Silicones are high value polymers that exhibit properties which are unmatched by organic polymers due in large part to the unusual behavior of the Si-O bond. Although symmetric linear polysiloxanes with the same functional group at both termini are commonly made on industrial scales, very few reports have explored their heterotelechelic analogues (two different functional groups) due to limitations in the asymmetric polymerization of cyclicsiloxane oligomers. Here, we present a versatile and scalable strategy to obtain heterotelechelic PDMS through ring opening polymerization with a functional initiator. The functional initiator allows modification of the α chain end while termination introduces functionality on the ω end. These materials were characterized with 1H, 13C, and 29Si NMR spectroscopy. MADLI-TOF was used to verify chain end fidelity. This work lays down the platform to synthesize narrow-disperse heterobifunctional PDMS with versatile chain end functionality.

Versatile, narrow-disperse, heterobifunctional polydimethylsiloxane (PDMS)

ACS Spring 2022

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