DEVELOPMENT OF HIGH RESOLUTION ESR SPECTROSCOPY FOR DETAILED ANALYSIS OF RADICAL POLYMERIZATION

开发用于自由基聚合详细分析的高分辨率 ESR 光谱

• 批准号: 13650937
• 负责人: KAJIWARA Atsushi
• 金额: $ 2.43万
• 依托单位: Nara University of Education
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650937/
• 关键词: Radical polymerization; Electron spin resonance; ESR; Radical reaction; Molecular dynamics; Kinetics; Chain transfer reaction; magnetic resonance

In order to increase the resolution and sensitivity of ESR spectroscopy, several kinds of trials were made based on improvements of an irradiation lens or a cavity.The most effective trial to increase the resolution and sensitivity of ESR spectroscopy was optimizations of preparation of samples and technique of measurements. Many kinds of conditions, for example, temperature, concentrations of monomers and initiators, irradiation time, wavelength, intensity, shape of sample tube, etc, will influence the resolution and sensitivity. Careful optimizations of these conditions were very important for the high resolution and sensitivity.New results were obtained by careful optimization of the measurement conditions in the improved spectrometer. Detailed analysis of ESR spectra of methacrylates showed clear chain length dependence. It was a first clear experimental evidence for detection of polymeric propagating radicals. Detection of intermediate radicals of reversible addition fragmentation chain transfer (RAFT) systems was also tried. Well-resolved ESR spectra of intermediate radicals were clearly observed. From these spectra, styryl end radical was clearly distinguished from end radical of maleic anhydride.

为了提高ESR谱的分辨率和灵敏度，从改进辐照透镜或谐振腔等方面进行了多种尝试，其中样品制备和测量技术的优化是提高ESR谱分辨率和灵敏度的最有效途径。温度、单体浓度、引发剂浓度、辐照时间、波长、强度、样品管形状等条件都会影响分辨率和灵敏度。这些条件的优化对获得高分辨率和高灵敏度是非常重要的，通过对改进后的光谱仪测量条件的优化，获得了新的结果。甲基丙烯酸酯的ESR谱的详细分析显示出明确的链长依赖性。这是第一个明确的实验证据检测聚合物增长自由基。本文还尝试了可逆加成断裂链转移（RAFT）体系中间自由基的检测。清楚地观察到中间自由基的良好分辨的ESR谱。从这些光谱中，苯乙烯基端基和马来酸酐端基明显不同。

项目成果

Kazunobu Yamada, Atsushi Kajiwara, Tamaki Nakano, and Yoshio Okamoto: "Electron Spin Resonance Study of Stereospecific Polymerization of Vinyl Esters in Fluoroalcohols"Polym.J.. 33. 313-316 (2001)

Kazunobu Yamada、Atsushi Kajiwara、Tamaki Nakano 和 Yoshio Okamoto：“氟代醇中乙烯基酯立体定向聚合的电子自旋共振研究”Polym.J. 33. 313-316 (2001)

Mikiharu Kamachi, Atsushi Kajiwara: "ESR Study on Radical Polymerization and Its Application to Microemulsion Systems"Macromol. Symp.. 179. 53-74 (2002)

Mikiharu Kamachi、Atsushi Kajiwara：“自由基聚合的ESR研究及其在微乳液体系中的应用”Macromol。

Atsushi Kajiwara, Kumiyo Maeda, Noritake Kubo, Mikiharu Kamachi: "Origin of 16-Line Spectra Observed in ESR Study of Radical Polymerization of tert-Buty1 Methacrylate : Clear Evidence for ESR Detection of Polymeric Propagating Radicals"Macromolecules. 36.

Atsushi Kajiwara、Kumiyo Maeda、Noritake Kubo、Mikiharu Kamachi：“甲基丙烯酸叔丁酯自由基聚合的 ESR 研究中观察到的 16 线光谱的起源：聚合传播自由基的 ESR 检测的清晰证据”大分子。

Atsushi Kajiwara and Mikiharu Kamachi: "Electron Paramagnetic Resonance Study of Conventional Radical Polymerizations Using Radical Precursors Prepared by Atom Transfer Radical Polymerizations"Polymer Preprints. 43(2). 144-145 (2002)

Atsushi Kajiwara 和 Mikiharu Kamachi：“使用原子转移自由基聚合制备的自由基前体对常规自由基聚合的电子顺磁共振研究”聚合物预印本。

Fu-sheng Du, Ming-Qing Zhu, Hai-Qing Guo, Zi-Chen Li, Fu-mian Li, Mikiharu Kamachi, Atsushi Kajiwara: "An ESR Study of Reversible Addition-Fragmentation Chain Transfer Copolymerization of Styrene and Maleic Anhybride"Macromolecules. 35. 6739-6741 (2002)

杜福生、朱明清、郭海清、李子晨、李富勉、Mikiharu Kamachi、Atsushi Kajiwara：“苯乙烯与马来酸酐可逆加成-断裂链转移共聚的ESR研究”