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通过超声降解聚(氧化乙烯-嵌段-氧化丙烯)共聚物产物的质谱分析测定一级键断裂。

Determination of primary bond scissions by mass spectrometric analysis of ultrasonic degradation products of poly(ethylene oxide-block-propylene oxide) copolymers.

机构信息

Department of Chemistry and Materials Engineering, Kansai University, Suita, Osaka 564-8680, Japan.

出版信息

J Mass Spectrom. 2010 Jul;45(7):799-805. doi: 10.1002/jms.1771.

Abstract

Ultrasonic degradation of poly(ethylene oxide-block-propylene oxide) copolymers consisting of a hydrophilic and a hydrophobic portion was studied with the aim to determine the location of bonds involved in the initial scission of the copolymers. LC-APCI-IT-MS and LC-APCI-orbitrap-MS were used for the detailed structural analysis of degradation products. The results indicated that initial bond scissions occurred principally at the boundary regions between backbones of polyethylene oxide (PEO) and polypropylene oxide (PPO) chains. Further structural analysis revealed the presence of oxygen adducts in the degradation products. Comparison with a thermal degradation carried out in helium atmosphere, one can conclude that the oxygen adducts are formed by radical reaction with water or dissolving oxygen molecules. The study demonstrated that chemical reactions as well as physical bond stress scissions are involved in the ultrasonic degradation of the copolymers.

摘要

聚(氧化乙烯-嵌段-氧化丙烯)嵌段共聚物的超声降解研究,其目的是确定共聚物初始断裂涉及的键的位置。采用 LC-APCI-IT-MS 和 LC-APCI-轨道阱-MS 对降解产物进行详细的结构分析。结果表明,初始键的断裂主要发生在聚氧化乙烯(PEO)和聚氧化丙烯(PPO)链的主链之间的边界区域。进一步的结构分析表明,在降解产物中存在氧加合物。与在氦气气氛中进行的热降解进行比较,可以得出结论,氧加合物是通过与水或溶解氧分子的自由基反应形成的。该研究表明,在共聚物的超声降解中,既有化学反应又有物理键的应力断裂。

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