Copper and ZnO dual-catalyzed photo-assisted depolymerization of poly(methyl methacrylate) without deoxygenation

Abstract

Despite significant advancements in thermal and photothermal depolymerizations, the success of these techniques relies on tedious deoxygenation procedures. Herein, we report the development of the depolymerization technique efficient without prior deoxygenation, which was enabled by copper/ligand complexes and the inclusion (0.25 wt% relative to solvent) of zinc oxide (ZnO) nanocrystals activated by UV light. This approach was tested for poly(methyl methacrylate) (PMMA) prepared by atom transfer radical polymerization (ATRP); the effects of solvent polarity and the activity of ligands were investigated. Unexpectedly, a low-activity Cu-complex with 2,2‘-bipyridine ligand, in combination with a low-polarity solvent, 1,2,4-trichlorobenzene, enabled relatively high depolymerization yields in less than 1 h at 150 °C. Higher activity ATRP complexes with tris(2-pyridylmethyl)amine (TPMA) and N,N,N‘,N‘‘,N‘‘-pentamethyldiethylenetriamine (PMDETA) ligands, were less efficient, which was associated with their thermal decomposition and/or the excessive formation of radicals and premature termination of the chain ends. The presented facile approach was designed to be used even in partially aerated reactors, opening new avenues for efficient depolymerization.NSF [DMR 2202747, DMR 2324168]; J. W. Fulbright Commission in the Czech Republic [2022-21-1]; Ministry of Education, Youth and Sports of the Czech Republic [RP/CPS/2022/007, RP/CPS/2024-28/007]; Fonds de recherche du Quebec (FRQNT) [301734]; National Science Centre within the MINIATURA project [DEC-2023/07/X/ST5/01484]; Foundation for Polish Science (FNP)Carnegie Mellon University, CMU; Fundacja na rzecz Nauki Polskiej, FNP; Ministerstvo Školství, Mládeže a Tělovýchovy, MŠMT; Fonds de recherche du Québec, FRQ; US-UK Fulbright Commission, (2022-21-1, RP/CPS/2024-28/007, RP/CPS/2022/007); Fonds de recherche du Québec – Nature et technologies, FRQNT, (301734); Narodowe Centrum Nauki, NCN, (DEC-2023/07/X/ST5/01484); National Science Foundation, NSF, (DMR 2202747, DMR 2324168