic packing obtained by coating sulfonated polymer microspheres with polyvinyl alcohol (commercial reagent purchased without quaternary ammonium modification) as mentioned in the chinese patent CN 104226283B. As shown in fig. 2, it can be seen that the filler is weakly retained on the sample and has substantially no separation effect.
The above embodiments are only for further illustration of the technical solution and the advantages of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as within the protection scope of the present invention.
Claims (8)
1. An agglomeration type high-hydrophilicity strong anion exchanger, which is characterized in that: the agglomeration type high-hydrophilicity strong anion exchanger is prepared by agglomerating sulfonated polymer microspheres by quaternized polyvinyl alcohol;
the quaternized polyvinyl alcohol is prepared by the following steps: dispersing polyvinyl alcohol in water, adding sodium hydroxide and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride for continuous reaction, then carrying out suction filtration, washing with water, and drying to obtain quaternized polyvinyl alcohol;
the polymer microspheres are copolymer microspheres of chloromethyl styrene and divinylbenzene.
2. The agglomerated highly hydrophilic strong anion exchanger of claim 1, characterized in that: the mass volume ratio of the polyvinyl alcohol to the water is 1 g: 15mL, wherein the mass ratio of the polyvinyl alcohol to the sodium hydroxide to the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 4: 1: 5, the continuous reaction time is 7-9 h.
3. The agglomerated highly hydrophilic strong anion exchanger of claim 1, characterized in that: the agglomeration comprises the following specific reaction steps: stirring uniformly the quaternized polyvinyl alcohol, the sulfonated polymer microspheres and water at the reaction temperature of 50-70 ℃, filtering, and drying a filter cake; wherein the mass volume ratio of the quaternized polyvinyl alcohol to the sulfonated polymer microspheres to water is 2 g: 4 g: 50 mL.
4. A process for preparing the agglomerated highly hydrophilic strong anion exchanger of claim 1, characterized in that: comprises the following preparation steps:
1) preparing polymer microspheres;
preparing polymer microspheres by a suspension polymerization method, wherein the polymer microspheres are copolymer-based spheres of chloromethyl styrene and divinylbenzene;
2) sulfonating the polymer microspheres;
dispersing the copolymer-based spheres of chloromethyl styrene and divinylbenzene prepared in the step 1) in a sulfuric acid solution under the condition of ice-water bath; then continuously stirring and reacting at room temperature to prepare a suspension, pouring the suspension into an ice-water bath solution to terminate the reaction, and washing a filter cake to be neutral after suction filtration to obtain sulfonated polymer microspheres;
3) preparing quaternized polyvinyl alcohol;
dispersing polyvinyl alcohol in water, adding sodium hydroxide and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride at the temperature of 80-95 ℃, continuously reacting under the condition of magnetic stirring, filtering water, washing and drying to obtain quaternized polyvinyl alcohol;
4) agglomeration;
and (2) under the condition of reaction temperature of 50-70 ℃, uniformly stirring the quaternized polyvinyl alcohol prepared in the step 3), the sulfonated polymer microspheres prepared in the step 2) and water, performing suction filtration, and drying a filter cake to obtain the agglomeration type high-hydrophilicity strong anion exchanger.
5. The method for preparing the agglomerated highly hydrophilic strong anion exchanger according to claim 4, wherein: in the step 1), the particle size of the polymer microsphere is 8 μm; in the step 2), the mass-to-volume ratio of the chloromethyl styrene and divinylbenzene copolymer-based spheres to the sulfuric acid solution is 1 g: 2mL, wherein the mass fraction of the sulfuric acid solution is 60%, and the stirring reaction time is 20-40 min.
6. The method for preparing the agglomerated highly hydrophilic strong anion exchanger according to claim 4, wherein: in the step 3), the mass-to-volume ratio of the polyvinyl alcohol to the water is 1 g: 15mL, wherein the mass ratio of the polyvinyl alcohol to the sodium hydroxide to the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 4: 1: 5; in the step 4), the mass-to-volume ratio of the quaternized polyvinyl alcohol to the sulfonated polymer microspheres to water is as follows: 2 g: 4 g: 50 mL.
7. Use of an agglomerated highly hydrophilic strong anion exchanger according to claim 1 in packing materials for liquid chromatography columns, wherein: the agglomerated high-hydrophilicity strong anion exchanger is dispersed in the homogenate and is filled into a chromatographic column under the hydraulic condition.
8. Use of the agglomerated highly hydrophilic strong anion exchanger according to claim 7 in packing materials for liquid chromatography columns, characterized in that: the hydraulic conditions were 5000 psi.
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| CN102941130A (en) * | 2012-10-31 | 2013-02-27 | 浙江大学 | Preparation method of quaternized carbon nanotube agglomerated anionic chromatographic packing material |
| CN103521276A (en) * | 2013-10-12 | 2014-01-22 | 东华大学 | Carbon-nanotube-doped type basic anion exchange composite membrane, and preparation method and application thereof |
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| US4119580A (en) * | 1977-11-07 | 1978-10-10 | Dionex Corporation | Method for forming agglomerated ion exchange resin |
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