Plastic accumulation is becoming a more serious issue for the environment. For instance, by 2050, it is predicted that by mass, there will be more plastic in the ocean than fish. However, recycling through depolymerization remains challenging. Methods to depolymerize plastics must overcome the large enthalpy of monomer addition (ΔHadd). In this report, the effects of tensile force on the enthalpy of monomer addition are examined for an aqueous polymer. Abstraction of a hydrogen atom has been found to be critical in reducing the amount of force necessary to enable depolymerization. Only 2.3 nN of tensile force is required to achieve C-C bond cleavage if a radical is abstracted prior to application of tensile force, whereas 10.7 nN of force is required in the absence of a radical defect. A model system is introduced to test this hypothesis using atomic force microscopy. Computational studies on the model provide a force window to observe directly the necessity of a radical defect. The effect of force on the transition state of depolymerization is also discussed.

Depolymerization enabled by a combination of tensile force and radical abstraction

2019 Fall National Meeting

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