Doctor of Philosophy
Paul J. Ragogna and Elizabeth R. Gillies
Prior to this thesis, phosphorus-containing polymers and photopolymerization represented two distinct, non-overlapping fields of study. This thesis examined the prospect of combining these two approaches to create a system possessing the benefits of both techniques. By exploiting the chemistry of phosphorus, and using photopolymerization as a fabrication method, new materials were developed and assessed for their use in various applications.
Among the many phosphorus compounds that may be used in polymer science, phosphonium salts and primary phosphines were of specific focus. First, highly fluorinated phosphonium monomers were developed to create photopolymerized hydrophobic surfaces. A structure-activity relationship was established, as both the length and type of fluorinated chains used had a dramatic effect on the degree of hydrophobicity. After developing these hydrophobic salts, hydrophilic varieties possessing short alkyl chains were examined and incorporated into polymer networks. These molecules imparted hydrophilic behaviour to the resulting material and were used as a substrate to immobilize anionic gold nanoparticle. The low melting temperature of these salts allowed for the production of highly charged polyelectrolyte networks in seconds, without the need for solvent. Self-crosslinking phosphonium salts were also synthesized and unlike in the previous example, provided an opportunity to increase the stiffness and ion-content within the material simultaneously. The high charge, and low swelling nature of this system allowed it to serve as an excellent substrate for contact-printing applications. While these three approaches involve the photopolymerization of low molecular weight phosphonium salts, a new approach was developed that incorporated phosphonium polyelectrolyte into a photopolymer resin. Immobilization of the charged species within the resin provided a convenient means for the gel-phase synthesis of gold nanoparticles. Finally, using air-stable primary phosphines, phosphane-ene chemistry was used to generate a new class of polymer networks. This approach is analogous to thiol-ene chemistry but possesses the distinct advantages resulting from the ability to harness chemistry of phosphorus within the network.
Guterman, Ryan, "Exploring the Chemistry of Phosphorus for Photopolymer Applications" (2015). Electronic Thesis and Dissertation Repository. 2859.