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Branching number, pattern, and distribution of polyethylene (PE) significantly affect the crystalline structures at hierarchical length scales and thus dominate physical properties. Highly branched (HB) PE with over 100 branches per 1000 carbons (100b/1kC) can be synthesized from a sole ethylene feedstock using α-diimine nickel catalysts but results in complex 13C solution-state NMR spectra. In this study, we assign numerous 13C peaks that were unassigned in HBPEs synthesized via three nickel α-diimine catalysts. By application of an additive rule of 13C chemical shifts, several new microstructures are identified. The results successfully reveal new branching microstructures, including (i) the configuration of paired branches, (ii) continual paired branches, and (iii) methylated branch ends. Based on these new assignments, several insights into the chain-walking mechanisms of HBPEs are discussed. 

Highly branched polyethylene (PE) thermoplastic elastomer (TPE)s can be synthesized using Brookhart-type α-diimine nickel and palladium catalysts, which show a range of branching number and identity. In this work, we aim at elucidating the structure-property relationship of various PE-TPEs through solution-state and solid-state 13C NMR spectroscopy and mechanical tensile testing. By applying solid-state NMR spectroscopy, DSC, and XRD, it was revealed that small degrees of crystallinity (< 5%) yields polyethylenes that are sufficiently reinforced to exhibit TPE behavior. Across PE samples with similar branching numbers, we relate the effects of branch identity, crystallinity, and molecular weight on the tunable mechanical properties. The structure-property relationship of the PE-TPEs will be discussed. 

Recycling different plastics post-consumers causes downgraded performance due to the physical and chemical property differences conflicting with one another. These properties stem from the incompatibility of the blends to crystallize and blend. As there are millions of tons of waste every year, the ability to effectively blend two plastics such as polyethylene and polypropylene becomes crucial. In this poster, a molecular-level study of polyolefin blend co-crystallization will be explored by utilizing solid-state NMR spectroscopy. It is through NMR spectroscopic techniques and the use of selectively activating various parts of the blend through isotopes that aspects of the arrangement can be made. We will conduct studies into the co-crystallization of the blends utilizing deuterated polymers to access the chain-to-chain interface differences. This will give us the ability to see the relative extent of interaction as well as providing overall system kinetics. From these experiments, a diagram of the co-crystallization structure can be made as well as a defined system to analyze crystallization 

Carbon dioxide (CO2) has long been recognized as an ideal C1 feedstock comonomer for producing sustainable materials because it is renewable, abundant, and cost-effective. However, activating CO2 presents a significant challenge because it is highly oxidized and stable. A CO2/butadiene-derived δ-valerolactone (EVP), generated via palladium-catalyzed telomerization between CO2 and butadiene, has emerged as an attractive intermediate for producing sustainable copolymers from CO2 and butadiene. Owing to the presence of two active carbon–carbon double bonds and a lactone unit, EVP serves as a versatile intermediate for creating sustainable copolymers with a CO2 content of up to 29 wt % (33 mol %). In this Review, advances in the synthesis of copolymers from CO2 and butadiene with divergent structures through various polymerization protocols have been summarized. Achievements made in homo- and copolymerization of EVP or its derivatives are comprehensively reviewed, while the postmodification of the obtained copolymers to access new polymers are also discussed. Meanwhile, potential applications of the obtained copolymers are also discussed. The literature references were sorted into sections based on polymerization strategies and mechanisms, facilitating readers in gaining a comprehensive view of the present chemistry landscape and inspiring innovative approaches to synthesizing novel CO2-derived copolymers. 

ABSTRACT This work investigated the effect of isophthalate (iso) content in poly(ethylene terephthalate) (PET) materials on its degree of crystallinity (χ%) and mechanical properties. Melt blends were prepared from virgin (0 iso-wt.%) and bottle-grade (1.7 iso-wt.%) PET and subsequently spun into fibers. The mechanical and crystallinity properties were determined using differential scanning calorimetry (DSC), X-ray diffraction (XRD), and uniaxial tensile testing. The crystallinity results determined from DSC and XRD quantified the relationship between iso-content and χ% in the materials. It was found that melt-mixing of different isophthalate grades had a lesser effect on melting temperature (Tm) and χ% than chemically recycled random copolymers of terephthalate and isophthalate. It was further shown that random copolymers of <0.25 iso-wt.% had comparable crystallinity to the virgin high-modulus low-shrink (HMLS) materials. 

We report the design and synthesis of an α-diimine PdII catalyst that copolymerizes functionalized and long chain α-olefins to produce semicrystalline polyethylene materials. Through a chain-straightening polymerization mechanism, the catalyst afforded high-melting point polymers with Tm values of up to 120 °C. The chain-straightening polymerization operates with high [ω,1]-insertion selectivity at high alkene concentrations and with varying α-olefin chain lengths, including propylene. The Pd catalyst can copolymerize 1-decene and methyl decenoate into semicrystalline ester-functionalized polymers with incorporation percentages proportional to the comonomer ratio (up to 13 mol %). 13C nuclear magnetic resonance and isotope labeling studies revealed that the improved selectivity relative to those of other systems arises from a high selectivity for [2,1]-insertion (96%) coupled with rapid chain-walking for a total of 90 mol % of 1-decene undergoing net [10,1]-insertion.