Rutenberg, Isaac Michael (2005) Functionalized polymers and surfaces via ring-opening metathesis polymerization. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-08132004-132724
The research presented in this thesis focuses on the preparation of functionalized polymers using olefin metathesis polymerization methods. A portion of this research is also devoted to the development of applications for metathesis-derived polymers.
Three distinct types of olefin metathesis polymerizations can be recognized within this work. Ring-opening metathesis polymerization (ROMP) is the most prevalent type, followed by acyclic diene metathesis (ADMET) polymerization and a hybrid of the ROMP and ADMET mechanisms known as ring-opening-insertion metathesis polymerization (ROIMP).
Many of the concepts that appear throughout this thesis are introduced in Chapter 1. Olefin metathesis occupies a central role in each of the subsequent chapters; detailed descriptions of the mechanism and important olefin metathesis catalysts are provided. The chapter also includes background information regarding polymers, polymer properties and the application of ROMP in the construction of electronic devices.
Although the utility of ADMET does not yet seem to match that of ROMP, valuable information can be obtained from ADMET polymerizations. In an effort to elucidate catalytic activity, Chapter 2 details a comparison of the ADMET polymerizations of terminal and non-terminal dienes.
Experimental investigations involving ROIMP, a novel method for the production of A,B-alternating copolymers, is presented in Appendix A. The mechanism of ROIMP is conceptually very different from the mechanisms of either step growth or chain growth polymerizations. Efforts toward understanding the mechanism of ROIMP using a mathematical model are discussed in Chapter 3.
Polymeric chain transfer agents (PCTAs) suitable for ROMP reactions are polymers that contain a single, metathesis-active olefin. These polymers are the focus of Chapter 4 and can be used in the preparation of novel block copolymers. As an example, Appendix B presents the preparation of block copolymers consisting of polyacetylene and various commodity polymers.
Finally, the development of applications for surface-initiated ROMP (SI-ROMP) is discussed in Chapter 5 and Appendix C. Polymer films prepared using SI-ROMP are shown to be viable dielectric layers in thin-film transistors, and research is presented involving microcontact printing and dip pen nanolithography as methods for forming patterned SI-ROMP polymer films.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Subject Keywords:||block copolymers; conducting polymers; polymers; ring-opening metathesis polymerization; surfaces|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||13 August 2004|
|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 2004|
|Last Modified:||26 Dec 2012 02:57|
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