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

IF 5.2 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

{"title":"Comparison of the Swelling Behavior of Poly(N-Isopropylacrylamide) and Poly(N-Vinylisobutyramide) Thin Films under Water Vapor Exposure","authors":"Morgan P. Le Dû, Julija Reitenbach, David P. Kosbahn, Lukas V. Spanier, Robert Cubitt, Cristiane Henschel, André Laschewsky, Christine M. Papadakis, Peter Müller-Buschbaum","doi":"10.1021/acs.macromol.4c02802","DOIUrl":null,"url":null,"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.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"81 1","pages":""},"PeriodicalIF":5.2000,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c02802","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}

引用次数: 0

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.

Abstract Image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

聚（n -异丙基丙烯酰胺）和聚（n -乙烯基异丁酰胺）薄膜在水蒸气下膨胀行为的比较

聚（n -异丙基丙烯酰胺）（PNIPAM）以在水中表现出较低的临界溶液温度行为而闻名。PNIPAM的结构异构体，同样是lcst型聚合物聚（n -乙烯基异丁胺）（PNVIBAM），与薄膜中的PNIPAM在潮湿大气中的膨胀行为和吸水动力学进行了比较。基于光谱反射、傅里叶变换红外（FT-IR）光谱和飞行时间中子反射，膜内吸水量、吸水动力学及其分布与分子变化相关。观察到PNVIBAM的膨胀小于PNIPAM。FT-IR信号显示PNVIBAM的亲水性比PNIPAM低，而PNVIBAM中存在较大的疏水笼形物，这阻碍了水的引入。此外，n2干燥的PNIPAM膜仍然含有原生水，而PNVIBAM可以完全干燥。主层吸水的第一步描述了自由体积的填充，PNVIBAM的含水量达到3.8%，PNIPAM的含水量达到6%。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

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.