Supported group 4 permethylindenyl based catalysts displayed extremely high ethylene polymerisation activity affording popcorn shaped low molecular weights polyethylenes.

Polyethylenes of varying molecular weight and branch density, as well as polypropylenes of varying molecular weight and tacticity, were catalytically converted to lower-molecular-weight liquid products to showcase how these various properties in a mixed waste plastic stream could affect the final product. A Pt nanoparticle on a strontium titanate nanocuboid (Pt/STO) catalyst was used under solvent-free conditions in the presence of 170 psi of H2 at 300 °C for hydrogenolysis. The initial molecular weight of polyethylene was found to have a moderate effect on the yield to the final product (ranging from 55 wt% for M n ∼ 7600 Da to 67 wt% for M n ∼ 50,950 Da). The microstructure, defined as the length and density of branches in a polymer, of higher-molecular-weight polymers was the dominant factor in determining the yield (ranging from 67 wt% for M n ∼ 50,950 Da for linear low-density polyethylene (LLDPE) with C2 branches to 97 wt% for M n ∼ 38,850 Da for LLDPE with C6 branches). The same products (M n = C29–C46, Đ = 1.1–1.6) and distribution of undesired light gases (C1–C4 ≈ 90 mol%, C5–C8 ≈ 10 mol%) are obtained from conversions of PE of varying molecular weight. The tacticity of polypropylene at a given molecular weight had a significant effect on the molecular weight of the final product, while not strongly affecting conversion. Hydrogenolysis of isotactic polypropylene (iPP) produced ≈C18 with a wider polydispersity (Đ ∼ 1.4) compared to the narrow ≈C64 (Đ ∼ 1.0) and ≈C54 (Đ ∼ 1.0) products from atactic (aPP) and syndiotactic (sPP) polypropylene, respectively. The stereochemistry of the methyl groups dictates the shape and structure of the polymer in the melt, which in turn affects how the hydrocarbon chain interacts with the catalyst surface, thereby impacting the number of C–C scissions. These results show how various characteristics such as the molecular weight and structure of a waste plastic stream could affect the final product.

Well-defined group 4 permethylindenyl complexes displayed second order dependence on monomer concentration producing isotactic and heterotactic (Pr = 0.81) polylactides.

Chemical polymer upcycling by processive catalysts is a promising plastic waste remediation strategy, with the capability of producing selective, highvalue products from waste plastics with minimal energy input. We previously designed a novel processive catalyst with a mesoporous SiO 2 shell/Pt nanoparticle/SiO 2 core architecture (mSiO 2 /Pt/SiO 2 ) that deconstructs polyolefins within narrow pores. Here, we elucidate the mechanism of processive polyolefin hydrogenolysis using in situ magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and coarse-grained molecular dynamics simulations. We observe that most polyethylene−Pt interactions do not lead to C− C bond cleavage but rather to the release of the polymer via a dehydrogenation− rehydrogenation cycle. The porous architecture increases the likelihood that a released polymer is later cleaved and enables the catalyst to perform multiple successive cleavages to the same polymer chain. Both experiment and simulation show that the extent of processivity is strongly correlated with the length of the pores, with longer pores leading to a higher processivity.

Obtaining three-dimensional (3D) configurational information of surface organometallic complexes is a persistent challenge due to the low spatial sensitivity of most spectroscopic methods. We show that employing 17O-enriched supports enables...