Convenient Access to α‐Amino‐ω‐Hydroxyl Heterobifunctional PEG and PPO via a Sacrificial Hexahydro‐Triazine Star Strategy.

The anionic ring opening polymerizations of ethylene oxide (EO) and propylene oxide (PO) are performed by using 1,3,5‐triethanol hexahydro‐1,3,5‐triazine (TrAz) as a "sacrificial" trifunctional initiator. Well‐defined three‐arm star polymers are obtained with a narrow molecular weight distribution (Mw/Mn < 1.1). Molecular weights range from 3–15 kg mol−1. Since these star polymers possess an acid‐labile hexahydro‐triazine core, acidic hydrolysis leads to cleavage of the arms. This gives access to well‐defined α‐amino‐ω‐hydroxyl heterobifunctional poly(ethylene glycol) (PEG) and poly(propylene oxide) (PPO) in the molecular weight range of 1–5 kg mol−1 and low dispersity Mw/Mn < 1.1. The α,ω‐heterobifunctional polyethers are valuable structures for bioconjugation. Furthermore, an acid‐labile triazine star polymer is directly used as a polyol component for the synthesis of a polyurethane network, which is stable under ambient conditions but degrades rapidly under acidic conditions. [ABSTRACT FROM AUTHOR]