ESR Studies on Fracture Mechanism of Solid Polymers Induced by Mechanical Fracture

固体聚合物机械断裂诱导断裂机理的ESR研究

• 批准号: 03650736
• 负责人: SAKAGUCHI Masato
• 金额: $ 1.28万
• 依托单位: Ichimura Gakuen Junior College
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03650736/
• 关键词: ESR; Polymer Materials; Fracture Mechanism; Heterolytic Scission; Mechano anion; Mechano Cation; Ionic Yield; 高分子材料の機械的破壊; ポリビニリデンフルオライド; 炭素ー炭素結合の不均一切断; カチオン重合; イソブチルビニルエーテル; ポリイソブチルビニルエーテル; 機械的破壊; イオン的開裂; スピントラップ法; アニオンラジカル; 電子スピン共鳴法; テ

We speculated that a mehcano anion and a mechano cation were produced by a heterolytic carbon-carbon bond scission due to the mechanical fracture of solid polymer.The production of the mechano anions was assigned by a detection of tetracyano ethylene anion radical (TCNE^<・^^->) from polymers fractured with TCNE in vacuo in the dark at 77 K using ESR method. The mechano anions were obtained from polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), and polyvinylidenefluouride (PVDF).The yields of the mechano anions (ratios of the heterolytic carbon-carbon bond scission) were obtained as PTFE (16 %), PE (27 %), PP(37 %), and PVDF (85 %)The production of PVDF mechano cation was assigned by the detection of polyisobutylvinylether (PIBVE) produced by a cationic polymerization on isobutylvinylether (IBVE) initiated by PVDF mechano cation. The molecular weights of PIBVE were obtained as Mw=6.2 X 10^4, Mn=2.3 X 10^4.We concluded that the mechano anions and the mechano cations were produced by the homolytic carbon-carbon bond scission of polymer main chain due to mechanical fracture of solid polymers, and the ionic yield was affected by a polarity of the carbon-carbon bond due to an electron affinity of substitution groups attached to the polymer chain.

我们推测，由于固体聚合物的机械断裂，由于异解碳-碳键断裂，产生了机械阴离子和机械阳离子。机械阴离子的产生是通过检测四氰乙烯阴离子自由基来确定的（TCNE^<· ^^->) 使用 ESR 方法从在黑暗中、在黑暗中用 TCNE 断裂的聚合物中获得机械阴离子。 (PTFE)、聚乙烯 (PE)、聚丙烯 (PP) 和聚偏二氟乙烯 (PVDF)。机械阴离子的产率（异解碳-碳键断裂的比率）为 PTFE (16 %)、PE (27 %) )、PP(37 %) 和 PVDF (85 %)PVDF 机械阳离子的产生通过检测来确定由PVDF机械阳离子引发的异丁基乙烯基醚(IBVE)的阳离子聚合反应生成聚异丁基乙烯基醚(PIBVE)。PIBVE的分子量为Mw=6.2 X 10^4，Mn=2.3 X 10^4。我们得出机械阴离子。机械阳离子是由于机械作用导致聚合物主链碳-碳键均裂而产生的。固体聚合物的断裂，并且由于连接到聚合物链的取代基的电子亲和力，离子产率受到碳-碳键极性的影响。

项目成果

Masato Sakaguchi: "A Generation Mechanism of Triboelectricity due to the Reaction of Mechano Radicals with Mechano Anions which are Produced by Mecahnical Fracture of Solid Polymer" Colloid & Polym, Sci.270. 621-626 (1992)

坂口正人：“由于机械自由基与固体聚合物机械断裂产生的机械阴离子反应而产生摩擦电的机制”胶体

Masao SAKAGUCHI: ""A Generation Mechanism of Triboelectricity due to the Reaction of Mechano Radicals with Mechano Anions which are Produced by Mechanical Fracture of Solid Polymer"" Colloid & Polym.Sci.270. 621-626 (1992)

坂口正男：“由于机械自由基与固体聚合物机械断裂产生的机械阴离子反应而产生摩擦电的机制”胶体

Sakaguchi,Masato: "A Generation Mechanism of Triboelectricity due to the Reaction of Mechano radicals with Mechano anions which are Produced by Mechanical Fracture of Solid Polymer" Colloid & Polym.Sci.,. 270. 621-626 (1992)

坂口正人：“由于机械自由基与固体聚合物机械断裂产生的机械阴离子反应而产生摩擦电的机制”胶体