Comparison of the Swelling Behavior of Poly(N-Isopropylacrylamide) and Poly(N-Vinylisobutyramide) Thin Films under Water Vapor Exposure

IF 5.1 1区化学 Q1 POLYMER SCIENCE Macromolecules Pub Date : 2025-01-06 DOI:10.1021/acs.macromol.4c02802

Morgan P. Le Dû, Julija Reitenbach, David P. Kosbahn, Lukas V. Spanier, Robert Cubitt, Cristiane Henschel, André Laschewsky, Christine M. Papadakis, Peter Müller-Buschbaum

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Abstract

Poly(N-isopropylacrylamide) (PNIPAM) is known for exhibiting lower critical solution temperature behavior in water. A structural isomer of PNIPAM, the likewise LCST-type polymer poly(N-vinylisobutyramide) (PNVIBAM), is compared to PNIPAM in a thin film with respect to their swelling behaviors and water uptake kinetics in a humid atmosphere. Based on spectral reflectance, Fourier-transform infrared (FT-IR) spectroscopy, and time-of-flight neutron reflectometry, the amount and kinetics of uptaken water and its distribution inside the films correlate with molecular changes. It is observed that PNVIBAM swells less than PNIPAM. The FT-IR signals reveal a lower water affinity for PNVIBAM than for PNIPAM and larger hydrophobic clathrates in PNVIBAM, which hinders the introduction of water. Additionally, N₂-dried PNIPAM films still contain primary water, whereas PNVIBAM can be fully dried. The first step of water uptake of the main layer describes a filling of the free volume, reaching a water content of 3.8% in PNVIBAM and 6% in PNIPAM.

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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.