Methods to Accelerate the Rate of Head-to-tail Depolymerization of Poly(carbamates) in Low Polarity Environments
Open Access
Author:
Schmid, Kyle M
Graduate Program:
Chemistry
Degree:
Doctor of Philosophy
Document Type:
Dissertation
Date of Defense:
February 28, 2013
Committee Members:
Scott T Phillips, Dissertation Advisor/Co-Advisor Scott Trent Feldman, Committee Chair/Co-Chair RAYMOND LEE FUNK, Committee Member Ayusman Sen, Committee Member Robert Martin Rioux Jr., Committee Member
The design and synthesis of polymers that undergo end-to-end depolymerization in response to a chemical or physical signal has become an increasingly popular area of polymer chemistry. Specifically, depolymerizable polymers (and some oligomers/macromolecules) have been used in applications such as responsive capsules, self-healing systems, shape-shifting plastics and autonomous analyte-responsive pumps. One of the major classes of depolymerizable polymers is aromatic poly(carbamates). This type of polymer depolymerizes by forming azaquinone methide intermediates throughout the polymer backbone. The formation of azaquinone methide is slow (i.e., hours to days) in environments with low dielectric constants (i.e., solvents with a dielectric constant lower than water, or solid state polymeric materials), which limits their usefulness in the previously mentioned applications. This Thesis describes our efforts towards designing stable poly(carbamates) that rapidly depolymerize from head-to-tail in response to a specific signal in environments less polar than water.
