Preparation And Properties Of A New Superhydrophobic Material Based On Zirconium Phosphonate

Zirconium phosphates family materials have experienced the development from zirconium phosphates to zirconium phosphonates. This class of materials has been used in ion-exchanged, fuel cells, catalysis applications areas owing to their good mechanical and chemical properties. In recent years, zirconium phosphonates get more attention than zirconium phosphates due to their structural design and adjustability which can be introduced functional groups such as-NH2,-COOH, etc., or use different types of phosphonates to obtain a variety of tailored structure and properties materials. Now the reseach of zirconium phosphonates which contains S element are not much, we synthesised zirconium phosphonates contains S element by introducing sulfur atom to phosphonate, and then studied its structure and properties. A new organic phosphonic acid named [(3-ethylthio)-propyl]-phosphonate was synthesized using triethylphosphite, allyl bromide, and ethanethiol as raw materials by Arbuzov reaction and free radical addition, whose molecular formula is CH3CH2SCH2CH2CH2PO3H2. A new material zirconium [(3-ethylsulfanyl)-propyl]-phosphonate (noted as ZEPP) was synthesized via the reaction between [(3-ethylsulfanyl)-propyl]-phosphonate and ZrOCl2·8H2O by reflux, hydrothermal, HF precipitation method, and in situ synthesis methods, whose molecular formula is Zr(O3PCH2CH2CH2SCH2CH3)2.FT-IR results indicate that different methods have no influence on the chemical composition of the ZEPP. XRD and SEM characterization found the crystallinity degree of ZEPP-precipitation and ZEPP-confinement are much higher than ZEPP-reflux and ZEPP-hydrotherm. ZEPP-confinement is composed by many regular sphericals whose diameter is about9.5μm, both reaction time and temperature have an impact on the morphology of the product. ZEPP-precipitation is composed by many microspheres which the diameter of these microspheres is about1.0μm, and every sphere is composited by folded blades (average thickness of these fold blades is about0.5μm). XRD and SEM manifest its typical layered structure with interlayer spacing being about18.02A where the [(3-ethylthio)-propyl]-phosphonate in the layers may arranged as double decks and head to head. The formation of ZEPP-precipitation was also studied.The surface wettability of ZEPP-precipitation was investigated, the CA is about152°and the water droplets on the surface can retain for a long time, which show the super hydrophobicity property. The reasons can be explained that these non-polar organic chains, the air between folded blades and hierarchical micro-and nanoscale hierarchical structures provide sufficient roughness to make the material possesses superhydrophobic property possibly.Three different kinds of zirconium[(3-ethylsulfanyl)-propyl]-phosphonate-phosphate (noted as ZEPPx) were synthesized using mixed phosphate and [(3-ethylsulfanyl)-propyl]-phosphonate. The molecular formula is Zr(HPO4)x(O3PCH2CH2CH2SCH2CH3)2-x·nH2O (x=0.5,1,1.5), XRD shows all three mixed zirconium phosphonates and phosphates were layed compounds with single crystal phase and the interlayer distance were much larger than α-ZrP duing to the [(3-ethylthio)-propyl]-phosphonate. And the contract angle test showed all three mixed zirconium phosphonates and phosphates have hydrophobic properties.