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.

建立了一种在酸性介质中氧化甲苯硫醚合成芳香族锍衍生物的新方法。通过分子轨道计算证明了它们的极化结构。合成了一种超极化芳香族锍化合物（4-甲氧苯基）二甲基锍和（4-甲硫基苯基）甲基锍。结果表明，在紫外光照射下（360 nm），（4-甲硫基苯基）甲基锍可分解为甲基苯硫醚。在乙腈或甲醇等质子溶剂中，聚芳硫醚的分解反应得到促进，通过氧化聚合制备了硫醚键和硫醚键交替存在的聚芳硫醚。该聚锍可转化为相应的高分子量和高熔融温度的聚硫醚。聚硫鎓也可在光照下分解，以80%的收率回收了4-甲硫基苯硫基苯作为起始原料。这种光降解作用也适用于其它工程塑料的化学放大降解。

项目成果

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.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。

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”。