含有非热塑性共聚单体的 NIPAM 基共聚物微凝胶的体积相变

IF 2.2 4区 化学 Q3 CHEMISTRY, PHYSICAL Colloid and Polymer Science Pub Date : 2024-07-18 DOI:10.1007/s00396-024-05288-1
Jannis Krüger, Sergej Kakorin, Thomas Hellweg
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引用次数: 0

摘要

我们利用光子相关光谱(PCS)和原子力显微镜(AFM)分析了含有非热膨胀共聚单体 N-叔丁基丙烯酰胺(NtBAM)的 N-异丙基丙烯酰胺(NIPAM)基微凝胶的膨胀行为。以前对 PNIPAM-co-NtBAM 微凝胶溶胀的热力学分析依赖于经典的 Flory-Rehner 理论。然而,这种方法难以准确描述 NtBAM 含量较高时的溶胀曲线。我们目前的研究将 NtBAM 的 Flory-Huggins 相互作用参数 \(\chi _{FH}\)的原始表达式与最近调整的希尔类模型相结合,该模型考虑了聚(NIPAM)微凝胶体积相变过程中的协同效应。这种方法在拟合质量上优于其他方法。观察结果表明,随着 NtBAM 含量的增加,膨胀微凝胶的流体力学半径呈指数下降。此外,在体积相变过程中,离开聚合物链的水分子数量呈指数衰减,这可能是由于一个 NtBAM 单体对相邻 NIPAM 单体的水合作用产生了立体影响。摩尔相互作用焓(\Delta H_{SP}= \text {-49 kJ / mol}\ )和熵(\Delta S_{SP} = \text {-177 J /( mol K)}\ )是从溶胀曲线的拟合中得到的。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Volume phase transition of NIPAM based copolymer microgels with non-thermoresponsive comonomers

We analyze the swelling behavior of N-isopropylacrylamide (NIPAM)-based microgels incorporating the non-thermoresponsive comonomer N-tert-butylacrylamide (NtBAM) using photon correlation spectroscopy (PCS) and atomic force microscopy (AFM). Previous thermodynamic analysis of PNIPAM-co-NtBAM microgel swelling relied on the classical Flory-Rehner theory. However, this approach struggled to accurately describe swelling curves at higher NtBAM content. Our present work combines the original expression for the Flory-Huggins interaction parameter \(\chi _{FH}\) for NtBAM with a recently adapted Hill-like model for the interaction parameter \(\chi _{Hill}\) that accounts for cooperative effects in the volume phase transition in poly(NIPAM) microgels. This approach outperforms other methods in fitting quality. The observed results are revealing an exponential decrease in hydrodynamic radius upon increasing NtBAM content for swollen microgels. In addition, an exponential decay of the number of water molecules leaving the polymer chain during the volume phase transition is found, which can be attributed to the steric influence of one NtBAM monomer on the hydration of neighboring NIPAM monomers. The molar interaction enthalpy \(\Delta H_{SP}= \text {-49 kJ / mol}\) and entropy \(\Delta S_{SP} = \text {-177 J /( mol K)}\) were obtained from the fits of the swelling curves.

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来源期刊
Colloid and Polymer Science
Colloid and Polymer Science 化学-高分子科学
CiteScore
4.60
自引率
4.20%
发文量
111
审稿时长
2.2 months
期刊介绍: Colloid and Polymer Science - a leading international journal of longstanding tradition - is devoted to colloid and polymer science and its interdisciplinary interactions. As such, it responds to a demand which has lost none of its actuality as revealed in the trends of contemporary materials science.
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