Abstract Understanding segmental dynamics of polymer chains is important to decipher the microscopic behavior in order to modulate the bulk properties of polymers. Study of electron spin resonance (ESR) spectroscopy of polymer chain segments is useful to understand internal dynamics of polymer chains in solution. In this paper, poly(oligoethylene glycol methacrylate-co-2,2,6,6-tetramethyl piperidin-4-yl methacrylate)s, OEG-TMPMs, were synthesized. The synthesized OEG-TMPMs were characterized by nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetric (TG) techniques. The TMPM moiety in OEG-TMPMs was oxidized to 2,2,6,6-tetramethyl-1-piperinidyloxy-4-yl methacrylate (TMP) to generate nitroxide radicals. These nitroxide radical-containing OEG-TMPs were analyzed with Fourier transform-infrared (FT-IR) spectroscopy, cyclic voltammetry (CV) and ESR spectroscopy. The effect of side chain length on the segmental mobility of OEG-TMPs was studied. The results showed that the longer pendent chains as in OEG-TMP-4 imparted higher flexibility to the backbone of the polymer and increased rotational freedom of nitroxide radicals as compared to restricted mobility in the case of shorter polymer side chains.

中文翻译：

---

自旋标记的乙二醇基聚合物的合成及其分段运动的研究

摘要 了解聚合物链的链段动力学对于解读微观行为以调节聚合物的整体性质非常重要。聚合物链段的电子自旋共振 (ESR) 光谱研究有助于了解溶液中聚合物链的内部动力学。在本文中，合成了聚（低聚乙二醇甲基丙烯酸酯-co-2,2,6,6-四甲基哌啶-4-甲基丙烯酸酯），OEG-TMPMs。合成的 OEG-TMPM 通过核磁共振 (NMR) 光谱、凝胶渗透色谱 (GPC)、差示扫描量热法 (DSC) 和热重 (TG) 技术进行表征。OEG-TMPMs 中的 TMPM 部分被氧化为 2,2,6,6-tetramethyl-1-piperinidyloxy-4-yl methacrylate (TMP) 以生成氮氧自由基。用傅立叶变换红外 (FT-IR) 光谱、循环伏安法 (CV) 和 ESR 光谱分析这些含有氮氧自由基的 OEG-TMP。研究了侧链长度对 OEG-TMPs 链段迁移率的影响。结果表明，与较短聚合物侧链的受限流动性相比，OEG-TMP-4 中较长的悬垂链赋予聚合物主链更高的柔韧性，并增加了氮氧自由基的旋转自由度。