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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 × 10 6 tons, but currently only 3.0 × 10 4 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.

A 5-dimensional Smith-Ewart based model is developed to understand differences for reversible addition-fragmentation chain transfer (RAFT) miniemulsion polymerization with theoretical agents mimicking cases of slow fragmentation, cross-termination, and ideal exchange while accounting for chain length and monomer conversion dependencies due to diffusional limitations. The focus is on styrene as a monomer, a water soluble initiator, and a macro-RAFT agent to avoid exit/entry of the RAFT leaving group radical. It is shown that with a too low RAFT fragmentation rate coefficient it is generally not afforded to consider zero-one kinetics (for the related intermediate radical type) and that with significant RAFT cross-termination the dead polymer product is dominantly originating from the RAFT intermediate radical. To allow the identification of the nature of the RAFT retardation it is recommended to experimentally investigate in the future the impact of the average particle size ( d p ) on both the monomer conversion profile and the average polymer properties for a sufficiently broad d p range, ideally including the bulk limit. With decreasing particle size both a slow RAFT fragmentation and a fast RAFT cross-termination result in a stronger segregation and thus rate acceleration. The particle size dependency is different, allowing further differentiation based on the variation of the dispersity and end-group functionality. Significant RAFT cross-termination is specifically associated with a strong dispersity increase at higher average particle sizes. Only with an ideal exchange it is afforded in the modeling to avoid the explicit calculation of the RAFT intermediate concentration evolution.

In the present work, statistical analysis (16 processing conditions and 2 virgin unmodified samples) is performed to study the influence of antioxidants (AOs) during acrylonitrile-butadiene-styrene terpolymer (ABS) melt-blending (220 °C) on the degradation of the polybutadiene (PB) rich phase, the oxidation onset temperature (OOT), the oxidation peak temperature (OP), and the yellowing index (YI). Predictive equations are constructed, with a focus on three commercial AOs (two primary: Irganox 1076 and 245; and one secondary: Irgafos 168) and two commercial ABS types (mass- and emulsion-polymerized). Fourier transform infrared spectroscopy (FTIR) results indicate that the nitrile absorption peak at 2237 cm -1 is recommended as reference peak to identify chemical changes in the PB content. The melt processing of unmodified ABSs promotes a reduction in OOT and OP, and promotes an increase in the YI. ABS obtained by mass polymerization shows a higher thermal-oxidative stability. The addition of a primary AO increases the thermal-oxidative stability, whereas the secondary AO only increases OP. The addition of the two primary AOs has a synergetic effect resulting in higher OOT and OP values. Statistical analysis shows that OP data are influenced by all three AO types, but 0.2 m% of Irganox 1076 displays high potential in an industrial context.