AROMA: Anionic ring-opening monomer addition of allyl glycidyl ether to methoxy poly(ethylene glycol) for the synthesis of sequence-controlled polymers

Abstract

Herein, a new method to synthesise epoxide-based sequence-controlled polymers via anionic ring-opening monomer addition, a form of anionic ring-opening polymerisation, is presented. This technique allows in combination with post-polymerisation modification (PPM) reactions for the successful preparation of modified mPEG-b-oligo(allyl glycidyl ether) featuring the incorporation of one repeating unit on average at a time. Due to the possible introduction of a vast variety of molecules to the polymeric system via PPM reactions, a multitude of advanced functional polymeric materials can be generated. This, in combination with the chain extension reactions, allows for the synthesis of well-controlled and programmable architectures with particular properties. The structure of the sequence-controlled polymer was confirmed via 1H NMR spectroscopy, size exclusion chromatography, attenuated total reflection Fourier-transform infrared spectroscopy, and differential scanning calorimetry.

Tailored Polyurethane Synthesis from AB-Type Monomers

“…To achieve a further flexible molecular design, postpolymerization modification of the CC double or CC triple bond was investigated (Scheme , Table ). Here, for the double bond, (1) thiol–ene reaction and (2) 1,3-dipolar cycloaddition with nitrile- N -oxide species were chosen for the modification reaction, − while for the triple bond, (1) thiol–yne reaction, 1,3-dipolar cycloaddition by (2) nitrile- N -oxide species, and (3) azide species by copper-catalyzed azide–alkyne cycloaddition (CuAAC) were selected to implement diverse types of modifications …”

“…In all the reactions, standard reaction conditions based on known protocols were applied, − and the details are given in ESI . In short, all modifications worked properly to provide the desired fully modified products, except the thiol–yne reaction between polyO4 and benzyl mercaptan (Scheme D, Table , PU61 ), which resulted in only a partial (50%) modification.…”