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Chemical upcycling of plastic waste into high-value materials has the potential to contribute to a more sustainable plastic economy. We report the synthesis of high-value ionomers directly from commodity polyolefins enabled by amidyl radical mediated C−H functionalization. The use of thiosulfonates as a linchpin functionality for the group transfer of a variety of heteroaryl groups provided tunable incorporation of ionizable functionality onto a variety of polyolefin substrates, including postconsumer polyethylene packaging waste. Synthetic, structural, and thermomechanical studies provided a comprehensive understanding of both structure−reactivity and structure−property relationships for polyolefin ionomers. X-ray scattering experiments conducted in the solid and melt states confirm the presence of ionic multiplets that serve as physical cross-links both below and above the melting temperature of polyolefin crystallites. The incorporation of ionic groups into the polyolefins yielded materials with significantly enhanced melt strength and tensile toughness. We anticipate that this approach to access performance-advantaged polyolefin ionomers from commodity substrates or plastic waste will enhance sustainability efforts and lead to new opportunities for this versatile class of thermoplastics.
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C–H Functionalization of Polyolefins to Access Reprocessable Polyolefin Thermosets
Upcycling plastic waste into reprocessable materials with performance-advantaged properties would contribute to the development of a circular plastics economy. Here, we modify branched polyolefins and postconsumer polyethylene through a versatile C−H functionalization approach using thiosulfonates as a privileged radical group transfer functionality. Cross-linking the functionalized polyolefins with polytopic amines provided dynamically cross-linked polyolefin networks enabled by associative bond exchange of diketoenamine functionality. A combination of resonant soft X-ray scattering and grazing incidence X-ray scattering revealed hierarchical phase morphology in which diketoenamine-rich microdomains phase-separate within amorphous regions between polyolefin crystallites. The combination of dynamic covalent cross-links and microphase separation results in useful and improved mechanical properties, including a ∼4.5-fold increase in toughness, a reduction in creep deformation at temperatures relevant to use, and high-temperature structural stability compared to the parent polyolefin. The dynamic nature of diketoenamine cross-links provides stress relaxation at elevated temperatures, which enabled iterative reprocessing of the dynamic covalent polymer network with little cycle-to-cycle property fade. The ability to convert polyolefin waste into a reprocessable thermoformable material with attractive thermomechanical properties provides additional optionality for upcycling to enable future circularity.
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- PAR ID:
- 10523120
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 145
- Issue:
- 50
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 27450 to 27458
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/jacs.3c08682
