Synthesis of Polyarylene sulfonium as a Novel Polymer and Its Properties based on the Hyper-polarizedpi-Conjugate Structure

基于超极化π共轭结构的新型聚合物聚亚芳基锍的合成及其性能

• 批准号: 09650982
• 负责人: YAMAMOTO Kimihisa
• 金额: $ 2.5万
• 依托单位: Keio University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650982/
• 关键词: Polysulfonium; Hyper-polarization; Electronic Materials; pi-Conjugate structure

Poly[ary] or alkyl 4-(phenylthio)phenylsulfonium trifluoromethanesulfonate]s were synthesized by a sulfoxide-acid reaction from the corresponding arylsulfoxides. The nucleophilic reaction of the resulting poly(sulfonium) salts were investigated in order to elucidate the chemical reactivity. The dealkylation of the sulfonium salts with a nucleophile such as halide ions takes place effectively to yield poly(arylene sulfide), which is also compared to the controlled reaction of the corresponding monomeric sulfonium salts. Kinetic analysis by means of UV-vis spectroscopy reveals that the dealkylation proceeds quantitatively to convert to the thioether bond from the sulfonium one. The reaction rate constants of the dealkylation by the halide ions are in the order of I > Br > CLWe developed the direct synthesis of polysulfonium ion. Benzene allows to react with sodium methanesulfinate in trifluoromethane sulfonic acid. First phenylene polymers linked by sulfonium group were obtained by the simple and one-post synthesis. We also found that many sulfonium compounds were synthesized by the superacidified reaction of sulfides and ethers as a direct synthesis of sulfonium derivatives. The properties of novel sulfonium compounds are investigated in progress.

聚[Ary]或烷基4-（苯基硫硫代）苯基硫硫磺酰甲磺酸盐由来自相应的芳基硫氧化物的硫氧化物酸反应合成。研究了所得聚（磺硫）盐的亲核反应，以阐明化学反应性。磺基盐与亲核试剂（如卤化物离子）的交易二烷基化有效地产生了聚（芳基硫化物），这也与相应单体磺基盐的受控反应进行了比较。通过UV-VIS光谱法分析动力学分析表明，DealKylation数量地进行了从磺基硫的硫纤维转换为硫醚键。卤离子离子的反应速率常数按照i> br> clwe的顺序开发了多硫磺基离子的直接合成。苯允许在三氟甲烷磺酸中与甲硫酸钠反应。通过简单和一柱合成获得了由硫基团连接的第一苯基聚合物。我们还发现，许多磺基化合物是通过硫化物和醚的超固定反应作为磺基衍生物的直接合成而合成的。研究了新型磺基化合物的特性。

项目成果

K.Yamamoto et al.: "Synthesis and Nucleopjhilic Dealkylation of Poly[alkyl-(4-(phenylthio) phenyl) sulfonium trifluoromethanesulfonate]s" Macromolecules. 31. 1202-1207 (1998)

K.Yamamoto 等人：“聚[烷基-(4-(苯硫基)苯基)三氟甲磺酸锍]大分子的合成和亲核脱烷基化”。

K.Yamamoto et al.: "Synthesis and Nucleopjhilic Dealkylation of Poly[alkyl-(4-(phenylthio)phenyl)sulfonium trifluoromethanesulfonate]s" Macromolecules. 31. 1202-1207 (1998)

K.Yamamoto 等人：“聚[烷基-(4-(苯硫基)苯基)三氟甲磺酸锍]大分子的合成和亲核脱烷基化”。

K.Yamamoto et al.: "Superacidified Reaction of Sulfides and Esters for the Direct Synthesis of Sulfonium Derivetives" J.Org.Chem.63. 7522-7524 (1998)

K.Yamamoto 等人：“用于直接合成锍衍生物的硫化物和酯的超酸化反应”J.Org.Chem.63。

K.Yamamoto et al.: "Synthesis and Nucleophilic Dealkylation of Poly[alkyl-4(phenylthio)phenyl sulfonium trifluoromethane sulfonatels." Macromolecules,. 31(in press). (1998)

K.Yamamoto 等人：“聚[烷基-4（苯硫基）苯基锍三氟甲磺酸盐的合成和亲核脱烷基化”。

K.Yamamoto et al.: "Superacidified Reaction of Sulfides and Esters for the Direct Synthesis of Sulfonium Derivertives" J.Org.Chem.63. 7522-7524 (1998)

K.Yamamoto 等人：“用于直接合成锍衍生物的硫化物和酯的超酸化反应”J.Org.Chem.63。