Iron(III)-Mediated AGET ATRP of Methyl Methacrylate Using Vitamin C Sodium Salt as a Reducing Agent

Vitamin C sodium salt (VC‐Na) is used as a reducing agent for the iron‐mediated AGET ATRP (atom transfer radical polymerization using activators generated by electron transfer) of methyl methacrylate (MMA) with FeCl3/tris‐(3,6‐dioxa‐heptyl) amine (TDA‐1) as a catalyst complex and ethyl 2‐bromoisobutyrate (EBiB) as an initiator in the absence/presence of a limited amount of air. As compared with the reported iron‐mediated AGET ATRP of MMA, the current catalyst system shows a faster polymerization rate. For example, a conversion of 82.3% is obtained in 3.1 h with a molar ratio of [MMA]0/[EBiB]0/[FeCl3.6H2O]0/[TDA‐1]0/[VC‐Na]0 = 500:1:1:3:0.5 at 90 °C. The kinetics of polymerizations of MMA in bulk or anisole demonstrate features of “living” or controlled free‐radical polymerization, such as the number‐average molecular weights increasing linearly with monomer conversion and maintaining narrow molecular weight distributions ($\overline {M} _{w} $/$\overline {M} _{n} $ = 1.20–1.44). Vitamin C sodium salt is used as a reducing agent in an iron‐mediated AGET ATRP using polar MMA as a model monomer, ethyl 2‐bromoisobutyrate as an initiator, and FeCl3/tris‐(3,6‐dioxa‐heptyl) amine as a catalyst complex. The polymerization shows features of “living” or controlled radical polymerization and higher activity compared to the reported iron‐mediated AGET ATRP of MMA.