N-Ferrocenylsulfonyl-2-methylaziridine: the first ferrocene monomer for the anionic (co)polymerization of aziridines

Abstract

N-Ferrocenylsulfonyl-2-methylaziridine (fcMAz) is the first aziridine-based monomer functionalized at the sulfonamide and the first organometallic aziridine for the anionic ROP. It was polymerized to homo and copolymers (block or statistical) with adjustable molecular weights.

4‐Styrenesulfonyl‐(2‐methyl)aziridine: The First Bivalent Aziridine‐Monomer for Anionic and Radical Polymerization

“…StMAz showed similar reactivity to previously reported aziridine monomers, which allowed us to prepare copolymers with nonfunctional aziridines to further adjust the degree of functionalization. In addition, the free radical polymerization of StMAz leaves the aziridine‐group untouched as a potential receptive for nucleophiles.…”

The living anionic polymerization of activated aziridines: a systematic study of reaction conditions and kinetics

“…At all temperatures, the polymerization remains living, and the addition of new monomer allows the formation of block copolymers. 7,8,15…”

“…4,9 We have developed new monomers and initiator-systems during the last few years, expanding this still rather unexplored approach to polysulfonamides and amines. [5][6][7][8]15,16 With a similar ring-strain of 111 kJ mol −1 for ethylene imine as for ethylene oxide (114 kJ mol −1 ), the anionic ringopening polymerization should be feasible. 17,18 In contrast to unsubstituted ethylene imine, which can only be polymerized via a cationic mechanism, leading to branched PEI ( poly(ethylene imine)), 19 N-protected aziridines can also be polymerized anionically, due to their activating group.…”

Full and partial hydrolysis of poly(2-oxazoline)s and the subsequent post-polymerization modification of the resulting polyethylenimine (co)polymers

“…[38][39][40] The branching was minimized by Goethals et al using N-(2-tetrahydropyranyl)aziridine (THPA), which could be cleaved under mild conditions to obtain L-PEI. 41,42 The polymerization of activated sulfonamide aziridines via living anionic polymerization was recently explored by Bergman 43 and Wurm et al 42,44,4546 The obtained polyaziridines or polysulfonamide could partially (desulfonylated) to obtain L-PEI either via hydrolytic cleavage 47 or via reductive removal with a catalyst. 42 Scheme 3.…”