Structures and Segmental Dynamics in Single-Chain Polymer Nanoparticles-Based All-Polymer Nanocomposites

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-03-19 DOI:10.1021/acs.macromol.5c00570

Peizhi Zhao, Zhiwei Yan, Yuling Liang, Rongchun Zhang

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Abstract

All-polymer nanocomposites are attracting dramatic attention due to their unique mechanical and viscoelastic properties. In this study, via multiscale solid-state nuclear magnetic resonance (NMR) methods, it is clearly revealed that a polystyrene (PS)-based single-chain polymer nanoparticle (SCNP) is in closer proximity with linear poly(vinyl methyl ether) (PVME) chains compared to linear PS chains, leading to dramatically different phase separation structures as demonstrated by ¹H spin diffusion NMR experiments. High-resolution solid-state ¹H NMR spectroscopy at ultrafast magic-angle-spinning (MAS) beyond 90 kHz directly reveals the subtle difference in proximity as well as the hydrogen bonding interactions between PVME and PS (or PS-SCNP) at a molecular level. Due to closer proximity between the PS-SCNP and PVME, the segmental dynamics of PVME is also slowed down by its hydrogen bonding interactions with PS-SCNP as revealed by variable-contact-time cross-polarization (CP) experiments. Particularly, ¹H fast field cycling NMR experiments at variable temperatures clearly reveal the enhanced glassy and Rouse dynamic heterogeneity of PVME in the PS-SCNP/PVME blend. To the best of our knowledge, this is the first study to apply solid-state NMR spectroscopy to reveal the sophisticated interplay of structures and segmental dynamics in all-polymer nanocomposites at a molecular level, obtaining consistent results with molecular simulations, which could be helpful for the fundamental understanding of the unusual viscoelastic behaviors of all-polymer nanocomposites.

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.