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1. Molecular Basis for Thermal Stability and Re-organization of Polymer Crystal: Single Crystal vs. Bulk Crystal

   Huang, Zheng; Jin, Fan; Miyoshi, Toshikazu (March 2025, APS)

   Semicrystalline polymers exhibit different re-organization behaviors during heating depending on crystal growth methods. Upon heating, solution-grown crystals (SGCs) undergo lamellar doubling while melt-grown crystals (MGCs) show a gradual increase in lamellar thickness. However, the molecular-level mechanisms driving these distinct reorganization processes remain unresolved. In this study, we investigate the morphological development, crystalline chain dynamics, chain packing, and chain-folding structures of poly (L-Lactic Acid) in both SGCs and MGCs upon heating by using solid-state NMR spectroscopy and in-situ Small Angle X-ray Scattering (SAXS). By comparing the hierarchical semicrystalline structures and crystalline chain dynamics in SGCs and MGCs, it is found that the chain-folding structure and the presence or absence of entanglements are key factors influencing the thermal stability and different reorganization mechanisms of mobile polymer crystals. 

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2. Elucidations of Chain-Level Structure of Semicrystalline Polymer Freeze-Dried from a Dilute Solution by Solid-State NMR spectroscopy

   Hosseini, Leilasadat; Sun, Chenxuan; Miyoshi, Toshikazu (March 2025, APS)

   Chain entanglements play a crucial role in polymer crystallization, yet their effects on crystallization remain not fully understood. Freeze-drying is one way to potentially preserve disentangled states of long polymer chains. In fact, it is known that freeze-drying (FD) significantly accelerates the crystallization kinetics of semicrystalline polymers. However, the chain-level structure of the FD polymer chains without a long-range order (glass) has been a debatable matter. In this study, we investigate the effect of freeze-drying on single chain-level structures of 13CH3 enriched poly(L-lactic Acid) and 13CH enriched poly(D-lactic acid) racemate by using 1H-1H spin diffusion via 13C detection solid-state NMR spectroscopy. Spatial distributions of PLLA and PDLA glassy chains in the range of a few Å – 30 nm are evaluated via 1H-1H spin diffusion. This analysis provides core-shell morphology of single chains where the outer shell layers include both PDLA and PLLA mixture and the inner core possess a single component. 

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3. Entanglement Effect on Folding Behaviors of Semi-crystalline Polymer during Melt-Crystallization

   Huang, Zheng; Miyoshi, Toshikazu; Sun, Chenxuan; Jin, Fan (March 2024, American Physical Society)

   In the earlier theoretical research, impact of entanglement on folding during crystallization was minimized. The combination of 13C isotope labeling and NMR spectroscopy allows us to quantitatively determine stem to stem distance as well as chain folding distance, hence, we are able to probe chain-level structure. Our recent work indicated that polymer chains are possible to fold prior to crystallization. In this poster, we would like to investigate the folding structure of a semi-crystalline polymer in melt-grown crystals (mgc) by using solid-state NMR spectroscopy and SAXS measurement. First, various 13C enriched poly(L-lactic acid) (PLLA) samples with different molecular weights (Mw = 2.5k – 300k g/mol) across critical entanglement length (Mc = 16k g/mol) were prepared in order to observe the molecular weight dependence of folding structure of PLLA. We revealed that entanglements influence the folding number during crystallization. Second, we attempt to observe the entanglement effect through diluting entanglement density, i.e., blending the PLLA above and below the Mc with different ratio and molecular weight. Based on the experimental results, we would like to highlight the impact of entanglements on folding of semicrystalline polymer in the melt-grown crystal. 

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4. Chain-Straightening Polymerization of Olefins to Form Polar Functionalized Semicrystalline Polyethylene

   https://doi.org/10.1021/acs.organomet.2c00366  

   Eagan, James M.; Padilla-Vélez, Omar; O’Connor, Kyle S.; MacMillan, Samantha N.; LaPointe, Anne M.; Coates, Geoffrey W. (September 2022, Organometallics)

   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. 

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5. Tuning Conjugated Polymer Chain Packing for Stretchable Semiconductors

   https://doi.org/10.1002/adma.202104747  

   Xu, Jie; Wu, Hung‐Chin; Mun, Jaewan; Ning, Rui; Wang, Weichen; Wang, Ging‐Ji_Nathan; Nikzad, Shayla; Yan, Hongping; Gu, Xiaodan; Luo, Shaochuan; et al (September 2021, Advanced Materials)

   Abstract In order to apply polymer semiconductors to stretchable electronics, they need to be easily deformed under strain without being damaged. A small number of conjugated polymers, typically with semicrystalline packing structures, have been reported to exhibit mechanical stretchability. Herein, a method is reported to modify polymer semiconductor packing‐structure using a molecular additive, dioctyl phthalate (DOP), which is found to act as a molecular spacer, to be inserted between the amorphous chain networks and disrupt the crystalline packing. As a result, large‐crystal growth is suppressed while short‐range aggregations of conjugated polymers are promoted, which leads to an improved mechanical stretchability without affecting charge‐carrier transport. Due to the reduced conjugated polymer intermolecular interactions, strain‐induced chain alignment and crystallization are observed. By adding DOP to a well‐known conjugated polymer, poly[2,5‐bis(4‐decyltetradecyl)pyrrolo[3,4‐c]pyrrole‐1,4‐(2H,5H)‐dione‐(E)‐1,2‐di(2,2′‐bithiophen‐5‐yl)ethene] (DPPTVT), stretchable transistors are obtained with anisotropic charge‐carrier mobilities under strain, and stable current output under strain up to 100%. 

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