Progress in Reaction Mechanisms and Reactor Technologies for Thermochemical Recycling of Poly(methyl methacrylate)

Chemical or feedstock recycling of poly(methyl methacrylate) (PMMA) by thermal degradation is an important societal challenge to enable polymer circularity. The annual PMMA world production capacity is over 2.4 × 106 tons, but currently only 3.0 × 104 tons are collected and recycled in Europe each year. Despite the rather simple chemical structure of MMA, a debate still exists on the possible PMMA degradation mechanisms and only basic batch and continuous reactor technologies have been developed, without significant knowledge of the decomposition chemistry or the multiphase nature of the reaction mixture. It is demonstrated in this review that it is essential to link PMMA thermochemical recycling with the PMMA synthesis as certain structural defects from the synthesis step are affecting the nature and relevance of the subsequent degradation reaction mechanisms. Here, random fission plays a key role, specifically for PMMA made by anionic polymerization. It is further highlighted that kinetic modeling tools are useful to further unravel the dominant PMMA degradation mechanisms. A novel distinction is made between global conversion or average chain length models, on the one hand, and elementary reaction step-based models on the other hand. It is put forward that only by the dedicated development of the latter models, the temporal evolution of degradation product spectra under specific chemical recycling conditions will become possible, making reactor design no longer an art but a science.