| Porous polymer monolithic column or porous polymer microsphere prepared by a high internal phase emulsion（HIPE）template method has the advantages of high porosity and low density due to its unique structure.It has potential application value in oil-water separation,energy storage material and catalyst support.However,due to the poor environmental adaptability of common St/DVB porous materials,they do not have the characteristics of acid and alkali resistance and high salt resistance,so it is difficult to play the application value in harsh environment.To solve this problem,in recent years,porous polymer materials containing fluorine have been further studied.Due to the strong electronegativity of fluorine atoms,porous polymer materials have excellent acid and alkali resistance,high-temperature resistance and high salt resistance.However,the existence of fluorinated monomers makes it difficult to stabilize high internal phase emulsions,and most of the polymerization uses heat-induced polymerization,which requires extra heating and makes the emulsion more easily demulsified.So far,porous materials containing fluorine are mostly brittle materials,which require complex analytical processes after adsorption of organic solvents and are easy to be damaged under external force.Studies on fluorinated emulsions are all W/O high internal phase emulsions,and after polymerization of oil phase monomers,the whole material contains fluorine Poly HIPEs.In some applications,it is not convenient to use porous microspheres.In order to solve the problems in the above studies,porous polymer materials containing fluorine were prepared by combining high internal phase emulsion containing fluorine with the characteristics of fast reaction rate,few byproducts and mild reaction conditions of sulfhydryl group.In order to change the morphology and mechanical properties of the porous materials,the high internal phase emulsion of mercaptan was used as the template to improve the resilience of the porous materials,combined with organic fluorine and silicon,and then the flexibility and tensile properties of the porous materials were improved by mercaptan isocyanate click polymerization.Finally,the porous microspheres were synthesized by the fluorine emulsion of W/O/W double mercaptan.The three porous fluorine-containing materials have excellent properties and application value.The details are as follows:（1）In order to solve the difficult stability of high internal phase emulsion containing fluorine and the inherent brittleness of porous polymer materials containing fluorine,the mercaptane-ene click chemical reaction and high internal phase emulsion template method were combined to prepare porous super-elastomers containing fluorine.Mercaptan,as a phototriggered crosslinked monomer,can trigger mercaptan-ene click polymerization and crosslinking by UV light.This reaction can be completed at room temperature without heating,which is very favorable to the stability of high internal phase emulsion containing fluorine.The effects of the contents of trifluoroethyl methacrylate（TFEMA）and tetramethyltetravinyl cyclotetrasiloxane（V4）in continuous phase and the volume fraction of internal phase on the stability of high internal phase emulsion and the pore structure and properties of porous materials after photoinitiated polymerization were investigated.The results show that the porous structure and morphology of the fluoro-silicon porous material are successfully constructed,which has excellent mechanical elasticity and can be restored to the original state under 90%compressive strain.The water contact Angle can reach 134.8°,showing hydrophobicity,and the adsorption capacity of trichloromethane is 23 times of its own weight.Moreover,after extruding the oil,the adsorption capacity of the oil was not significantly reduced after repeated use for 10 times.（2）In order to further improve the mechanical properties of the material,flexible fluorine-containing Poly HIPEs doped with silica nanoparticles were prepared.With high internal phase emulsion as a template,Hypermer B246 and Si O2as stabilizers,trimethylol propane tri（3-mercaptopropionate）（TMPTMP）as crosslinking agent,polypentathritol hexaacrylate（DPEHA）and trifluoroethyl methacrylate（TFEMA）as alene monomers,Toluene diisocyanate（TDI）is an isocyanate polymeric monomer.The porous polymer material with stretchability was prepared by combining two click reactions of mercaptan and mercaptan isocyanate.The effects of stirring speed,Si O2content,DPEHA and TDI ratio on the structure and properties of porous materials were investigated.The results showed that the tensile strain increased from 30%to 125%.It also shows excellent wear resistance and thermal stability,and the thermal decomposition temperature reaches 300℃.（3）The traditional nano Ti O2photocatalyst is easy to agglomerate when degrading pollutants,which is not easy to recover,and is easy to be ingested by aquatic organisms,resulting in enrichment of biological chain.Fluorinated Poly HIPE porous microspheres are an ideal catalyst carrier,which can solve the above problems and is suitable for harsh environment.According to this idea,a high internal phase emulsion containing mercaptan（W/O）was prepared first,and then a double emulsion containing W/O/W was prepared by adding a secondary PVP solution through mutation phase conversion.Fluorine-containing porous microspheres were prepared by the click chemical reaction of mergene-ene.The effects of PVP molecular weight,PVP content and the addition of secondary external phase on the fluorine-containing porous microspheres were discussed.It was found that these three factors have great effects on the morphology and particle size of the microspheres.Finally,Ti O2nanoparticles were introduced into the oil phase to prepare Ti O2composite photocatalyst supported by porous microspheres containing fluorine,and the degradation of methylene blue was tested.The results showed that the fluorine-containing porous microspheres as the support of Ti O2greatly improved the catalytic degradation ability of methylene blue. |
