A Surprise from 1954: Siloxane Equilibration Is a Simple, Robust, and Obvious Polymer Self-Healing Mechanism

Tetramethylammonium silanolate-initiated ring-opening copolymerization of octamethylcyclotetrasiloxane (D(4)) and bis(heptamethylcyclotetrasiloxanyl)ethane (bis-D(4)) renders cross-linked network polymers that contain ethylene bridges and active silanolate end groups. These "living" reactive anionic species are not neutralized by ambient atmosphere exposure (are stable to water, oxygen, CO(2)) and promote thermally activated equilibration among different network isomers and cyclic oligomers. The cross-link density of these living networks can be controlled by the ratio of D(4):bis-D(4), and the density of active chain ends is determined from the initiator:monomer ratio. We report that samples prepared with…

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  Center for Hierarchical Manufacturing, National Science Foundation