Abstract
AbstractBatch radical polymerization of 5–40 wt% non‐ionized acrylic acid (AA) in aqueous solution has been studied between 35 and 90 °C under variation of initiator concentration and type as well as upon addition of different levels of 2‐mercaptoethanol as chain‐transfer agent (CTA). Chain‐length‐dependent termination was taken into account in a model developed to describe the system, as high amounts of CTA have an impact on polymerization kinetics due to reduced chain length. The model also considers the 1,5‐hydrogen shift (backbiting) reaction that transforms the secondary propagating radical into a tertiary midchain radical, with the backbiting reaction quantified via 13C NMR. The model developed is the most comprehensive treatment to date of this complex polymerization system and is able to represent monomer conversion profiles and polymer molar mass distributions over a wide range of conditions.
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