Swager, Timothy Manning (1988) Precursor routes to conducting polymers from the ring-opening metathesis polymerization of cyclic olefins. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-08152005-160834
Chapter 1 provides an introduction to the field of conductive polymers. The perspective is that of a chemist who is also interested in the physics of conductive polymers. The concepts discussed in this chapter are referred to throughout the other chapters, and should be a good primer for newcomers to this field as well as a reference to the literature for others. This chapter sets the stage for the theme of this thesis, which is the use of soluble precursor polymers in the synthesis of conductive polymers. Recent work was cited in this chapter which is not available in existing reviews of conductive polymers. The method of ring-opening metathesis polymerization (ROMP) is discussed in Chapter 2. The concepts discussed therein are again referred to throughout the following chapters. The ideas of catalyst matching for different monomers are discussed, and particular emphasis is given to the steric requirements of the catalysts. The ROMP of derivatives of dimethylene cyclobutene is discussed in Chapter 3. However, the primary focus of the chapter is on the polymer polydiisopropylidenecyclobutene. This material is distinctly different from other conductive polymers in the fact that it has a structure consisting of triene units that are mutually orthogonal to each other. A detailed study of this material with a variety of spectroscopies and measurements is presented. The synthesis of polybenzvalene, and the isomerization of this material to polyacetylene, is discussed in Chapter 4. This work constitutes a new precursor method to this fundamentally important polymer, as well as a demonstration of the far reaching scope of ROMP. Polybenzvalene is also a high energy material and has unusual explosive properties which are also discussed. In Chapter 5, new precursor routes to conductive polymers based on the elimination and hydrolysis of ketals are presented. This work has been primarily focused on structural chemistry and how to best transform the precursor polymers into conductive polymers. The majority of the effort has been focused on the, poly (quinone bisketals); however, another example of this concept is presented briefly.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Subject Keywords:||chemistry, Olefin Metathesis, Conducting Polymers, Cross Conjugation, Polyacetylene, Precursor Polymers|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Awards:||The Herbert Newby McCoy Award, 1988|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||16 May 1988|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||16 Aug 2005|
|Last Modified:||30 Mar 2017 17:02|
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