Orthogonally deconstructable and depolymerizable polysilylethers entropy-driven ring-opening metathesis polymerization

The synthesis of novel polysilylethers via entropy-driven ring-opening metathesis polymerization (ED-ROMP) of cyclic bifunctional silyl ether-based monomers is reported. These polymers display good thermal stability and ultra-low T g (88 °C). Moreover, they are rapidly deconstructable via the cleavage of the silicon-oxygen linkages with acid or fluoride triggers, and they were 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. The synthesis of low T g polysilylethers via entropy-driven ring-opening metathesis polymerization is reported. These polymers can be depolymerized through olefin metathesis or deconstructed with acid or fluoride.