posted on 2024-03-20, 11:37authored byVincent Nieboer, Noé Fanjul-Mosteirín, Peter Olsén, Karin Odelius
Defined macromolecular
architecture using anionic ring-opening
copolymerization (ROcP) of lactones and cyclic carbonates offers facile
routes toward copolymers with unique material properties, ranging
from thermoplastic to elastomeric. However, monomers with a slow ROP
rate are hampered by competing backbiting reactions, scrambling the
macromolecular sequence, and, thereby, a loss of material properties
occurs. We here solve this issue by controlling the rate of backbiting.
Through our approach, we show how block structures previously inaccessible
can be synthesized from monomers with vastly different ROP rates,
covering small lactones and even including macrolactones. This control
can also be extended beyond block structures to include random and
gradient architectures by tuning monomer concentration to the relative
ROP and backbiting rate.