Methodologies for Metal Functionalization of Phosphorus Based Photopolymer Networks
Abstract
Photopolymer networks with phosphonium cation, alkyl phosphine and olefin functionality were designed, synthesized and functionalized with metals by metathesis, coordination and hydrometallation reactions, respectively. The materials were strategically designed so that the metal functionalization step could be monitored and quantified. In some cases, this involved characterization by IR, NMR, or X-ray spectroscopic techniques, or by comparison to molecular analogues. It was found that by using a bi-functional photopolymer network, the material could be bi-metallized by orthogonal mechanisms. All metallized polymer networks were tested for their suitability as precursors to metal-containing ceramics. The polymers were pyrolyzed, and on analysis it was found that this methodology mostly favors metal oxides, but metal phosphates and phosphides can also be achieved. Further findings showed that tuning the amount of metal in the polymer precursor has the effect of controlling the amount of metal in the ceramics after pyrolysis. Selected polymer networks were patterned before being metallized and pyrolyzed and this was found to be an effective way of forming patterned ceramics.