CN-122006682-A - High-capacity super-hydrophilic ion chromatographic column filler and preparation method thereof

CN122006682ACN 122006682 ACN122006682 ACN 122006682ACN-122006682-A

Abstract

The invention discloses a high-capacity super-hydrophilic ion chromatographic column filler and a preparation method thereof, relates to the technical field of new materials, and solves the problem that certain ion peaks are seriously trailing due to strong hydrophobicity of the filler. The filler takes PS-DVB as a base ball, sulfonic acid groups are grafted on benzene rings through covalent bonds, the sulfonic acid groups are combined with long molecular chains containing tertiary amine groups through ionic bonds, the long molecular chains are generated by reacting amine nucleophilic reagents with first double epoxy reagents, the tertiary amine groups at one end of the long molecular chains form ionic bonds with the sulfonic acid groups on the surface of the base ball, the long chains are anchored on the surface of the base ball, the epoxy groups at the tail ends of the long molecular chains and second double epoxy reagents or hydrolysis products thereof react in a ring-opening manner to form cross-linking bonds, a multi-layer network structure is constructed, one epoxy group of the second double epoxy reagents reacts with tertiary amine groups in the anchored long molecular chains in a nucleophilic manner to generate quaternary ammonium groups, and the other epoxy groups of the second double epoxy reagents react with tertiary amine nucleophilic reagents to generate quaternary ammonium salt functional groups.

Inventors

SONG WANG
XIE YONGHONG
MA ZHIBIN
LIU CHAO
LIU YANMAN
WANG BINLI

Assignees

四川长青松科技有限公司

Dates

Publication Date: 20260512
Application Date: 20260409

Claims (10)

1. The high-capacity super-hydrophilic ion chromatographic column packing is characterized by comprising the following structures: styrene-divinylbenzene copolymer is taken as a base ball, and sulfonic acid groups are grafted on benzene rings on the surface of the base ball through covalent bonds to form hydrophilic layers and ionic bonding anchor points; the sulfonic acid group is combined with a long molecular chain containing tertiary amino through an ionic bond; The long molecular chain is generated by the reaction of amine nucleophilic reagent and first double epoxy reagent, the long molecular chain contains tertiary amino, the tertiary amino at one end of the long molecular chain forms an ionic bond with a sulfonic acid group on the surface of a base sphere, and a long chain is anchored on the surface of the base sphere; One epoxy group of the second bisepoxy reagent reacts with tertiary amine groups in the anchored long molecular chain to generate quaternary ammonium groups, and the other epoxy group of the second bisepoxy reagent reacts with tertiary amine nucleophilic reagents to generate quaternary ammonium salt functional groups which exist in an OH - type form and serve as active sites for ion exchange.
2. The packing material of claim 1, wherein the amine nucleophile is methylamine, ammonia, ethylamine, ethanolamine, diethanolamine, dimethylamine or other primary or secondary amine.
3. The packing material of claim 1, wherein the tertiary amine nucleophilic reagent is trimethylamine, tetramethyl-methyl-diamine, tetramethyl-ethylene-diamine, tetramethyl-propylene-diamine, tetramethyl-propanol-diamine, tetramethyl-butanediamine or 1, 3-diamino-2-propanol.
4. The high capacity super hydrophilic ion chromatography column packing of claim 1, wherein the bisepoxy agent is 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol diglycidyl ether), or 1, 6-hexanediol diglycidyl ether.
5. A method for preparing a high capacity ultra-hydrophilic ion chromatography column packing, for preparing the packing of any one of claims 1-4, comprising the steps of: Step S100, hydrophilizing the surface of polystyrene-divinylbenzene copolymer (PS-DVB) base spheres; Weighing PS-DVB base balls with the crosslinking degree of 60%, dispersing in isopropanol water solution), carrying out ultrasonic treatment and suction filtration, transferring a filter cake obtained after suction filtration into a beaker, adding glacial acetic acid, stirring at a low speed, dispersing uniformly, then adding methanesulfonic acid, continuously stirring, mixing uniformly, standing at room temperature for reaction, diluting with ultrapure water after the reaction is finished, and carrying out suction filtration with ultrapure water, sodium hydroxide, methanol and ultrapure water respectively, thus obtaining hydrophilic balls containing methylsulfonic acid groups; step 200, synthesizing quaternary ammonium salt functional groups with a multilayer network structure; The method comprises the steps of stirring and dispersing hydrophilic spheres and ultrapure water fully to form uniform suspension, respectively adding amine nucleophilic reagent and first double epoxy reagent into the suspension to react under the water bath condition to obtain a reactant, carrying out suction filtration on the reactant, repeatedly carrying out suction filtration on the reactant by using ultrapure water until the pH value of filtrate is neutral, stirring and dispersing the washed filter cake and ultrapure water fully to obtain uniform suspension, adding second double epoxy reagent into the uniform suspension to carry out water bath reaction, carrying out suction filtration after the reaction is finished, mixing the filter cake obtained by suction filtration with the ultrapure water and tertiary amine nucleophilic reagent under the water bath condition to carry out stirring reaction, and carrying out suction filtration and washing by using the ultrapure water, sodium hydroxide and the ultrapure water after the reaction is finished to obtain the OH - high-capacity super-hydrophilic ion chromatographic column packing.
6. The method for preparing a high capacity super hydrophilic ion chromatographic column packing according to claim 5, wherein the molar ratio of the sulfonic acid group on the surface of the base sphere to the anchored tertiary amine group is 1:2-4.
7. The method for preparing high capacity super hydrophilic ion chromatographic column packing according to claim 5, wherein the molar ratio of amine group of the amine nucleophilic reagent to epoxy group of the first double epoxy reagent is 1:0.8-1.2.
8. The method for preparing a high capacity super hydrophilic ion chromatographic column packing as defined in claim 5, wherein the molar ratio of the epoxy groups of the first bisepoxy reagent to the epoxy groups of the second bisepoxy reagent is 1:1.5-3.
9. The method for preparing a high capacity super hydrophilic ion chromatographic column packing as defined in claim 5, wherein the molar ratio of tertiary amine group of the tertiary amine reagent to epoxy group of the second diepoxy reagent is 1:2.5-3.5.
10. The method for preparing high-capacity super-hydrophilic ion chromatographic column packing according to claim 5, wherein the mass ratio of PS-DVB base balls to methanesulfonic acid is 1:1.8-2.5.

Description

High-capacity super-hydrophilic ion chromatographic column filler and preparation method thereof Technical Field The invention relates to the technical field of new materials, in particular to a high-capacity super-hydrophilic ion chromatographic column filler and a preparation method thereof. Background Ion chromatography is widely applied to detection of ionic compounds in various water qualities, such as surface water, underground water, tap water, bottled drinking water and the like, and different water qualities contain complex ionic species and different contents due to different water source sites, transportation, storage, treatment conditions and the like, so that detection of certain ions with ultralow contents, such as iodide ions, perchloric acid and the like, is difficult. The current widely used ion chromatographic column filler is mainly of latex agglomeration type, the preparation of the filler takes sulfonated polystyrene-divinylbenzene (PS-DVB) microspheres as base spheres, the surfaces of the base spheres are provided with a large amount of negative charges, quaternized nanometer latex particles are used as functional groups, the surfaces of the latex particles are provided with a large amount of positive charges, after the base spheres and the latex particles are mixed, the base spheres and the latex particles form a whole through electrostatic adsorption, the base spheres are used as a support and are wrapped by the latex particles, and redundant quaternary ammonium groups with positive charges on the surfaces of the latex particles are anion exchange sites. The disadvantages of latex agglomerated ion chromatographic column packing are obvious: The latex particles and the base balls are tightly attached, so that the number of quaternary ammonium groups on the surfaces of the latex particles capable of being used for anion exchange is limited, namely, the capacity of a column is low, the service life is short, and the detection of low-concentration ions in a complex matrix sample can not be dealt with; secondly, the filler has strong nonpolar adsorption effect on bromine, nitric acid, iodine and perchloric acid plasma, so that peak-shaped trailing is serious, sensitivity is insufficient, detection requirements cannot be met, thirdly, the latex is synthesized by only using a non-water-soluble monomer, the selectivity of other available monomers is limited, the application range of a chromatographic column is limited, fourthly, the PS-DVB base ball is sulfonated by usually using concentrated sulfuric acid, so that the operation is inconvenient, the synthesis of the latex consumes a long time, the process control difficulty is high, the uniformity of the size of the latex particles is difficult to ensure, and fifth, the latex particles adsorbed on the surface of the base ball are ensured to be a single layer and not to be accumulated (as shown in figure 1), so that the column is excessively high, the base ball is required to be filled firstly, then the latex is slowly injected, the process takes a few days to finish the filling of a finished column, and the production process is time and labor are wasted. Disclosure of Invention The invention provides a high-capacity super-hydrophilic ion chromatographic column filler and a preparation method thereof, which solve the problem that certain ion peaks are seriously trailing due to strong hydrophobicity of the filler. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: The invention discloses a high-capacity super-hydrophilic ion chromatographic column packing, which has the following structure: styrene-divinylbenzene copolymer is taken as a base ball, and sulfonic acid groups are grafted on benzene rings on the surface of the base ball through covalent bonds to form hydrophilic layers and ionic bonding anchor points; the sulfonic acid group is combined with a long molecular chain containing tertiary amino through an ionic bond; The long molecular chain is generated by the reaction of amine nucleophilic reagent and first double epoxy reagent, the long molecular chain contains tertiary amino, the tertiary amino at one end of the long molecular chain forms an ionic bond with a sulfonic acid group on the surface of a base sphere, and a long chain is anchored on the surface of the base sphere; One epoxy group of the second bisepoxy reagent reacts with tertiary amine groups in the anchored long molecular chain to generate quaternary ammonium groups, and the other epoxy group of the second bisepoxy reagent reacts with tertiary amine nucleophilic reagents to generate quaternary ammonium salt functional groups which exist in an OH - type form and serve as active sites for ion exchange. As a specific embodiment, the amine nucleophile is methylamine, ammonia, ethylamine, ethanolamine, diethanolamine, dimethylamine or other primary or secondary amine. As a specific embodiment, the tertiary amine nucleophile is