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Plastics offer innumerable societal benefits but simultaneously contribute to persistent environmental pollution, dominated by polyethylene (PE) and isotactic polypropylene (iPP). Melt blending and reformulating postconsumer PE andiPP into useful materials presents a promising recycling approach. However, such repurposed plastics are generally mechanically inferior due to an inability to efficiently separate polyolefins in mixed waste streams; phase separation of PE andiPP results in brittleness as a consequence of poor interfacial strength. Recently, we demonstrated that a small amount (1 wt%) of a poly(ethylene)-block-poly(ethyl ethylene-ran-ethylene)-block-poly(ethylene) (EXE) triblock copolymer, synthesized by low-cost anionic polymerization of 1,3-butadiene followed by solution hydrogenation, restores tensile toughness to levels equivalent to virgin polyolefins. Unfortunately, low-temperature solvent insolubility of EXE, driven by crystallization of the E blocks containing 1.5 ethyl branches per 100 backbone repeat units (EB), presents a challenge for industrial hydrogenation. Comparable toughness (ca. > 400% strain at break) was achieved in the present work with 1.5 ≤ EB ≤ 6.5, accompanied by reduced EXE crystallinity and dissolution in cyclohexane down to room temperature at the highest EB content. This remarkable toughening behavior is attributed to a synergy between chain entanglements between the E end blocks and semicrystalline PE homopolymer and formation of E block “crystal nodules” that prevent chain pullout, along with topological constraints between the X loops and semicrystallineiPP. Our findings overcome barriers to commercial production of EXE with existing industrial facilities, providing a cost-effective strategy for recycling PE andiPP.
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Threading-the-Needle: Compatibilization of HDPE/ i PP blends with butadiene-derived polyolefin block copolymers
Management of the plastic industry is a momentous challenge, one that pits enormous societal benefits against an accumulating reservoir of nearly indestructible waste. A promising strategy for recycling polyethylene (PE) and isotactic polypropylene ( i PP), constituting roughly half the plastic produced annually worldwide, is melt blending for reformulation into useful products. Unfortunately, such blends are generally brittle and useless due to phase separation and mechanically weak domain interfaces. Recent studies have shown that addition of small amounts of semicrystalline PE- i PP block copolymers (ca. 1 wt%) to mixtures of these polyolefins results in ductility comparable to the pure materials. However, current methods for producing such additives rely on expensive reagents, prohibitively impacting the cost of recycling these inexpensive commodity plastics. Here, we describe an alternative strategy that exploits anionic polymerization of butadiene into block copolymers, with subsequent catalytic hydrogenation, yielding E and X blocks that are individually melt miscible with PE and i PP, where E and X are poly(ethylene- ran -ethylethylene) random copolymers with 6 wt% and 90 wt% ethylethylene repeat units, respectively. Cooling melt blended mixtures of PE and i PP containing 1 wt% of the triblock copolymer EXE of appropriate molecular weight, results in mechanical properties competitive with the component plastics. Blend toughness is obtained through interfacial topological entanglements of the amorphous X polymer and semicrystalline i PP, along with anchoring of the E blocks through cocrystallization with the PE homopolymer. Significantly, EXE can be inexpensively produced using currently practiced industrial scale polymerization methods, offering a practical approach to recycling the world’s top two plastics.
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- PAR ID:
- 10462340
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 120
- Issue:
- 34
- ISSN:
- 0027-8424
- 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/10.1073/pnas.2301352120
