有机硅格氏试剂及羟丙基二硅氧烷的合成与表征

发布时间：2018-07-03 14:20

本文选题：有机硅格氏试剂 + 六甲基磷酰三胺　；参考：《山东大学》2017年硕士论文

【摘要】：与碳原子相比,硅原子既具有相似性,又具其独特性。碳的格氏试剂是有机化学中至关重要的中间体,另外,关于硅金属键的研究中缺乏硅镁键的报道,因此我们提出了以氯硅烷、镁为原料制备有机硅格氏试剂的研究思路。我们以带有不同烷基的氯硅烷、镁屑为原料,六甲基磷酰三胺(HMPA)等为溶剂,成功制备了四种带有不同烷基的有机硅格氏试剂,分别是三甲硅基氯化镁、二甲基苯基氯化镁、甲基二苯基硅基氯化镁、三苯基硅基氯化镁。我们不仅得到了各个反应的最佳反应温度、反应物配比、催化剂等,还对各产物进行了1 HNMR、29SiNMR表征。通过冷却有机硅格氏试剂,我们发现产物中产生了无色透明针状晶体,对得到的晶体进行测试,得知配合物分子式为MgCl2·2HMPA。通过所得晶体结构,我们推测有机硅格氏试剂中也可能存在类似碳格氏试剂中的Schlenk平衡。该晶体的得出进一步验证了有机硅格氏试剂的产生。羟烃基二硅氧烷是合成高性能有机硅改性聚氨酯材料及有机硅改性聚脲等材料的重要原材料。1,3-双(γ-羟丙基)-1,1,3,3-四甲基二硅氧烷是羟烃基封端剂中应用较多的一种,其主要制备方法有硅氢加成法和有机金属合成法,但是硅氢加成法需要羟基保护,反应步骤繁琐,有机金属合成法对操作要求高,不适于工业生产。我们用新的合成方法成功制备了 1,3-双(丫-羟丙基)-1,1,3,3-四甲基二硅氧烷。我们通过乙酸烯丙酯与二甲基氢氯硅烷发生硅氢加成反应生成碳官能硅基羧酸酯,该羧酸酯在酸性条件下水解后通过简单提纯便可直接得到1,3-双(γ-羟丙基)四甲基二硅氧烷。该方法步骤简单、操作方便,并且反应中副反应少,产物收率高且纯度高。
[Abstract]:Compared with carbon atoms, silicon atoms have both similarity and uniqueness. Grignard reagent of carbon is an important intermediate in organic chemistry. In addition, there is no report of silicon and magnesium bond in the study of silicon metal bond. Therefore, we put forward the research idea of preparing organic silicon Grignard reagent using chlorosilane and magnesium as raw material. Four organosilyl Grignard reagents with different alkyl groups were successfully prepared by using chlorosilane with different alkyl groups, magnesium chips as raw materials, hexamethylphosphoryltriamine (HMPA) as solvent, trimethylsilyl magnesium chloride and dimethyl phenyl magnesium chloride, respectively. Methyl diphenylsilyl magnesium chloride, triphenylsilyl magnesium chloride. Not only the optimum reaction temperature, reactant ratio and catalyst were obtained, but also the products were characterized by 1HNMR-29Si NMR. By cooling the organosilicon Grignard reagent, we found that colorless and transparent needle-like crystal was produced in the product. The obtained crystal was tested and the molecular formula of the complex was found to be MgCl _ 2 _ 2H _ MPA. Based on the crystal structure, we speculate that the Schlenk equilibrium may also exist in the organosilicon Grignard reagents similar to the carbon Grignard reagents. The result of the crystal further verifies the production of organosilicon Grignard reagent. Hydroxyalkyldisiloxane is one of the most important raw materials for the synthesis of high performance silicone modified polyurethane and silicone modified polyurea. The main preparation methods are hydrosilyl addition method and organometallic synthesis method, but hydrosilyl addition method needs hydroxyl protection, the reaction steps are complicated, and the organometallic synthesis method is not suitable for industrial production because of its high operational requirements. A new synthetic method has been developed for the preparation of 1'3'- bis (A- hydroxypropyl)-1'1'1'3'3 '-tetramethyl disiloxane. The carboxylic ester was synthesized by the addition reaction of allyl acetate and dimethylhydrochlorosilane. The carboxylic ester was hydrolyzed under acidic conditions and purified simply to obtain 1k3- bis (纬 -hydroxypropyl) tetramethyl disiloxane directly. The method is simple, easy to operate, less side reaction, high yield and high purity.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ264.1

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