Anionic Polymerization of <i>para</i>-(1-Ethoxy ethoxy)styrene: Rapid Access to Poly(<i>p</i>‑hydroxystyrene) Copolymer Architectures

Abstract

Living anionic polymerization of <i>para</i>-(1-ethoxy ethoxy)­styrene (<i>p</i>EES) resulting in molecular weights between 2700 and 69 000 g mol^–1 and polydispersity indices ≤1.09 is introduced. P<i>p</i>EES can be used as a precursor for the synthesis of well-defined poly­(<i>p</i>-hydroxystyrene) (PHS) architectures, enabling facile and rapid acidic deprotection at room temperature within a few minutes. In addition, a series of block copolymers containing <i>p</i>EES and 2-vinylpyridine (2VP) have been synthesized by anionic block copolymerization, with varied block ratios (<i>X</i>_2VP) between 0.13 and 0.83. Characterization by ¹H NMR spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) was carried out, and all polymers have been deprotected, leading to the respective PHS-<i>b</i>-P2VP block copolymers. Furthermore, PHS-<i>b</i>-P2VP has been used as a macroinitiator for the anionic ring-opening polymerization of ethylene oxide (EO) to generate ((PHS-<i>g</i>-PEO₅₁)₁₃-<i>b</i>-P2VP₄₀) graft-block copolymers