Convenient Access to α‐Amino‐ω‐Hydroxyl Heterobifunctional PEG and PPO via a Sacrificial Hexahydro‐Triazine Star Strategy. Issue 9 (1st March 2019)

• Record Type: Journal Article
• Authors: Blankenburg, Jan; Frey, Holger
• Is Part Of: Macromolecular rapid communications. Volume 40:Issue 9(2019)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2019-03-01
• Subjects: aminals -- amine protecting groups -- anionic ring opening polymerization -- heterobifunctional -- polyethylene glycol -- polypropylene oxide -- poylethers; Macromolecules -- Periodicals; Polymers -- Periodicals; Chemistry -- Periodicals; 547.705
• DOI: 10.1002/marc.201900020
• Languages: English
• ISSNs: 1022-1336

Abstract

Abstract: 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 ( M w / M n < 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 M w / M n < 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 : The cyclic aminal hexahydro‐1, 3, 5‐triazine is employed as a "sacrificial" initiator for the anionic ring‐opening polymerization of ethylene oxide (EO) and propylene oxide (PO) to produce well‐defined three‐arm star polymers. Acidic hydrolysis of the star polymer core gives access to well‐defined α‐amino‐ω‐hydroxyl heterobifunctional poly(ethylene glycol) (PEG) as well as poly(ethylene oxide) (PPO).