Facile access to highly functionalized polyacrylamide with ultra-high molecular weight: Multicomponent initiators-based free radical polymerization

We report a novel multicomponent initiators-based copolymerization strategy for synthesizing of acrylamide (AM) and 2-acrylamide-2-methylpropane sulfonic acid (AMPS) copolymers, denoted by P(AM-co-AMPS), with an ultra-high content of AMPS (≥50 mol%) and an ultra-high molecular weight (>10⁷ g/mol), while achieving a high conversion rate of monomer (∼100.0 %). The multicomponent initiators contain a redox couple, an azo compound, and a catalyst. Our investigation into the mechanism suggested that the synergistic effect in different rate constant for initiator decomposition between redox and azo initiators was responsible for actualizing ultra-high molecular weight copolymers with high conversion rates of monomer. Moreover, copolymers with 75 mol% and 100 mol% of AMPS were synthesized to verify the advantage of the multicomponent initiators-based strategy, both of which exhibited ultra-high molecular weights and ultra-high monomer conversion rates. This study fills a long-standing gap in research on the polyacrylamide family by providing highly functionalized P(AM-co-AMPS) with an ultra-high molecular weight. Moreover, it reveals how multicomponent initiators reconcile the contradiction between the ultra-high molecular weight and the high conversion rate in copolymerization.