Chemical Recycling of Polyethylene by Tandem Catalytic Conversion to Propylene.

Although polyethylene (PE) and polypropylene (PP) are by far the world's largest volume plastics, only a tiny fraction of these energy-rich polyolefins are currently recycled. Depolymerization of PE to its constituent monomer, ethylene, is highly endothermic and conventionally accessible only through unselective, high-temperature pyrolysis. Here, we provide experimental demonstrations of our recently proposed tandem catalysis strategy, which uses ethylene to convert PE to propylene, the commodity monomer used to make PP. The approach combines rapid olefin metathesis with rate-limiting isomerization. Monounsaturated PE is progressively disassembled at modest temperatures via many consecutive ethenolysis events, resulting selectively in propylene. Fully saturated PE can be converted to unsaturated PE starting with a single transfer dehydrogenation to ethylene, which produces a small amount of ethane (1 equiv per dehydrogenation event). These principles are demonstrated using both homogeneous and heterogeneous catalysts. While selectivity under batch conditions is limited at high conversion by the formation of an equilibrium mixture of olefins, high selectivity to propylene (≥94%) is achieved in a semicontinuous process due to the continuous removal of propylene from the reaction mixture.

Regression formulas for density functional theory calculated 1H and 13C NMR chemical shifts in toluene-d8.

This study aimed at investigating the performance of a series of basis sets, density functional theory (DFT) functionals, and the IEF-PCM solvation model in the accurate calculation of (1)H and (13)C NMR chemical shifts in toluene-d(8). We demonstrated that, on a test set of 37 organic species with various functional moieties, linear scaling significantly improved the calculated shifts and was necessary to obtain more accurate results. Inclusion of a solvation model produced larger deviations from the experimental data as compared to the gas-phase calculations. Moreover, we did not find any evidence that very large basis sets were necessary to reproduce the experimental NMR data. Ultimately, we recommend the use of the BMK functional. For the (1)H shifts the use of the 6-311G(d) basis set gave linearly scaled mean unsigned (MU) and root-mean-square (rms) errors of 0.15 ppm and 0.21 ppm, respectively. For the calculation of the (13)C chemical shifts the 6-31G(d) basis set produced MUE of 1.82 ppm and RMSE of 3.29 ppm.

Assessment of a Cost-Effective Approach to the Calculation of Kinetic and Thermodynamic Properties of Methyl Methacrylate Homopolymerization: A Comprehensive Theoretical Study.

In this work, we carried out a comprehensive density functional theory (DFT) study on the basis of a trimer-to-tetramer radical reaction model to assess a cost-effective approach to perform the calculation of kinetic and thermodynamic properties of methyl methacrylate (MMA) free-radical homopolymerization. By comparing results from several different functionals (PBE, M06-2X, wB97XD, KMLYP, and MPW1B95), in conjunction with a series of basis sets (6-31G(d,p), 6-31+G(d,p), 6-31G(2df,p), 6-311G(d,p), 6-311+G(d,p), 6-311+G(2df,p), 6-311+G(2df,2p)), we show that calculations using M06-2X/6-311+G(2df,p)//B3LYP/6-31G(2df,p) provide an activation energy of 5.25 kcal mol(-1) for the homopropagation step, which is within 1 kcal mol(-1) of the experimental value. However, this method predicts a heat of polymerization of 17.37 kcal mol(-1) that is larger than the experimental value by 3.5 kcal mol(-1). MPW1B95/6-311+G(2df,p) on the B3LYP/6-31G(2df,p) geometries produces a heat of polymerization value within 1 kcal mol(-1) of experimental data, yet overestimates the activation energy by 3 kcal mol(-1). In addition, we evaluated the performance of ONIOM MO:MO calculations on the geometry optimization of species comprising our MMA polymerization model and found that ONIOM(B3LYP/6-31G(2df,p):B3LYP/6-31G(d)) is capable of producing geometries in very good agreement with the full B3LYP/6-31G(2df,p) calculations. Subsequent calculations of energies using M06-2X/6-311+G(2df,p) based on the ONIOM geometries provided an activation energy value comparable to that based on the full B3LYP/6-31G(2df,p) geometries.