Anionic Polymerization of Azidoalkyl Glycidyl Ethers and Post-Polymerization Modification

Abstract

Polyethers like poly(ethylene glycol) have been widely used for a variety of valuable applications, although their functionalization still poses challenges due to the absence of functional handles along the polymer backbone. Herein, a series of novel azide-functionalized glycidyl ether monomers are presented as a universal approach to synthesize functional polyethers by post-polymerization modification. Three azide-functionalized glycidyl ether monomers possessing different alkyl spacers (ethyl, butyl, and hexyl) were designed and synthesized by a simple two-step substitution reaction. Organic superbase-catalyzed anionic ring-opening polymerization can proceed under mild conditions compatible with an azide pendant group, affording wellcontrolled azide-functionalized polyethers with low dispersity (Đ < 1.2). The azide pendant groups on the resulting polymers were readily modified to a variety of functional groups via copper-catalyzed azide−alkyne cycloaddition reactions and Staudinger reduction. Furthermore, copolymerization of azidohexyl glycidyl ether with allyl glycidyl ether was demonstrated to provide an additional orthogonal functional handle. We anticipate that this work provides a new platform for the preparation of diverse functional polyethers.

Antimicrobial PEGtides: A Modular Poly(ethylene glycol)-Based Peptidomimetic Approach to Combat Bacteria

“…This glycidyl ether-based ternary monomer system included three compoundsABGE, IBGE, and EEGE (Figure 1a)which were selected on the basis of previous studies. 30,31 All monomers were synthesized by a simple substitution reaction (typical isolated yields of 41− 76%) and purified by a fractional distillation to high purity (>99%; Figure 1a Copolymerization proceeded via organic superbase t-BuP 4catalyzed anionic ring-opening polymerization of the monomers using benzyl alcohol as an initiator in toluene at room temperature (Figure 1e). The highly basic t-BuP 4 was chosen, as it allowed controlled polymerization of the respective monomers at room temperature.…”

Synthesis of functional and architectural polyethers via the anionic ring-opening polymerization of epoxide monomers using a phosphazene base catalyst

“…Ree's group established a useful polymer platform for the assembly of functional diblock polymers through the t-Bu-P 4 -catalyzed block copolymerization of M6 and allyl glycidyl ether (M14) followed by a series of postpolymerization modifications, including the thiol-ene reaction [32]. Remarkably, azidobearing glycidyl ethers are compatible with the t-Bu-P 4catalyzed AROP protocol, as reported by Kim's group [33]. Azido-bearing monomers (M16-18) were successfully polymerized using t-Bu-P 4 to produce side-chain azidofunctionalized polyethers.…”

Solvent‐Free Mechanochemical Post‐Polymerization Modification of Ionic Polymers

“…Ammonium‐functionalized polyether was synthesized using anionic ring‐opening polymerization (AROP) with a novel epoxide monomer, azidohexyl glycidyl ether (AHGE), as reported previously by our group (Figure S1) [34] . The polymerization of AHGE was conducted with the organic superbase t ‐BuP 4 using benzyl alcohol as an initiator in toluene at room temperature.…”