以chlorosilane改質D4R unit, Si8O208-

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姓名

愛美嘉(Widho-Retno Amijaya) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

以chlorosilane改質D4R unit, Si8O208-
(Modification of D4R unit, Si8O208-, with Chlorosilane)

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摘要(中)

Silsesquioxane是一分子的球型矽化物(spherosilicates)，其分子式為[RSiO2.5]n，R為有機或無機官能團，n可介於4及30之間，一般為6、8、10或12。本研究主要是將D4R silicate (Si8O20)8-¬¬以dimethylchlorosilane改質成dimethylsilylated D4R unit ((HSiMe2O)8-Si8O12)，或以trimethylchlorosilane改質成trimethylsilylated D4R unit ((SiMe3O)8-Si8O12)。Dimethylsilylated D4R unit ((HSiMe2O)8-Si8O12)可當做中間物用於合成具有化學活性的H-terminated D4R unit，而H-terminated D4R unit可連接其他官能基，如：methacrylate, epoxy group, or long chain alkyl group。
Octaanion的矽烷化(silanation)一般於兩相系統(two phase system)中進行，亦即octaanion的hydrated tetramethyl ammomium salt在水相溶液中，而silane則溶於有機相溶液中進行反應。文獻中以dimethylchlorosilane及trimethylchlorosilane改質的octaanion的產率分別為83%及93%，而octaanion中chlorosilane及Si莫耳比為4:1。根據文獻資料，此反應使用大量過量的chlorosilane，所以此反應系統仍有可改進的空間。
本研究一開始先研究hexane-methanol-water tertiary system的相圖，並確認出其形成單相的區域，之後再測試含有octaanion salt的相界(phase boundary)變化。由研究中所得之含有octaanion salt的hexane-methanol-water tertiary system的單相區域，在反應中有助於octaanion salt的溶解，且有利octaanion salt與silane的反應過程。因此，經由此改質法可得到較高的產率，並減少chlorosilane的使用量。本研究結果以FTIR, DSC, TGA, and NMR等方式鑑定。

摘要(英)

Silsesquioxane is molecular spherosilicates with the formula [RSiO2.5]n, where R is an inorganic or organic group and n can be between 4 and about 30, but typically 6, 8, 10 or 12. We focus our effort to modify D4R silicate (Si8O20)8- with dimethylchlorosilane and trimethylchlorosilane to make dimethylsilylated D4R unit ((HSiMe2O)8-Si8O12) and trimethylsilylated D4R unit ((SiMe3O)8-Si8O12) respectively. Dimethylsilylated D4R unit ((HSiMe2O)8-Si8O12) can be used as an intermediate for synthesizing spherical siloxanes owing the chemical reactivity of the a H-terminated D4R unit to connect with another function for example; methacrylate, epoxy group, or long chain alkyl group.
The silanation of octaanion is typically carried out in a two phase system, where the hydrated tetramethyl ammomium salt of octaanion exists in the aqueous phase, while the silane dissolved in an organic phase. The yield for octaanion silanized with dimethylchlorosilane and trimethylchlorosilane was 83% and 93% respectively (molar ratio chlorosilane to Si in octaanion = 4 : 1). Since they used a large excess of chlorosilane, there is a large room to improve the reaction system.
We will start by examining the phase diagram of hexane-methanol-water tertiary system and identify the region where a single phase is formed, and test the shift of phase boundary when octaanion salt is included. The reaction will then be carried out as much as possible in the single phase domain to facilitate the dissolution of the salt as well as its immediate reaction with silane. We believe that through such modification higher yield can be achieved with less amount of chlorosilane. The result will then be characterized with FTIR, DSC, TGA, and NMR.

關鍵字(中)

★ Trimethylsilylated D4R unit
★ Dimethylsilylated D4R Unit
★ Octaanion
★ 改質
★ 的矽烷化
★ D4R Unit

關鍵字(英)

★ Dimethylsilylated D4R Unit
★ Octaanion
★ D4R unit
★ Silanation
★ Modification
★ Trimethylsilylated D4R unit

論文目次

Abstract…………………………………………………………………2
Acknowledgements………………………………………………………3
Table of Contents…………………………………………………….4
List of Figures………………………………………………………………….8
List of Tables………………………………………………………………….10
CHAPTER 1. GENERAL INTRODUCTION AND SCOPE OF THIS THESIS.11
1.1 Silsesquioxane introduction and history………….11
1.1.1 Polyhedral Oligomeric Silsesquioxane (POSS)…….11
1.1.1.1 Introduction……………………………………………..11
1.1.1.2 Classification of POSS…………………………………12
1.1.2 General Step to Synthesis POSS………………………13
1.1.3 History…….…………………………...……………….16
1.2 Synthesis D4R Silicates (Si8O20)8-…………………18
1.2.1 Synthesis D4R silicates by sol-gel approach…….18
1.2.2 Ways to synthesis D4R silicates (Si8O20)8-………19
1.2.3 Property of Octa(tetraammonium)silsesquioxane ([Me4N]8[OSiO1.5]8.xH2O) salt............................21
1.3 Silane functionalized cubic siloxane…………..…22
1.3.1 Silanization Process………………………………………………………………..22
1.3.2 Silanization with different silane…………………22
1.3.2.1 Dimethylsilylated D4R unit ((HSiMe2O)8-Si8O12)…23
1.3.2.1.1 Procedure to synthesize dimethylsilylated D4R unit.....................................................23
1.3.2.1.2 Property of dimethylsilylated D4R unit ((HSiMe2O)8-Si8O12)…..............................................25
1.3.2.2 Trimehtylsilylated D4R unit ((SiMe3O)8-Si8O12)…25
1.3.2.2.1 Procedure to synthesize trimethylchlorosilane D4R unit………….........................................25
1.3.2.2.2 Property of trimethylsilylated D4R unit ((SiMe3O)8-Si8O12)……............................................27
1.4 Scope of this thesis………………………………………………………….......27
CHAPTER 2. EXPERIMENTAL………………………….……………….30
2.1 Materials………………………………………………………..30
2.1.1 TEOS (tetraethylorthosilicate)………………………….30
2.1.2 TMAOH (tetramethylammonium hydroxide)…………………31
2.1.3 Dimethylchlorosilane……………………………………….31
2.1.4 Trimethylchlorosilane………………………………………31
2.1.5 Hexane………………………………………………………………….31
2.1.6 Methanol……………………………………………………….32
2.1.7 Ethanol………………………………….…………………...32
2.2 Reaction and Calculation…………………….………………32
2.2.1 D4R silicates, Si8O208-……………………………………32
2.2.2 Dimethylsilylated D4R unit, ((HSiMe2O)8-Si8O12)….34
2.2.3 Trimethylsilylated D4R unit, ((SiMe3O)8-Si8O12)….35
2.2.4 Dimethyl-trimethylcilylated D4R unit, Si8O20 {SiH(CH3)2}4 {Si(CH3)3}4.....................................36
2.3 Methods……………………………………………………………37
2.3.1 Preparation D4R silicates, (Si8O20)8-………….……37
2.3.2 Silanization of D4R silicates with chlorosilane…..38
2.3.2.1 Dimethylsilylated D4R unit, ((HSiMe2O)8-Si8O12)..38
2.3.2.2 Trimethylsilylated D4R unit, ((SiMe3O)8-Si8O12).39
2.3.2.3 Dimethyl-trimethylsilylated D4R unit, Si8O20 {SiH(CH3)2}4 {Si(CH3)3}4.....................................40
2.4 Characterizations……………..……………………….41
2.4.1 EA (Elemental Analysis)……………..……………………41
2.4.2 FTIR (Fourier Transform Infrared Spectroscopy)..42
2.4.3 Differential Scanning Calorimetry (DSC)………….42
2.4.4 Thermogravimetric Analysis (TGA)………………....42
2.4.5 Nuclear Magnetic Resonance (NMR)……………………42
CHAPTER 3. RESULT AND DISCUSSION…………...…………………52
3.1 D4R silicates, Si8O208-………………………………………52
3.1.1 Elemental Analysis Result…………………………………52
3.1.2 FTIR Spectra of octaanion TMA8 Si8 O20 x H2O…………………………………............................54
3.1.3 Thermal Analysis of octaanion TMA8 Si8 O20 x H2O….55
3.1.4 Solid State 29Si Nuclear Magnetic Resonance…………57
3.2 Silanization of D4R Silicates……………………..……..58
3.2.1 Dimethylsilylated D4R unit……………………………….58
3.2.1.1 FTIR Spectra Result…………………………………….58
3.2.1.2 Nuclear Magnetic Resonance…………………………….60
3.2.1.2.1 Solid State 29Si Nuclear Magnetic Resonance…..60
3.2.1.2.2 Liquid 1H Nuclear Magnetic Resonance…………….61
3.2.1.3 Thermal analysis of dimethylsilylated D4R unit...63
3.2.1.3.1 Thermogravimetric Analysis………………………….63
3.2.1.3.2 Differential Scanning Calorimetry…………………65
3.2.2 Trimethylsilylated D4R unit …………………...………66
3.2.2.1 FTIR Spectra Result………………………………………66
3.2.2.2 Nuclear Magnetic Resonance…………………………….67
3.2.2.2.1 Solid State 29Si Nuclear Magnetic Resonance……67
3.2.2.2.2 Liquid 1H Nuclear Magnetic Resonance…………….69
3.2.2.3 Thermal analysis of trimethylsilylated D4R unit…72
3.2.2.3.1 Thermogravimetric Analysis………………………….72
3.2.2.3.2 Differential Scanning Calorimetry…………………74
3.2.3Dimethyl-trimethylsilylated D4R unit ……………….…75
3.2.3.1 FTIR Spectra Result………………………………………75
3.2.3.2 Differential Scanning Calorimetry……………………77
3.2.3.3 Liquid 1H Nuclear Magnetic Resonance……………….78
CHAPTER 4. CONCLUSION………………………...………………….82
References List……………………………………………………..83

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指導教授

蔣孝澈(Anthony S.T. Chiang)

審核日期

2009-8-21

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