Interfacial and ion-pairing catalysis for oxygen-tolerant large-scale ATRP in ab initio emulsion

A cooperative interfacial and ion-pairing catalysis, coupled with a molecular oxygen reduction reaction (ORR), to scale up an Atom Transfer Radical Polymerization of n-butyl acrylate (BA) from 20 mL to 10 L (scale-up factor = 500) in ab initio emulsion conditions is introduced. The polymerization is driven by the regeneration of [CuIL]+ through CuII/Cu0 comproportionation. [CuIL]+ simultaneously converts O2 to H2O2 (which is then degraded by sodium pyruvate) and drives the polymerization of butyl acrylate. The anionic surfactant sodium dodecyl sulfate (SDS) facilitates catalyst transport inside and outside the micelles by ion-pairing catalysis. n-Butyl acrylate polymerizations are investigated on a small scale with Cu0 wire and on a larger scale with Cu0 powder. On a 10 L scale, the polymerization yielded controlled PBA-Br (Mn = 32.3 × 103; Ð = 1.39, ∼1.64 kg) after 9 h. Chain extension of PBA-Br macroinitiators proved their livingness. An on-line electrochemical monitoring was also introduced to determine the instantaneous CuI and CuII concentrations at the Cu0 wire surface during the polymerization.