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  1. A novel precision single-ion conductor with phenylsulfonyl(trifluoromethylsulfonyl)imide lithium salt covalently bound to every fifth carbon of a polyethylene backbone, p5PhTFSI-Li, was synthesized via ring opening metathesis polymerization (ROMP) followed by post polymerization modification. The conversion of poly(4-phenylcyclopentene), bearing 94% sulfonate anions, to trifluoromethanesulfonimide (TFSI) anions was highly efficient (∼90%) as determined by 19 F NMR analysis and corroborated through other spectroscopic methods. The flexible hydrocarbon backbone combined with a bulky TFSI anion led to an observable glass transition temperature of 199 °C even at these high levels of ionization. A high thermal stability up to 375 °C was also observed. Blending of p5PhTFSI-Li with poly(ethylene oxide) at various compositions was performed to investigate electrochemical performance and transference numbers with respect to the lithium electrode using a combination of impedance and polarization methods. At 90 °C and a 50 : 50 wt% blend composition, this system displayed the highest reported conductivity (2.00 × 10 −4 S cm −1 ) of a system with a demonstrated lithium-ion transference number near unity. Such performance is also atypical of single ion conductors produced through post-polymerization modification, which we attribute to the high yield of TFSI conversion. Investigations into the complex miscibility and phase behavior of these blends at various compositions was also probed by a combination of microscopy and differential scanning calorimetry, which is discussed with reference to computational predictions of how charge correlations affect polymer blend phase behavior. 
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  2. Hydrolytic degradation of commercially available 3D printing filament, i.e. poly (lactic acid) with broad molecular weight distribution was induced by incubating 3D-printed parts in deionized water at 3 temperatures. Small changes in orthogonal dimensions occurred due to relaxation of printing stresses, but no mass or volume loss were detected over the time-frame of the experiments. Molecular weight decreased while polydispersity remained constant. The most sensitive measure of degradation was found to be nondestructive, small-amplitude oscillatory tensile measurements. A rapid decay of tensile storage modulus was found with an exponential decay time constant of about an hour. This work demonstrates that practical monitoring of commercially available PLA degradation can be achieve with linear viscoelastic measurements of modulus. 
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  3. Abstract

    Equilibrium ring opening metathesis polymerization of low strained cycloolefins is opportunistic for the development of novel materials capable of chemical recycling to monomer (CRM). However, many of the potential materials for CRM contain complex side chains complicating predictions of their ring strain energies (RSE). The effects of different conformational considerations on RSE predictions using density functional theory (DFT) are explored. New homodesmotic equations are investigated to capture changes in olefin conformation upon polymerization. The employment ofcis‐2‐butene as a corrective factor with a 2,7‐nonadiene linear analog bearing onecisand onetransolefin (H2cis) resulted in RSEs similar to previously reported ΔHpvalues. Different consideration of possible conformers aside from their lowest energy counterparts leads to a range of predicted RSE values. Similarly, the application of a Boltzmann distribution resulted in negligible differences in RSE. Therefore, RSE predictions using the lowest energy structures with H2ciscalculated at B3LYP/6‐31+G* in toluene is a sufficient approach for predicting RSE of monomers with multiple conformers. This method can be used to screen a monomer's potential for CRM to reduce the time, cost, waste, and effort necessary to research new materials towards a more circular polymer economy.

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