Y. Wang, R. Yang, W. Luo, Z. Li, Z. Zhang, C. Wu, N. Hadjichristidis
Macromolecules, 52, 10, pp. 3888-3896, (2019)
Using the easily accessible 2-azaallyl anions as initiators, the one-pot synthesis of well-defined primary amine-ended telechelic polyaziridines (α-NH2 PAzs) has been achieved through the ring-opening polymerization (ROP) of N-sulfonyl aziridines followed by hydrolysis of the diphenylketimine moiety (—N═C—Ph2). The 2-azaallyl anions were synthesized from the reaction of diphenylketimine or N-[aryl-methylene]-α-phenylbenzenemethanamine with potassium bis(trimethylsilyl) amide (KHMDS) in situ and used to initiate the ROP of aziridines leading to well-defined α-(Ph2C═N)-α′-aryl-ω-NH PAzs. Along with the diphenylketimine group (—N═C—Ph2), aryl functionalities, such as pyridine and triphenylphosphine moieties, can also be incorporated to the chain end. Chain extension has been applied for the synthesis of poly(N-sulfonyl aziridine)-block-poly(ε-caprolactone) (PAz-b-PCL) block copolymers by utilization of the primary amine end group as initiating sites for the ROP of ε-caprolactone catalyzed by tin 2-ethyl hexanoate (SnOct2). Taking advantage of this synthetic approach, core cross-linked multiarm star (CCS) polymers with an outermost shell having amino and triphenylphosphine functionalities have been synthesized via “arm-first” strategy.