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Fundamental Chemistry of Chlorophosphazenes and Polysilanes

Stiel, Jason A
http://rave.ohiolink.edu/etdc/view?acc_num=akron1467990664

Abstract Details

2016, Doctor of Philosophy, University of Akron, Chemistry.
Polyphosphazenes and polysilanes make up two of the three largest classes of inorganic backbone polymers. Polyphosphazenes were first synthesized by Stokes over 100 years ago, and now they make up a library of over 700 different polymers. The major advantage polyphosphazenes have over organic polymers is that almost all polyphosphazenes are derived from the same parent polymer [PCl2N]n. However, polyphosphazenes have yet to be used commercially due to the irreproducibilities and high cost in the synthesis of [PCl2N]n. Polysilanes have interesting bonding characteristic due to a s*- delocalization along the silicon backbone, but this delocalization is still not fully understood. The main commercial use for polysilanes is as a fibrous silicon carbide precursor. This application does not take advantage of this unique delocalization of the polymer. More fundamental research is needed to advance the bonding characteristic of the silicon backbone. Throughout the literature, this delocalization has often been compared to conjugated carbon p system, and if this is true it should for Si to interact with electron rich metals. Fundamental chemistry associated with the ring-opening polymerization (ROP) of [PCl2N]3 is the main focuses of this dissertation, where the initial step of ROP and the superacidity of perchlorinated group 13 & 15 Lewis acids are explored. This dissertation is divided into five chapters: introduction, examining the mechanism of the ROP, determining the relative strength and stability of group 13 & 15 Lewis acids, an introduction and exploration into the bonding characteristic of the s*- delocalization of polysilane, and a conclusion. Chapter I will provide an overview of the chemistry of polyphosphazenes. Chapter II is an investigation into the possible species and steps in the ROP of [PCl2N]3 and into the effects of initiators on the process by 31P NMR. In chapter III, the relative superacidities of perchlorinated group 13 & 15 Lewis acids is discussed with emphases on PCl5. Chapter IV is an overview of polysilanes and an examination of the s*-delocalization of polysilane through entrapment of transition metals in cyclosilanes. Chapter V is the conclusions of this dissertation.
Claire Tessier (Advisor)
Wiley Youngs (Committee Member)
Chris Ziegler (Committee Member)
Yi Pang (Committee Member)
Chrys Wesdemiotis (Committee Member)
195 p.
Chemistry
Phosphazenes; superacid; polysilane; NMR monitoring polymerization

Recommended Citations

Citations

  • Stiel, J. A. (2016). Fundamental Chemistry of Chlorophosphazenes and Polysilanes [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1467990664

    APA Style (7th edition)

  • Stiel, Jason. Fundamental Chemistry of Chlorophosphazenes and Polysilanes. 2016. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1467990664.

    MLA Style (8th edition)

  • Stiel, Jason. "Fundamental Chemistry of Chlorophosphazenes and Polysilanes." Doctoral dissertation, University of Akron, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1467990664

    Chicago Manual of Style (17th edition)

akron1467990664
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This open access ETD is published by University of Akron and OhioLINK.