A Plasma-Initiated Graft Polymerization of Methyl Methacrylate in the Presence of a Reverse ATRP Catalyst

Controlled Radical Polymerization Initiated by Solvated Electrons

“…The chemical structures of polymeric products from SEIP‐L were analyzed by FT‐IR and 1 H NMR (Figures S5 and S6, Supporting Information). The preserved bands at 2954, 1727, 1191, and 1149 cm⁻ 1 in polymers, assigned to the stretching vibrations of C‐H and C = O, antisymmetric and symmetric stretching vibrations of C‐O of PMMA, respectively, together with the disappearing band at 1638 cm −1 , assigned to the C = C stretching vibration of MMA, [ 25,42 ] confirmed the addition occurring via the vinyl group, but not the carbonyl group of MMA. Thus, the polymerization yielded PMMA with similar structure to that from benzoyl peroxide (BPO), as indicated by their almost same FT‐IR and 1 H NMR spectra (Figures S5–S7, Supporting Information).…”

“…Apart from these alkali metal solutions, plasma and electron radiations are rich in electrons and known nowadays to involve e sol − reduction in their reactions. [5,[8][9][10] Interestingly, both radiations caused polymerizations exhibiting unique behaviors, e.g., long-lived growing species, [23][24][25][26] monomer selectivity [26,27] and solvent effect. [28] Although the polymerizations were well inhibited by radical scavengers, [23][24][25] their unusual behaviors do not conform to traditional radical mechanism.…”

“…[5,[8][9][10] Interestingly, both radiations caused polymerizations exhibiting unique behaviors, e.g., long-lived growing species, [23][24][25][26] monomer selectivity [26,27] and solvent effect. [28] Although the polymerizations were well inhibited by radical scavengers, [23][24][25] their unusual behaviors do not conform to traditional radical mechanism. These diverse phenomena presented in the polymerizations starting from various e sol − systems, therefore, reflect the elusive reactivity of e sol − in activating monomers.…”

“…[28] Although the SEIP-L presented great discrepancies in kinetic parameters from RP, it gave analogous characters to plasma-initiated polymerization, like long-lived growing species, solvent effect and lower k p value (10 −2 -10 −3 L mol −1 s −1 ). [23][24][25]28] The plasma-initiated polymerization can be largely classified as a radical process due to its inhibiting nature, howbeit the unusual behaviors puzzled researchers for years. Reminded by the one-electron transfer initiation in both polymerizations, we conceive that they may involve charged radicals in propagating reactions.…”

Electric Field Effect of the Plasma-Initiated Polymerization of Methyl Methacrylate: A Negatively Charged Long-Lived Radical

“…The polymerization was suggested to arise from a radical initiation, due to its inhibiting property of radical scavengers like 1,1-diphenyl-2-picrylhydrazyl (DPPH) and hydroquinone [ 11 ]. The other confirmation of the radical mechanism was its initiating capacities in the controlled radical polymerizations of ATRP, DT and RAFT, when appropriate mediating agents were applied [ 12 , 13 , 14 ]. However, there are some unique polymerization behaviors in PIP that cannot be well explained by traditional radical mechanisms.…”