苯基及三氟丙基取代氨基硅烷的制备与表征

methyltrifluoropropylsilane;
design and variance analysis; synthesis.
IV
杭州师范大学硕士学位论文
苯基及三氟丙基取代氨基硅烷的制备与表征
目
录
摘 要 ............................................................................................................................................. II Abstract......................................................................................................................................... III 目 录 ............................................................................................................................................. V 第一章 绪论........................................................................................................................... 1 1.1 有机氨基硅烷 ........................................................................................................... 1 1.1.1 前言 ........................................................................................................... 1 1.1.2 有机氨基硅烷合成研究进展 ................................................................... 1 1.1.2.1 氯硅烷氨（胺）解合成有机氨基硅烷 ................................................... 2 1.1.2.2 通过 Si-M（金属）键与氯硅烷反应合成有机氨基硅烷 ...................... 3 1.1.2.3 N-M（金属）与有机硅烷反应合成有机氨基硅烷 ............................... 4 1.1.2.4 有机胺与含氢硅烷偶联反应制取有机氨基硅烷 ................................... 5 1.1.3 有机氨基硅烷的化学性质 ....................................................................... 6 1.1.3.1 水解反应 ................................................................................................... 7 1.1.3.2 与含有羟基化合物的醇解反应 ............................................................... 7 1.1.3.3 与各种酸类物质反应 ............................................................................... 7 1.1.3.4 与其他元素的氯化物反应 ....................................................................... 7 1.1.3.5 与金属反应 ............................................................................................... 7 1.1.4 有机氨基硅烷的应用 ............................................................................... 8 1.1.5 小结 ........................................................................................................... 8 1.2 含氟硅的二胺基化合物 ........................................................................................... 8 1.2.1 前言 ........................................................................................................... 8 1.2.2 新型聚酰亚胺二胺单体的合成研究 ....................................................... 9 1.2.2.1 含硅二胺单体的合成 ............................................................................... 9 1.2.2.2 含氟二胺单体合成 ................................................................................. 12 1.2.3 含氟硅二胺单体合成聚酰亚胺特性 ..................................................... 16 1.2.4 小结 ......................................................................................................... 17 本章参考文献......................................................................................................................... 18 第二章 双（N,N-二乙基）胺化合物的制备 ..................................................................... 21 2.1 前言......................................................................................................................... 21 2.2 实验部分................................................................................................................. 21 2.2.1 原料及试剂 ............................................................................................. 21 2.2.2 测试方法和仪器 ..................................................................................... 21 2.2.3 实验操作过程 ......................................................................................... 22 2.2.3.1 实验条件的探索 ..................................................................................... 22 2.2.3.2 原料及试剂的提纯 ................................................................................. 25 2.2.3.3 双（N,N-二乙基）胺化合物的制备 ..................................................... 25 2.3 结果与讨论............................................................................................................. 27 2.3.1 双（N,N-二乙基）胺甲基苯基硅烷 ..................................................... 27 2.3.1.1 双（N,N-二乙基）胺甲基苯基硅烷最佳合成条件确定 ..................... 27 2.3.1.2 双（N,N-二乙基）胺甲基苯基硅烷正交实验结果的验证 ................. 30
杭州师范大学硕士学位论文
苯基及三氟丙基取代氨基硅烷的制备与表征
trifluoropropylsilane and its value is the lowest in those three aminophenol isomers. The influences of substituting groups on the yield of the synthetic products have also been investigated. On the basis of the research conducted in Chapter Two and Chapter Three, a few conclusions have been summarized and are drawn in Chapter Four. Key Words: bis-(N, N-diethyl)amino-methylphenylsilane; bis-(aminobenzoyl)methylphenylsilane; bis-(N,N-diethyl)aminoorthogonal experiment
IIBaidu Nhomakorabea
杭州师范大学硕士学位论文
苯基及三氟丙基取代氨基硅烷的制备与表征
Abstract
As a novel polymeric material with high performance, silicones have been widely applied in many fields, such as aerospace, photo electronics, electrinic appliance, chemicals, medicals and so on, due to its excellent properties like moisture-proof, insulation, high- and low-temperature endurable, anti-aging and physiologically inert, et. al. In this thesis, organic aminosilanes and diamine monomers containing silicon and/or fluoro atoms have been synthesized from special cholosilanes, viz., methylphenyldichlorosilane and methyltrifluoropropyldichlorosilane. The thesis is consisted of four chapters. In Chapter One, the progresses in the studies of organic aminosilanes and diamine monomers containing silicon and/or fluoro atoms have been reviewed in detail. The methods of preparation and application of organic aminosilanes and diamine monomers containing silicon and/or fluoro atoms have been systematically summarized. The defects or deficiency of current researching method have been discussed in detail. Thus the research target and technical route for this thesis have been presented. In Chapter Two, two kinds of novel organic aminosilanes have been prepared from the reactions between diethylamine and methylphenyldichlorosilane or methyltrifloropropyldichlorosilane under low temperature, respectively. The orthogonal experiment design method has been used and the effects of temperature, reaction solvents, the feeding ratio and the reaction time on the yield of objective products have been investigated. The optimal results have been determined based on variance analysis and validated by checking experiments. The synthesized target products have been characterized by GC-MS, FT-IR, 1H NMR and 13C NMR. In Chapter Three, the reactions between methyltrifluoropropyldichlorosilane and aminophenols with different stereo hindrances have been investigated. The p-aminophenol can easily react with methyltrifluoropropyldichlorosilane and the yield is higher than the other two isomers, because the amino group and the phenolic hydroxyl are located at para positions and the amino group has little stereo hindrance on the reacting of phenolic hydroxyl group with Si-Cl bond of methyltrifluoropropyldichlorosilane. The yield for the reaction between m-aminophenol and methyltrifluoropropyldichlorosilane is somewhat lower than that of p- aminophenol because of the stereo hindrance of meta-positioned amino groups. When p-aminophenol is substituted by o-aminophenol, the main product between o-aminophenol and methyltrifluoropropyldichlorosilane is bis-(2-nitrobenzoyl)-methyltrifluoropropylsilane, which is resulted from the oxidization of bis-(2-aminobenzoyl)-methyltrifluoropropylsilane. The yield of bis-(2-aminobenzoyl) methyltrifluoropropylsilane is estimated from the completely reduction of bis-(2-nitrobenzoyl)-methylIII
硕 士 学 位 论 文
论文题目 作者姓名 指导教师
苯基及三氟丙基取代氨基硅烷的制备与表征 胡从达 蒋 剑 雄 (教 授)
伍川 (副教 授) 学科专业 所在学院 提交日期 有 机 化 学
材 料 与 化 学 化 工 学 院 2009 年 6 月 8 日
杭州师范大学硕士学位论文
苯基及三氟丙基取代氨基硅烷的制备与表征
I
杭州师范大学硕士学位论文
苯基及三氟丙基取代氨基硅烷的制备与表征
摘
要
有机硅高分子材料具有优异的防潮、 绝缘、 耐高低温、 耐老化以及生理惰性等优良性能， 已经成为新型高分子的后起之秀，并在航空航天、光电子电器、化工、医疗等领域得到广泛 的应用。本论文以特种氯硅烷（甲基苯基二氯硅烷和甲基三氟丙基二氯硅烷）为原料，合成 有机氨基硅烷及含氟硅二胺单体。全文共分为四部分。 第一章： 主要综述了有机氨基硅烷和含氟硅二胺单体的研究现状和进展， 系统总结了有 机氨基硅烷和含氟硅二胺单体的制备和应用方法， 详细讨论了现有合成方法存在的缺陷和不 足，并由此提出了本课题的研究目标和研究思路。 第二章： 以甲基苯基二氯硅烷或甲基三氟丙基二氯硅烷为原料， 分别与二乙胺在低温下 反应合成了一种新型的有机氨基硅烷。通过正交试验的方法，考察反应温度、反应介质、原 料摩尔比以及反应时间等因素对目标产物收率的影响， 利用方差分析确定最佳反应条件， 并 对最佳反应条件进行了实验验证； 利用红外光谱、 核磁共振等手段对产物结构进行了表征和 确认。 第三章：主要考察了甲苯溶剂回流条件下，甲基三氟丙基二氯硅烷与不同空间位阻的 氨基苯酚化合物发生取代反应过程中的影响因素， 对氨基苯酚中氨基和酚羟基处于对位， 空 间位阻最小，其与甲基三氟丙基二氯硅烷反应所得产物收率最高；由于空间位阻影响，间氨 基苯酚与甲基三氟丙基二氯硅烷反应所得产物收率次之； 邻氨基苯酚与甲基三氟丙基二氯硅 烷反应，所得产物中的氨基被氧化为硝基，将硝基化合物折算为对应氨基化合物，其收率在 氨基苯酚化合物同分异构体中最低。此外，还考察了取代基种类对合成产物收率的影响。 第四章：对本文研究结果进行了总结，形成了本文的结论。 关键词：双（N,N-二乙基）胺甲基苯基硅烷；双（N,N-二乙基）胺甲基三氟丙基硅烷； 双（氨基苯氧基）甲基苯基硅烷；正交实验与方差分析；合成
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