Effect of Temperature on Formation of Polymer in Oxidation of Methyl Linoleate

Methyl Linoleate 산화중 중합체 형성에 미치는 온도의 영향

  • Published : 1996.06.30

Abstract

To investigate the effect of heating conditions on the polymerization of methyl linoleate, the esters were heated at $60^{\circ}C,\;90^{\circ}C,\;120^{\circ}C$ and $150^{\circ}C$, respectively, with sparging oxygen for different periods of time. On the basis of the peroxide curve obtained at each of the four temperatures, four heating times were chosen for the analysis of the polymers and total oxidation products. Significant linear relationships were found between polymer contents and total oxidation product contents. The contents of polymers and their linkage types were analyzed by High Performance Size Exclusion Chromatography. The polymers formed at four temperatures were qualitatively identified as dimers. The dimers with peroxide linkages were detected from methyl linoleate oxidized at $60^{\circ}C\;and\;90^{\circ}C$ but they were not detected from methyl linoleate oxidized at $120^{\circ}C\;and\;150^{\circ}C$. Therefore, all dimers formed at $120^{\circ}C\;and\;150^{\circ}C$ seemed to be the ones with ether linkage or carbon to carbon linkage. The degradation rate of the dimers with peroxide linkages at $90^{\circ}C$ was faster than at $60^{\circ}C$.

Methyl linoleate의 중합체 형성에 미치는 온도의 영향을 조사하기 위해 산소를 주입하인서 $60^{\circ}C,\;90^{\circ}C,\;120^{\circ}C,\;150^{\circ}C$)에서 산화시켰다. 각 온도에서 시간에 따른 과산화물가의 변화 곡선을 기초로하여 각 온도에서 4가지의 산화 시간을 선정하였다. 중합체 함량 및 중합체 결합 특성은 High Performance Size Exclusion Chromatography로 분석하였다. 각 온도에서 만화 시간에 따른 총 산화물 함량과 중함체 함량사이에는 높은 상관관계를 나타냈다. 모든 온도에서 생성된 중합체는 이중체로 확인되었으며, $60^{\circ}C$$90^{\circ}C$에서는 C-O-O-C 결합상태인 이중체를 확인할 수 있었으나, $120^{\circ}C$$150^{\circ}C$에서는 C-O-O-C결합형태를 갖는 이중체는 확인할 수 없었다. 따라서 $120^{\circ}C$$150^{\circ}C$에서 생성된 이중체는 C-O-C/C-C결합 형태인 것으로 추정되었다. 또한, C-O-O-C결합 형태의 이중체는 $60^{\circ}C$보다는 $9^{\circ}C$에서 보다 쉽게 파괴되는 경향을 나타냈다.

Keywords