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1. Chain Trajectory, Chain Packing, and Molecular Dynamics of Semicrystalline Polymers as Studied by Solid-State NMR

   https://doi.org/10.3390/polym10070775  

   Wang, Shijun; Hong, You-Lee; Yuan, Shichen; Chen, Wei; Zhou, Wenxuan; Li, Zhen; Wang, Kun; Min, Xu; Konishi, Takashi; Miyoshi, Toshikazu (July 2018, Polymers)

   Chain-level structure of semicrystalline polymers in melt- and solution-grown crystals has been debated over the past half century. Recently, 13C–13C double quantum (DQ) Nuclear Magnetic Resonance (NMR) spectroscopy has been successfully applied to investigate chain-folding (CF) structure and packing structure of 13C enriched polymers after solution and melt crystallization. We review recent NMR studies for (i) packing structure, (ii) chain trajectory, (iii) conformation of the folded chains, (iv) nucleation mechanisms, (v) deformation mechanism, and (vi) molecular dynamics of semicrystalline polymers. 

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2. Comparative Study of Polymer-Grafted BaTiO3 Nanoparticles Synthesized Using Normal ATRP as Well as ATRP and ARGET-ATRP with Sacrificial Initiator with a Focus on Controlling the Polymer Graft Density and Molecular Weight

   https://doi.org/10.3390/molecules28114444  

   Apata, Ikeoluwa E.; Tawade, Bhausaheb V.; Cummings, Steven P.; Pradhan, Nihar; Karim, Alamgir; Raghavan, Dharmaraj (June 2023, Molecules)

   Structurally well-defined polymer-grafted nanoparticle hybrids are highly sought after for a variety of applications, such as antifouling, mechanical reinforcement, separations, and sensing. Herein, we report the synthesis of poly(methyl methacrylate) grafted- and poly(styrene) grafted-BaTiO3 nanoparticles using activator regeneration via electron transfer (ARGET ATRP) with a sacrificial initiator, atom transfer radical polymerization (normal ATRP), and ATRP with sacrificial initiator, to understand the role of the polymerization procedure in influencing the structure of nanoparticle hybrids. Irrespective of the polymerization procedure adopted for the synthesis of nanoparticle hybrids, we noticed PS grafted on the nanoparticles showed moderation in molecular weight and graft density (ranging from 30,400 to 83,900 g/mol and 0.122 to 0.067 chain/nm2) compared to PMMA-grafted nanoparticles (ranging from 44,620 to 230,000 g/mol and 0.071 to 0.015 chain/nm2). Reducing the polymerization time during ATRP has a significant impact on the molecular weight of polymer brushes grafted on the nanoparticles. PMMA-grafted nanoparticles synthesized using ATRP had lower graft density and considerably higher molecular weight compared to PS-grafted nanoparticles. However, the addition of a sacrificial initiator during ATRP resulted in moderation of the molecular weight and graft density of PMMA-grafted nanoparticles. The use of a sacrificial initiator along with ARGET offered the best control in achieving lower molecular weight and narrow dispersity for both PS (37,870 g/mol and PDI of 1.259) and PMMA (44,620 g/mol and PDI of 1.263) nanoparticle hybrid systems. 

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3. Synthesis and characterization of a nematic fully aromatic polyester based on biphenyl 3,4′-dicarboxylic acid

   https://doi.org/10.1039/C9PY00683D  

   Heifferon, Katherine V.; Spiering, Glenn A.; Talley, Samantha J.; Hegde, Maruti; Moore, Robert B.; Turner, S. Richard; Long, Timothy E. (August 2019, Polymer Chemistry)

   Melt acidolysis polymerization of hydroquinone with a kinked monomer, biphenyl 3,4′-bibenzoate, afforded a novel liquid crystalline polymer (LCP), poly( p -phenylene 3,4′-bibenzoate) (poly(HQ-3,4′BB)). Selection of hydroquinone diacetate (HQ a ) or hydroquinone dipivilate (HQ p ) facilitated either a tan or white final polymer, respectively. 1 H NMR spectroscopy confirmed consistent polymer backbone structure for polymers synthesized with either derivative of hydroquinone. Poly(HQ-3,4′BB) exhibited the onset of weight loss at about 480 °C, similar to commercially available Vectra® LCP. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) revealed a glass transition temperature ( T g ) of 190 °C and an isotropic temperature ( T i ) near 330 °C. The observation of a melting temperature ( T m ) depended upon the thermal history of the polymer. Wide-angle X-ray scattering (WAXS) and polarized optical microscopy (POM) confirmed the formation of a nematic glass morphology after quench-cooling from the isotropic state. Subsequent annealing at 280 °C or mechanical deformation induced crystallization of the polymer. Rheological studies demonstrated similar shear thinning behavior for poly(HQ-3,4′BB) and Vectra® RD501 in the power law region at 340 °C. Zero-shear viscosity measurements indicated that HQ a afforded higher melt viscosities after identical polymerization conditions relative to HQ p , suggesting higher molecular weights. 

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4. Characterization of the Slow Molecular Dynamics of Poly( l ‐Lactic Acid) in α and α′ Phases, in a Glassy State, and in a Complex with Poly( d ‐Lactic Acid) by Solid‐State NMR

   https://doi.org/10.1002/macp.201700451  

   Chen, Wei; Zhou, Wenxuan; Makita, Yuta; Wang, Shijun; Yuan, Shichen; Konishi, Takashi; Miyoshi, Toshikazu (January 2018, Macromolecular Chemistry and Physics)

   Abstract Recently, slow molecular dynamics of poly(l‐lactic acid) (PLLA) by using 1D and 2D exchange NMR are investigated. In this work, slow molecular dynamics of PLLA chains in the α′, a stereocomplex (SC) with poly(d‐lactic acid), and glassy states are investigated in terms of centerband‐only detection of exchange (CODEX) NMR. The mixing‐time dependence of the CODEX data demonstrates that the molecular dynamics of stems become slower in the order of α′, α, and SC. The temperature dependence of the correlation time 〈τ_c〉 of the helical jump motions in the α and SC phases simply exhibits Arrhenius behaviors, with activation energy,E_a, values of 91 ± 1 and 97 ± 1 kJ mol⁻¹, respectively. In contrast, the temperature dependence of 〈τ_c〉 in the α′ sample exhibits two Arrhenius lines with substantially differentE_avalues of 273 ± 12 and 16 ± 14 kJ mol⁻¹at temperatures below and above 84 °C. The obtained kinetics of molecular dynamics not only establish the relationship between packing structure and dynamics in PLLA polymorphs and in the SC, but also allow for an understanding of the coupled dynamics between the crystalline and amorphous regions at approximatelyT_g. 

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5. Elucidating the impact of extreme nanoscale confinement on segmental and chain dynamics of unentangled poly(cis-1,4-isoprene)

   https://doi.org/10.1140/epje/i2019-11907-7  

   Kinsey, Thomas; Mapesa, Emmanuel; Cosby, Tyler; He, Youjun; Hong, Kunlun; Wang, Yangyang; Iacob, Ciprian; Sangoro, Joshua (October 2019, The European physical journal. E, Soft matter)

   Broadband dielectric spectroscopy is employed to probe dynamics in low molecular weight poly(cis-1,4-isoprene) (PI) confined in unidirectional silica nanopores with mean pore diameter, D, of 6.5nm. Three molecular weights of PI (3, 7 and 10kg/mol) were chosen such that the ratio of D to the polymer radius of gyration, Rg, is varied from 3.4, 2.3 to 1.9, respectively. It is found that the mean segmental relaxation rate remains bulk-like but an additional process arises at lower frequencies with increasing molecular weight (decreasing D/Rg). In contrast, the mean relaxation rates of the end-to-end dipole vector corresponding to chain dynamics are found to be slightly slower than that in the bulk for the systems approaching D/Rg ∼ 2, but faster than the bulk for the polymer with the largest molecular weight. The analysis of the spectral shapes of the chain relaxation suggests that the resulting dynamics of the 10 kg/mol PI confined at length-scales close to that of the Rg are due to non-ideal chain conformations under confinement decreasing the chain relaxation times. The understanding of these faster chain dynamics of polymers under extreme geometrical confinement is necessary in designing nanodevices that contain polymeric materials within substrates approaching the molecular scale. 

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