Ferrocene-containing multifunctional polyethers: Monomer sequence monitoring via quantitative ¹³C NMR spectroscopy in bulk

Ferrocenyl glycidyl ether (fcGE) and allyl glycidyl ether (AGE) are copolymerized via living anionic ring-opening polymerization to generate polyfunctional copolymers with molecular weights up to 40-300 g/mol and low molecular weight dispersities (M_w/M_n < 1.18). Copolymerizations were carried out in bulk at 100 °C and unexpectedly found to proceed without any isomerization of the allyl double bonds. The copolymerization behavior of fcGE and AGE was monitored by in situ quantitative ¹³C NMR kinetic measurements in bulk, evidencing the formation of random copolymers under these conditions, showing no gradient of comonomer incorporation. The redox-active behavior of the copolymers and homopolymers of fcGE was studied by cyclic voltammetry (CV). In order to demonstrate possible postmodification reactions, the random copolymers were modified with N-acetyl-l-cysteine methyl ester via a thiol-ene addition. All polymers have furthermore been characterized by ¹H NMR spectroscopy, DOSY ¹H NMR spectroscopy, size exclusion chromatography (SEC), and MALDI-ToF mass spectrometry.