Optical Characteritics of Hyperpolarized Polysulfonium

超极化聚锍的光学特性

• 批准号: 05650865
• 负责人: YAMAMOTO Kimihisa
• 金额: $ 1.41万
• 依托单位: Research Institute for Production Development
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05650865/
• 关键词: Polysulfonium; Hyperpolarization; Poly (arylene thioether); Photo-degradation; ポリアリーレンスルフイド

A new synthesis of aromatic sulfonium derivatives was established by oxidation of methylphenyl sulfide in acidic media. The polarized structure of the sulfonium compounds was proved by their molecular orbital calculation. (4-Methoxyphenyl) dimethyl sulfonium and (4-methylthiophenyl) methyl sulfonium were synthesized as a hyperpolarized aromatic sulfonium. It was found that (4-methylthiophenyl) methyl sulfonium decomposes to methylphenyl sulfide by UV-irradiation (360nm). The decomposition promotes in acetonilrile or protic solvents, such as methanol.Poly (arylene sulfonium) which has sulfonium and thioether bonds alternatively has been prepared by oxidative polymerization. The polysulfonium is feasible to convert to the corresponding polythioether with a high molecular weight and a high melting temperature. The polysulfonium also decomposes by light-irradiation and 4-methylthio-phenylthiobenzene is receovered in 80% yield as a starting low material. This photodegradation is applicable to the chemical amplified decomposition of other engineerng plastics.

通过甲基苯硫醚在酸性介质中的氧化反应，建立了芳香族锍衍生物的新合成方法。通过分子轨道计算证明了锍化合物的极化结构。合成了(4-甲氧基苯基)二甲基锍和(4-甲硫基苯基)甲基锍作为超极化芳香族锍。发现(4-甲硫基苯基)甲基锍在紫外线照射(360nm)下分解为甲基苯基硫醚。在乙腈或甲醇等质子溶剂中促进分解。通过氧化聚合制备了交替具有锍键和硫醚键的聚(亚芳基锍)。聚锍可以转化为相应的高分子量、高熔融温度的聚硫醚。聚锍也通过光照射分解，并以80％的收率回收4-甲硫基-苯硫基苯作为起始原料。这种光降解适用于其他工程塑料的化学放大分解。

项目成果

K.Oyaizu,N.Iwasaki,K.Yamamoto,H.Nishide,and E.Tsuchida: "Acid-Promoted Electron Transfer to Facilitate Oxidative Polymerization of diaryl Disulfides" Bull.Chem.Soc.Jpn.67. 1456-1461 (1994)

K.Oyaizu、N.Iwasaki、K.Yamamoto、H.Nishide 和 E.Tsuchida：“酸促进电子转移以促进二芳基二硫化物的氧化聚合”Bull.Chem.Soc.Jpn.67。

E.Shouji, S.Nishimura, K.Yamamoto, and E.Tsuchida: "IPoly (sulfonium cation) for Synthesis of High Molecular Weight Poly (phenylene sulfide)" Chem.Lett.403-406 (1994)

E.Shouji、S.Nishimura、K.Yamamoto 和 E.Tsuchida：“用于合成高分子量聚苯硫醚的 IPoly（锍阳离子）” Chem.Lett.403-406 (1994)

K.Yamamoto,E.Shouji,H.Nishide,E.Tsuchida: "Aryl Sulfide Formation Using the Sulfoxide‐Acid System for Synthesis of PPS via Poly(sulfonium cation)as a Precursor" J.Amer.Chem.Soc.115. 5819-5820 (1993)

K. Yamamoto、E. Shouji、H. Nishide、E. Tsuchida：“使用亚硫酸系统通过聚（锍阳离子）作为前体合成 PPS 形成芳基硫醚”J.Amer.Chem.Soc.115。 5819-5820 (1993)

E.Tsuchida,K.Yamamoto,M.Jikei,K.Miyatake,and H.Nishide: "Thermal Polymerization of Diaryl Disulfides to Yield Poly (arylene sulfide)." Macromolecules. 26. 4113-4117 (1993)

E.Tsuchida、K.Yamamoto、M.Jikei、K.Miyatake 和 H.Nishide：“二芳基二硫化物热聚合生成聚（亚芳基硫醚）”。

E.Tsuchida,M.Jikei,K.Miyatake,K.Yamamoto,and H.Nishide: "Synthesis of Oligo (2,3,5,6-tetramethylphenylene selenide)." Macromolecules. 26. 4732-4733 (1993)

E.Tsuchida、M.Jikei、K.Miyatake、K.Yamamoto 和 H.Nishide：“Oligo（2,3,5,6-四甲基亚苯基硒化物）的合成”。