波谱学杂志 ›› 2006, Vol. 23 ›› Issue (2): 187-192.

• 4 • 上一篇    下一篇

丙烯腈γ辐射聚合的NMR研究

  

  1. 新疆大学 理化测试中心,新疆 乌鲁木齐830046
  • 收稿日期:2005-10-14 修回日期:2005-10-26 出版日期:2006-06-05 发布日期:2006-06-05
  • 基金资助:

    波谱与原子分子物理国家重点实验室资助课题(T012406).

60Co γ Irradiation Induced Polymerization of Acrylonitrile Studied by NMR Spectroscopy

  1. The Center of Analysis and Measurement of Xinjiang University, Urumqi 830046, China
  • Received:2005-10-14 Revised:2005-10-26 Online:2006-06-05 Published:2006-06-05
  • Supported by:

    波谱与原子分子物理国家重点实验室资助课题(T012406).

摘要:

1H NMR、13C NMR谱、自旋-晶格弛豫时间(T1)和自旋-自旋弛豫时间(T2)研究了丙烯腈在60Co γ射线辐射聚合后的大分子结构变化与大分子链的运动. 结果表明随着辐射剂量增大,在单体形成聚合物的过程中,聚合物主链上出现了少量的-OH基团,继续增大辐射剂量, -OH部分被氧化. 对聚合物溶液的变温氢谱的研究表明,溶剂中的残余水与上述-OH形成氢键,且随着温度升高氢键被破坏,同时H2O与-OH之间还存在着质子交换. 利用13C NMR谱对丙烯腈辐射聚合的产物进行了序列结构分析. 对T1T2的研究表明,辐射剂量的增大并未影响到聚丙烯腈的链运动,证明了在丙烯腈的辐射聚合过程交联反应未发生.

关键词: NMR, 自旋-晶格弛豫时间(T1), 自旋-自旋弛豫时间(T2), 氢键, 质子交换,  序列结构

Abstract:

60Co γ irradiation induced polymerization of acrylinitrile (AN) was studied by 1H and 13C NMR spectroscopy. The results show that the signal intensities of AN monomer peaks decrease after irradiation, and this is accompanied by the appearance of a polymer peak, whose signal intensity increases with the irradiation dose. The sequence distribution of polyacrylonitrile was assigned using 13C NMR data. The results of variable temperature experiments indicate that there exist hydrogen bonds, as well as proton exchange, between residual water and the -OH group on the polymer. Relaxation time measurements show that the motion of polymer segments is not influenced significantly by the increase of irradiation dose.

Key words: NMR, spin-lattice relaxation time, spin-spin relaxation time, hydrogen bond, proton exchange, sequence structure

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