The Polymer Society of Korea

Abstract

The synthesis of well-defined poly(4-vinylphenol) (P4VPh) with a narrow dispersity (Ð) is a critical requirement for various advanced polymer applications. In this study, we established a synthetic route to high-fidelity P4VPh by combining nitroxide-mediated polymerization (NMP) with a controlled acidic hydrolysis. Initially, the homopolymerizations of 4-acetoxystyrene and 4-tert-butoxystyrene were conducted using an alkoxyamine initiator, yielding precursors with controlled number-average molecular weights and low dispersity based on the monomer-to-initiator ratios. To prevent the characteristic side reactions that occur during the deprotection of nitroxide-terminated polymers, we implemented solvent-dependent pathway control by adjusting the solvent/water composition. By optimizing the reaction medium, the transient carbocations generated under acidic conditions were effectively quenched, thereby inhibiting undesired reaction pathways that typically lead to a significant increase in dispersity. GPC and NMR analyses confirmed quantitative deprotection while maintaining the Ð of the pristine polymers. This protocol provides a reliable, metal-free platform for producing P4VPh with a precisely controlled molecular architecture.