Conjugated Microporous Polymers Grafted Silica Chromatographic Stationary Phases:Preparation And Its Separation Performances

Conjugated microporous polymers(CMPs)are a new type of three-dimensional network amorphous porous organic materials.According to the materials'excellent porosity,high specific surface area,tunable structures as well as good chemical and thermal stability,CMPs based materials have shown good application prospects in the fields of separation and analysis.CMPs are ideal materials for the preparation of novel kinds of chromatographic stationary phases owing to these features.Herein,we firstly prepared CMPs@SiO₂chromatographic stationary phase materials and post-modified MSA-CMPs@SiO₂chromatographic stationary phase materials,the separation performances of the developed stationary phase materials were also initially explored.The full text is divided into four chapters.The first chapter is divided into three parts.In the first part,the design and synthesis of CMPs materials and their composite materials are summarized.In the second part,the applications of CMPs materials and their composite materials are summarized.In the third part,the starting point and innovation point are summarized.In the second chapter,using 1,4-diiodobenzene and 1,3,5-triacetylenebenzene as functional monomers,CMPs@SiO₂chromatographic stationary phase materials were fabricated by in-situ polymerization on the surface of spherical silica through Sonogashira-Hagihara coupling reaction.Fourier transform infrared spectrometer,Brunauer-Emmett-Teller(BET)specific surface area and porosity analyzer,element analyzer,contact angle detector,scanning electron microscope and thermogravimetric analyzer were used to characterize the structure,morphology and stability of the above materials.The results demonstrated the CMPs@SiO₂chromatographic stationary phase materials have been successfully prepared.What's more,the materials have superhydrophobicity and good thermal stability.In addition,the alkynyl groups on the surface of CMPs materials can be further functionalized via thiol-yne click reaction.Thus,new CMPs-based stationary phase materials can be further prepared.Herein,using thiomalic acid(MSA)as the functional monomer,MSA-CMPs@SiO₂chromatographic stationary phase materials were also fabricated.The synthesized MSA-CMPs@SiO₂stationary phase materials were characterized.The characterization methods included Fourier transform infrared spectrometer,thermogravimetric analyzer as well as contact angle detector.The results proved that the MSA-CMPs@SiO₂stationary phase materials have been successfully prepared and have hydrophilicity.In the third chapter,firstly,hydrophobic compounds and hydrophilic compounds were used to evaluate the retention mechanism of the packed CMPs@SiO₂column.The truth that the CMPs@SiO₂column had reversed-phase retention mechanism was confirmed.Hydrophobic polycyclic aromatic hydrocarbons,alkylbenzenes,anilines,phenols,monosubstituted benzenes and hydrophilic amides were further used to investigate the separation performances of the CMPs@SiO₂column.The results were also compared with the commercial C₁₈column.The CMPs@SiO₂column can achieve rapid separation with good separation selectivity.The new column was successfully used for monitor and analysis of the hydrolysis states of silane coupling agents and was also utilized to identify and analyze the quality of cooking oils.Secondly,hydrophobic alkylbenzenes and hydrophilic amides were used to evaluate the retention mechanism of the MSA-CMPs@SiO₂column.The results demonstrated that the MSA-CMPs@SiO₂column possessed reversed phase/hydrophilic mixed-mode retention mechanisms.It can be used to rapidly separate of a variety of hydrophilic and hydrophobic compounds.The fourth chapter summarizes the research contents and results of the full work.