Oxo-Additives for Polyolefin Degradation: Kinetics and Mechanism

Virgin and environmentally aged polypropylene (PP) micropowders (V-PP and E-PP, respectively) were used as reference microplastics (MPs) in comparative photo- and thermo-oxidative ageing experiments performed on their mixtures with a natural ferrous sand (NS) and with a metal-free silica sand (QS). The ferrous NS was found to catalyze the photo-oxidative degradation of V-PP after both UV and simulated solar light irradiation. The catalytic activity in the V-PP/NS mixture was highlighted by the comparatively higher fraction of photo-oxidized PP extracted in dichloromethane, and the higher carbonyl index of the bulk polymer extracted with boiling xylene, when compared with the V-PP/QS mixture. Similarly, NS showed a catalytic effect on the thermal degradation (at T = 60 °C) of E-PP. The results obtained indicate that, under suitable environmental conditions (in this case, an iron-containing sediment or soil matrix, combined with simulated solar irradiation), the degradation of some types of MPs could be much faster than anticipated. Given the widespread presence of iron minerals (including the magnetite and iron-rich serpentine found in NS) in both coastal and mainland soils and sediments, a higher than expected resilience of the environment to the contamination by this class of pollutants is anticipated, and possible routes to remediation of polluted natural environments by eco-compatible iron-based minerals are envisaged. Graphical abstract

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Catalytic Upcycling of Polyolefins

Sun,

Dong,

Gao

et al. 2024

Chem. Rev.

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The large production volumes of commodity polyolefins (specifically, polyethylene, polypropylene, polystyrene, and poly(vinyl chloride)), in conjunction with their low unit values and multitude of short-term uses, have resulted in a significant and pressing waste management challenge. Only a small fraction of these polyolefins is currently mechanically recycled, with the rest being incinerated, accumulating in landfills, or leaking into the natural environment. Since polyolefins are energy-rich materials, there is considerable interest in recouping some of their chemical value while simultaneously motivating more responsible end-of-life management. An emerging strategy is catalytic depolymerization, in which a portion of the C−C bonds in the polyolefin backbone is broken with the assistance of a catalyst and, in some cases, additional small molecule reagents. When the products are small molecules or materials with higher value in their own right, or as chemical feedstocks, the process is called upcycling. This review summarizes recent progress for four major catalytic upcycling strategies: hydrogenolysis, (hydro)cracking, tandem processes involving metathesis, and selective oxidation. Key considerations include macromolecular reaction mechanisms relative to small molecule mechanisms, catalyst design for macromolecular transformations, and the effect of process conditions on product selectivity. Metrics for describing polyolefin upcycling are critically evaluated, and an outlook for future advances is described.

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Oxo-Additives for Polyolefin Degradation: Kinetics and Mechanism

Cited by 3 publications

References 132 publications

Biodegradation of Plastics

Biodegradation of Plastics

Natural iron-containing minerals catalyze the degradation of polypropylene microplastics: a route to self-remediation learnt from the environment

Catalytic Upcycling of Polyolefins

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