2026-09-19T01:29:27Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/1589212025-04-07T08:46:20Zcom_1721.1_7582com_1721.1_7581col_1721.1_131023
Willard, Adam P.
Johnson, Alayna
Massachusetts Institute of Technology. Department of Chemistry
2025-03-27T16:58:19Z
2025-03-27T16:58:19Z
2025-02
2025-02-25T13:15:08.371Z
https://hdl.handle.net/1721.1/158921
The synthesis of a new polysilylether via entropy-driven ring-opening metathesis polymerization (ED-ROMP) of cyclic bifunctional silyl ether-based monomers is reported. High molecular weight polymers (up to 100 k) with narrow dispersities were achieved at modest temperature. These polymers display excellent thermal stability and ultra-low T_g (–88 ºC). The polymers are both rapidly deconstructable via the cleavage of the labile silicon-oxygen linkages with either acid or fluoride triggers and partially depolymerizable by the addition of exogenous metathesis catalyst. Analysis of the deconstructed polymer products provided insight into the polymer microstructure, showing that the ED-ROMP process was regiorandom. Altogether, this work offers a new class of deconstructable polymers with a range of potential applications. Incorporation of these bifunctional silyl ether-based monomers into copolymers could aid in the triggered deconstruction of otherwise nondegradable hydrocarbon backbones.
S.M.
Massachusetts Institute of Technology
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Polymer Deconstructability and Recyclability via Introduction of Cleavable Si−O Bonds
Thesis
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Master
Master of Science in Chemistry
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<Abstract>The synthesis of a new polysilylether via entropy-driven ring-opening metathesis polymerization (ED-ROMP) of cyclic bifunctional silyl ether-based monomers is reported. High molecular weight polymers (up to 100 k) with narrow dispersities were achieved at modest temperature. These polymers display excellent thermal stability and ultra-low T_g (–88 ºC). The polymers are both rapidly deconstructable via the cleavage of the labile silicon-oxygen linkages with either acid or fluoride triggers and partially depolymerizable by the addition of exogenous metathesis catalyst. Analysis of the deconstructed polymer products provided insight into the polymer microstructure, showing that the ED-ROMP process was regiorandom. Altogether, this work offers a new class of deconstructable polymers with a range of potential applications. Incorporation of these bifunctional silyl ether-based monomers into copolymers could aid in the triggered deconstruction of otherwise nondegradable hydrocarbon backbones.</Abstract>
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