Abstract: Reversible-deactivation radical polymerization(RDRP) regulated by single-molecule alkoxyamine features a simple process, produces polymers with light color and minimal odor, and is free of metal ion impurities. However, the design and synthesis of alkoxyamines capable of regulating the polymerization of methacrylate monomers remains a challenging task. In this paper, an innovative type of alkoxyamine{3-[(2-cyanopropan-2-yl)oxy] (isopropyl)amino}-2,2-dimethyl-3-phenylpropanenitrile (CPDMN) was synthesized via Schiff base reduction, potassium persulfate complex oxidation and radical coupling, and then the controlled polymerization behavior of methyl methacrylate (MMA) mediated by CPDMN was investigated. The experimental results demonstrate that the monomer conversion rate increases linearly with polymerization time, while the polymer molecular weight grows with prolonged reaction duration. Gel permeation chromatography traces exhibit symmetrical peaks without significant tailing, indicating characteristic features of controlled/living radical polymerization. Subsequent re-initiation experiments using poly(methyl methacrylate) macroinitiator (PMMA-ONR) with MMA, styrene (St), and ethyl methacrylate (EMA) further confirm the effective retention of alkoxyamine end-groups in the resulting polymers. Finally, the regulation performance of CPDMN on MMA in the presence of oxygen was investigated, achieving a monomer conversion rate of 91.2% and a PMMA molecular weight distribution of less than 1.5, which demonstrates that CPDMN can control the polymerization of MMA with oxygen tolerance. The as-synthesized CPDMN extends the range of monomers applicable to nitroxide-mediated polymerization (NMP), demonstrating promising potential for the synthesis of functional polymeric materials.

Key words: Nitroxide-mediated radical polymerization; Methyl methacrylate, Reversible deactivation radical polymerization, Oxygen-tolerant radical polymerization