Selective Ring-Opening Polymerization of Silyl Glycidyl Ether through Organocatalysis.

Silyl ether constitutes a multipurpose (macro)molecular functionality for being, e.g., SuFEx-clickable and easily cleavable as a hydroxyl precursor. Its direct incorporation by anionic polymerization is challenged by its base susceptibility. In this study, a two-component organocatalyst shows strict epoxy-selectivity in the anionic ring-opening polymerization (ROP) of commercially available tert-butyldimethylsilyl (R)-(-)-glycidyl ether (TBSGE). The silyl ether pendant groups are fully preserved in the resultant polyether and readily undergo acidic hydrolysis to yield well-defined linear polyglycerol (PGC). Combination of the ROP with mechanistically distinct polymerization chemistries delivers PGC-based polyurethane and a hybrid amphiphilic block copolymer. The SuFEx reaction with sulfonyl fluoride shows effective tuning of polyTBSGE into a sulfonate-functionalized polyether. We have thus exploited the chemoselectivity of organocatalysis to facilitate access to polymers carrying reactive pendant functionalities.