Date of Award

Spring 5-2017

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Polymers and High Performance Materials

Committee Chair

Dr. Derek L. Patton

Committee Chair Department

Polymers and High Performance Materials

Committee Member 2

Dr. Robson F. Storey

Committee Member 2 Department

Polymers and High Performance Materials

Committee Member 3

Dr. Sarah E. Morgan

Committee Member 3 Department

Polymers and High Performance Materials

Committee Member 4

Dr. Charles L. McCormick

Committee Member 4 Department

Polymers and High Performance Materials

Committee Member 5

Dr. Jason D. Azoulay

Committee Member 5 Department

Polymers and High Performance Materials

Abstract

Thiol-ene photopolymerizations provide a robust and versatile synthetic pathway to functional materials, and owing to the radical step-growth nature of polymerization and the resulting homogenous network structure, provide non-convoluted insight into how network chemistry influences and dictates macromolecular properties.

The first facet of this dissertation focuses on the design and synthesis of bio-inspired, thin film adhesives for dry and aqueous adhesion. Drawing inspiration from the intertidal marine mussel, Chapter II details the synthesis of adhesive networks containing a monofunctional catechol-based monomer. The inclusion of a catechol group resulted in significant improvements in adhesion on a variety of substrates. In Chapter III, the inclusion of simple hydrophobic groups in the adhesive thiol-ene networks to improve underwater adhesion is reported. The presence of hydrophobic groups effectively push water away from the adhesive resin/substrate interface, facilitating adhesive interaction underwater. Further, the influence of the catechol (a known radical scavenger) and the hydrophobic groups (commonly considered non-adhesive) on polymerization kinetics, thermal mechanical, and mechanical properties was determined.

The second facet of this dissertation focuses on the synthesis of semi-fluorinated polymer networks, as outlined in Chapter IV. Fluorine groups impart several advantageous properties to polymeric materials including increased mechanical strength, chemical and thermal stability, and unique optical and wetting properties. As such, the inclusion of the trifluorovinyl ether group in a thiol-ene photopolymerization resulted in the rapid and efficient synthesis of semi-fluorinated networks, exhibiting significant increases in thermomechanical and mechanical properties as a function of fluorine content.

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