阅读说明：本技术 一种超疏水色谱固定相材料及其制备方法和应用 (Super-hydrophobic chromatographic stationary phase material and preparation method and application thereof ) 是由 乔晓强 于程程 李新庭 岳旭阳 梁梦颖 秦新英 于 2019-10-25 设计创作，主要内容包括：本发明提供了一种超疏水色谱固定相材料及其制备方法和应用,所述材料为共轭微孔有机聚合物包覆球形二氧化硅形成的核壳型色谱固定相材料,其中,所述的共轭微孔有机聚合物壳层是由1,3,5-三乙炔基苯和1,4-二碘苯在球形二氧化硅表面原位生长制备而成。本发明的材料可实现在纯乙腈条件下分离疏水性的多环芳烃类物质,并可实现强极性醇类物质的高效色谱分离分析,显示了良好的分离性能。本发明提供的制备方法过程简单、反应条件温和,具有良好的制备重现性与稳定性,易于推广应用。(The invention provides a super-hydrophobic chromatographic stationary phase material, a preparation method and application thereof, wherein the material is a core-shell type chromatographic stationary phase material formed by coating spherical silicon dioxide with a conjugated microporous organic polymer, wherein a conjugated microporous organic polymer shell layer is prepared by in-situ growth of 1, 3, 5-triethylalkynyl benzene and 1, 4-diiodobenzene on the surface of the spherical silicon dioxide. The material can realize the separation of hydrophobic polycyclic aromatic hydrocarbon substances under the condition of pure acetonitrile, can realize the high-efficiency chromatographic separation analysis of strongly polar alcohol substances, and shows good separation performance. The preparation method provided by the invention has the advantages of simple process, mild reaction conditions, good preparation reproducibility and stability, and easy popularization and application.)

1. The super-hydrophobic chromatographic stationary phase material is characterized in that the material is a core-shell type chromatographic stationary phase material formed by coating spherical silicon dioxide with a conjugated microporous organic polymer, and the structure of the material is as follows:

wherein the conjugated microporous organic polymer shell layer is prepared by in-situ growth of 1, 3, 5-triethylynylbenzene and 1, 4-diiodobenzene on the surface of spherical silicon dioxide.

2. The superhydrophobic chromatographic stationary phase material of claim 1, wherein the spherical silica has a particle size of 3-10 μ ι η.

3. The superhydrophobic chromatographic stationary phase material of claim 1, wherein the reaction formula for preparing the conjugated microporous organic polymer is:

4. a method for preparing the superhydrophobic chromatographic stationary phase material according to any one of claims 1 to 3, comprising the steps of:

a. placing spherical silicon dioxide in a container, slowly adding anhydrous toluene and triethylamine to enable the spherical silicon dioxide to be suspended in a mixed solvent of the anhydrous toluene and the triethylamine, adding catalysts of bis (triphenylphosphine) palladium dichloride and cuprous iodide, uniformly mixing, continuously mechanically stirring, and reacting at room temperature for 1-2 hours under the protection of nitrogen;

b. adding 1, 3, 5-triethylalkynyl benzene and 1, 4-diiodobenzene into the reactant obtained in the step a, wherein the molar ratio of the 1, 3, 5-triethylalkynyl benzene to the 1, 4-diiodobenzene is 1-2: 1, and the total mass of the 1, 3, 5-triethylalkynyl benzene and the 1, 4-diiodobenzene is 20-50% of the mass of the spherical silica, continuously mechanically stirring, and carrying out reflux reaction at 80-110 ℃ for 24-48 hours under the protection of nitrogen;

c. after the reaction is finished, cooling the product to room temperature, washing the product for 3 to 5 times by using a mixed solution of methanol, dichloromethane and acetone in a volume ratio of 1: 1, and then drying the product in vacuum to constant weight to obtain the chromatographic stationary phase material.

5. The method for preparing a superhydrophobic chromatographic stationary phase material according to claim 4, wherein the molar ratio of the bis (triphenylphosphine) palladium dichloride and the cuprous iodide is 1: 1, and the molar amount of the bis (triphenylphosphine) palladium dichloride added is 5-10% of the molar amount of the monomeric 1, 3, 5-triethylynylbenzene.

6. Use of the superhydrophobic chromatographic stationary phase material of any of claims 1-3 in liquid chromatographic separation analysis.

7. The application of claim 6, wherein the superhydrophobic chromatographic stationary phase material is filled in a stainless steel chromatographic column during application, so that high-efficiency separation and analysis of hydrophobic polycyclic aromatic hydrocarbons, alkyl benzenes and hydrophilic alcohols can be realized.

Technical Field

The invention relates to a chromatographic stationary phase material and a preparation method thereof, in particular to a super-hydrophobic chromatographic stationary phase material and a preparation method and application thereof.

Background

The preparation and application of core-shell type structural materials are one of the hot spots of research in the field of material science. Generally, a core-shell structured material is an ordered core-shell structure with nanometer scale formed by uniformly coating one matrix material on the surface of another matrix material through physical or physicochemical action. Since the surface characteristics of the core material can be changed by the shell material coated outside, the prepared core-shell type structural material often exhibits different properties from the single core material or shell material. In addition, due to the inherent core-shell structure, the performance of the composite material has stronger controllability. Spherical silica is a common carrier material, and has many advantages of high mechanical strength, easy surface modification and the like, so that introduction of functional groups with different structures and shell materials on the surface of spherical silica is one of important research directions in the field of material science.

The conjugated microporous organic polymer is a novel microporous organic high polymer material which is constructed by surrounding full conjugated molecular chains, has a unique three-dimensional network structure, excellent porous performance and good chemical and thermodynamic stability, and shows good application prospects in the fields of sensing, gas storage, drug delivery, catalysis and the like. Although the conjugated microporous organic polymer material plays an important role in various fields, the research in the field of chromatographic stationary phase materials is less, and related reported documents are not found, so that the preparation of the superhydrophobic core-shell type chromatographic stationary phase material by using the conjugated microporous organic polymer material as a shell has important research significance and has wide application prospects in the field of chromatographic separation and analysis.

Disclosure of Invention

The invention aims to provide a super-hydrophobic chromatographic stationary phase material, a preparation method and application thereof, so as to provide a novel chromatographic stationary phase material with super-hydrophobicity and good separation performance, and provide more choices for chromatographic separation analysis.

The purpose of the invention is realized as follows: a super-hydrophobic chromatographic stationary phase material is a core-shell type chromatographic stationary phase material formed by coating spherical silicon dioxide with a conjugated microporous organic polymer, and has the structure as follows:

wherein the conjugated microporous organic polymer shell layer is prepared by in-situ growth of 1, 3, 5-triethylynylbenzene and 1, 4-diiodobenzene on the surface of spherical silicon dioxide.

The particle size of the spherical silicon dioxide is 3-10 mu m.

The reaction formula for preparing the conjugated microporous organic polymer is as follows:

。

the preparation method of the super-hydrophobic chromatographic stationary phase material comprises the following steps:

a. placing spherical silicon dioxide in a container, slowly adding anhydrous toluene and triethylamine to enable the spherical silicon dioxide to be suspended in a mixed solvent of the anhydrous toluene and the triethylamine, adding catalysts of bis (triphenylphosphine) palladium dichloride and cuprous iodide, uniformly mixing, continuously mechanically stirring, and reacting at room temperature for 1-2 hours under the protection of nitrogen;

b. adding 1, 3, 5-triethylalkynyl benzene and 1, 4-diiodobenzene into the reactant obtained in the step a, wherein the molar ratio of the 1, 3, 5-triethylalkynyl benzene to the 1, 4-diiodobenzene is 1-2: 1, and the total mass of the 1, 3, 5-triethylalkynyl benzene and the 1, 4-diiodobenzene is 20-50% of the mass of the spherical silica, continuously mechanically stirring, and carrying out reflux reaction at 80-110 ℃ for 24-48 hours under the protection of nitrogen;

c. after the reaction is finished, cooling the product to room temperature, washing the product for 3 to 5 times by using a mixed solution of methanol, dichloromethane and acetone in a volume ratio of 1: 1, and then drying the product in vacuum to constant weight to obtain the chromatographic stationary phase material.

The molar ratio of the bis (triphenylphosphine) palladium dichloride to the cuprous iodide is 1: 1, and the molar amount of the bis (triphenylphosphine) palladium dichloride is 5-10% of the molar amount of the 1, 3, 5-triethynyl benzene.

The application of the super-hydrophobic chromatographic stationary phase material in liquid chromatographic separation and analysis.

When the super-hydrophobic chromatographic stationary phase material is applied, the super-hydrophobic chromatographic stationary phase material is filled in a stainless steel chromatographic column, and the high-efficiency separation and analysis of hydrophobic polycyclic aromatic hydrocarbon, alkylbenzene and hydrophilic alcohol substances can be realized.

The invention has the beneficial effects that:

the shell layer of the conjugated microporous organic polymer has super-hydrophobic and porous performances, and the core-shell chromatographic stationary phase filler prepared from the shell layer material can realize separation of hydrophobic polycyclic aromatic hydrocarbon substances under the condition of pure acetonitrile, can realize high-efficiency chromatographic separation analysis of strongly polar alcohol substances, and shows good separation performance.

The preparation method of the super-hydrophobic core-shell type chromatographic stationary phase material provided by the invention has the advantages of simple process, mild reaction conditions, good preparation reproducibility and stability, and easy popularization and application.

Drawings

FIG. 1 is an infrared spectrum of a spherical silica and a superhydrophobic core-shell type chromatographic stationary phase material of the present invention.

FIG. 2 is a scanning electron micrograph of spherical silica (A) and a superhydrophobic core-shell type chromatographic stationary phase material (B) of the present invention.

FIG. 3 is a thermogravimetric analysis of spherical silica and a superhydrophobic core-shell chromatographic stationary phase material of the present invention.

FIG. 4 is a separation chromatogram of five polycyclic aromatic hydrocarbons.

FIG. 5 is a separation chromatogram of five alkylbenzene species.

FIG. 6 is a chromatogram for the separation of three alcohols.

Detailed Description