多环芳基聚硅氧烷的合成及在弹性石英毛细管气相色谱中的应用

【作者】 桑圣凯；

【导师】 吴波；

【作者基本信息】 山东大学 ， 分析化学， 2008， 硕士

【摘要】 本文作者首先研究了多种芳基取代环戊二烯酮合成。芳基取代的环戊二烯酮很早就已经有人研究了,从基本的芳香醛合成偶姻,经催化氧化成偶酰,再与脂肪酮或芳香酮经过一步或两步反应得到相应的芳基取代的环戊二烯酮。但是大家的注意力多集中于全芳基取代环戊二烯酮,很少有人研究含部分脂肪基取代的芳基环戊二烯酮。作者借鉴了过去研究者的方法合成了一系列的芳基取代环戊二烯酮:四苯基环戊二烯酮(Ⅰ):3,4—二(4—甲氧基苯基)—2,5—二苯基环戊二烯酮(Ⅱ);3,4—二(呋喃—2—基)—2,5—二甲基环戊二烯酮(Ⅲ);苊式环戊二烯酮(Ⅳ);2,5—二甲基—3,4—二苯基环戊二烯酮(Ⅴ):3,4—二苯基环戊二烯酮(Ⅵ):2—甲基—3,4—二苯基环戊二烯酮(Ⅶ):2—乙基—3,4—二苯基环戊二烯酮(Ⅷ),并通过红外和核磁对它们进行了表征。其中化合物(Ⅵ)(Ⅶ)(Ⅷ)没有见到文献报道。作者选择其中的四苯基环戊二烯酮(Ⅰ)与含双键的聚甲基硅氧烷通过Diels-Alder反应合成带有四苯基苯基的聚甲基硅氧烷高分子,在对其进行提纯后,用静态法涂敷在弹性石英毛细管上,对涂敷固定相的弹性石英毛细管柱各个方面进行评价,包括选择性、极性、柱效、内壁惰性、耐温性等。重点考察其对芳烃如苯基取代物、多环芳烃(PAH)的分离选择性。考察结果表明涂敷四苯基苯基聚甲基硅氧烷固定相的弹性石英毛细管柱具有不低于4000P/m的柱效,有比较好的惰性,属于中等极性的固定相(总相常数为737),最高使用温度为330℃。对液体石蜡、煤焦油和含有多环芳烃样品的分离证明四苯基苯基聚甲基硅氧烷固定相对烷烃和芳烃类物质有较好的分离效果。对于多环芳基取代的聚甲基硅氧烷固定相的研究是有意义的。更多还原

【Abstract】 At first the synthesis of a various of aryl-substituted cyclopentadienones are studied.Aryl-substituted cyclopentadienones were studied long ago.The benzoins, synthsised from the aromatic aldehydes,change to benzils through catalyzed oxidation.Then the benzils react with aryl- substituted ketones or alkyl- substituted ketones to form the aryl-substituted cyclopentadienones with one or two steps.But much attention were payed to the all aryl-substituted cyclopentadienones,few people studied the part aryl-substituted cyclopentadienones.The author synthesises a serious of aryl-substituted cyclopentadienones with the former researcher methods,such as 2,3,4,5-tetraphenylcyclopenta-2,4-dienone(Ⅰ),3,4-bis(4-methoxyphenyl)- 2,5-diphenylcyclopenta-2,4-dienone(Ⅱ),3,4-di(furan-2-yl)-2,5-dimethyicyclopenta-2, 4-dienone(Ⅲ),7,9-diphenyl-6bH-bicyclo[3.2.0]hepta-1(5),1,4-trieno[6,7-a]-acenaphthylen-8 (9bH)-one(Ⅳ),2,5-dimethyl-3,4-diphenylcyclopenta-2,4-dienone (Ⅴ),3,4-diphenylcyclopenta-2,4-dienone(Ⅵ),2-methyl-3,4-diphenylcyclo-penta-2, 4-dienone(Ⅶ),2-ethyl-3,4-diphenylcyclopenta-2,4-dienone(Ⅷ).They are all analysed with H-NMR and IR.The compounds(Ⅵ)、(Ⅶ)and(Ⅷ)are first peported in literature.2,3,4,5-Tetraphenylcyclopenta-2,4-dienone(Ⅰ)is choosed to react with vinyl polysiloxane to form tetraphenyl phenyl polysiloxane through Diels-Alder reaction. After purification the product is coated on fused silica capillary columns with static method.Chromatographic properties like selectivity,polarity,separation efficiency, inertness,bleeding and so on of the capillary were evaluated,especially the selectivity of aromatic hydrocarbon such as substitutes of benzene,polycyclic aromatic hydrocarbon(PAH).The investigation reveals that the fused silica capillary columns coated with tetraphenyl phenyl polysiloxane posseses superior separation efficiency(no less than 4000 P/m)and high intemess.It belongs to medium polar stationary phase(the constant of overall polarity is 737),the maximum allowable operating temperature is 330℃.The separation of the liquid paraffin,coal tar and polycyclic aromatic hydrocarbon confirms that tetraphenyl phenyl polysiloxane stationary phase has superior separation efficiency to alkanes and aromatic hydrocarbon compounds.It is significative to study the polysiloxane with polycyclic aromatic group.更多还原