Development of Functional Enyne Molecules to Control Degradability and Architecture in Metathesis Polymers
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Sui, Xuelin
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Abstract
Cascade metathesis reactions using Grubbs-catalysts are intramolecular reorganization reactions between adjacent unsaturated bonds to produce a conjugated 1,3-diene or triene, which has driven new insights into the preparation of functional polymers. However, the usage of the efficient cascade metathesis has not been well-studied with respect to other aspects of metathesis polymerization. In this dissertation, various functional enyne reagents were explored to mediate polymer degradation, ruthenium metal residue removal, and cyclic topology control of metathesis polymerization. Utilizing the unexpected metathesis reaction between terminal alkynes and ruthenium Fisher carbenes, various enyne molecules (Chapter 2) or diyne molecules (Chapter 3) are shown to copolymerize with cyclic enol ethers with low strain energy to give degradable alternating copolymers. Additionally, a fluorous enyne molecule can efficiently terminate the active ruthenium chain end in ring-opening metathesis polymerization (ROMP) to facilitate efficient ruthenium removal via straightforward sequestration methods (Chapter 4). Finally, the enyne derivatives can be utilized to give cyclic Grubbs-type initiators for the construction of cyclic macromolecular structures via ring-expansion metathesis polymerization (REMP) (Chapter 5).
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2023-04-19
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Dissertation