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Title Does the Varying Reactivity in the Transient Polymer Network through Dynamic Exchange Regulate the Closed-Loop Circularity in Polyolefin Vitrimers?
ID_Doc 15426
Authors Dey, I; Ajnas, NM; Rege, SS; Islam, SS; Misra, A; Samanta, K; Manna, K; Bose, S
Title Does the Varying Reactivity in the Transient Polymer Network through Dynamic Exchange Regulate the Closed-Loop Circularity in Polyolefin Vitrimers?
Year 2023
Published Acs Applied Materials & Interfaces, 15, 45
Abstract According to current projections, of the 400 mega tons of plastic produced globally, 70% is waste and of that only 16% is recycled and the rest is incinerated. This is estimated to contribute to ca. 16% of the net carbon emission by 2050. Such a massive amount of unmanaged plastic waste and the associated huge carbon footprint sets a significant challenge to tackle in the coming decades. To achieve net-zero carbon emission, closed-loop circular economy in plastics is crucial but collection, sorting and processing the postconsumer recycled (PCR) plastics poses humongous challenge in achieving this circularity, unless an effective strategy is designed. In a first of its kind, a designer biobased molecule was synthesized (here maleated castor oil, mCO) that is steric and thermally stable and forms in situ "homo-cross-linking" in the melt post grafting onto PCR-PP. This designer molecule, besides offering a transient network, helps bridge the fragmented PP chains which is usually not amenable from the traditional grafting (like maleic anhydride), thereby addressing a long-standing challenge of retaining the properties post grafting due to chain scission in the melt. The resulting maleated (m) PCR-PP now offers abundant functionality which helped us design single and dual covalent adaptable network (CANs) and evaluate their consequences on the structure-property correlation. The PCR-PP Vitrimers demonstrate a distinct rubbery plateau in the melt and reprocessability with >90% recovery in mechanical properties even after the fifth sequence of recycling. We propose here for the first time how the varying reactivity (single or dual) in the transient polymer network, through dynamic exchange, regulates the closed-loop circularity in PP Vitrimers. Our results begin to suggest that the varying reactivity should be taken into account as an additional design parameter, as it influences both the stress relaxation rates and the flow activation energy. We now understand that the topology reconfiguration is strongly dependent on this varying reactivity, which also controls the overall crystalline morphology and the structural properties in the Vitrimers. This study, in addition to opening new avenues for recycling PP, will help guide researchers working in this field from both academia and industry.
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