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• W4311557369 abstract "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 (Mw) 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]." @default.
• W4311557369 created "2022-12-27" @default.
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• W4311557369 date "2022-12-15" @default.
• W4311557369 modified "2023-09-27" @default.
• W4311557369 title "Observation and Modeling of a Sharp Oxygen Threshold in Aqueous Free Radical and RAFT Polymerization" @default.
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• W4311557369 doi "https://doi.org/10.1021/acs.jpcb.2c06067" @default.
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