Observation and Modeling of a Sharp Oxygen Threshold in Aqueous Free Radical and RAFT Polymerization

It is known that oxygen (O₂) stops radical polymerization (RP). Here, it was found that the reaction turn-off occurs abruptly at a threshold concentration of O₂, [O₂]_t, for both free RP and reversible addition-fragmentation chain-transfer polymerization (RAFT). In some reactions, there was a spontaneous re-start of conversion. Three cases were investigated: RP of (i) acrylamide (Am) and (ii) sodium styrene sulfonate (SS) and (iii) Am RAFT polymerization. A controlled flow of O₂ into the reactor was employed. An abrupt turn-off was observed in all cases, where polymerization stops sharply at [O₂]_t and remains stopped when [O₂] > [O₂]_t. In (i), Am acts as a catalytic radical-transfer agent during conversion plateau, eliminating excess [O₂], and polymerization spontaneously resumes at [O₂]_t. In no reaction, the initiator alone was capable of eliminating O₂. N₂ purge was needed to re-start reactions (ii) and (iii). For (i) and (ii), while [O₂] < [O₂]_t, O₂ acts a chain termination agent, reducing the molecular weight (M_w) and reduced viscosity (RV). O₂ acts as an inhibitor for [O₂] > [O₂]_t in all cases. The radical-transfer rates from Am* and SS* to O₂ are >10,000× higher than the initial chain propagation step rates for Am and SS, which causes [O₂]_t at very low [O₂].