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研究生：	陳兆彥 Chen, Chao-Yen
論文名稱：	表面起始聚合法製備以聚丙烯脫層之黏土奈米複合材料 Novel method to synthesize exfoliated PAN/DEA-MMT by surface-initiated redox polymerization
指導教授：	郭炳林 Kuo, Ping-Lin
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2007
畢業學年度：	95
語文別：	英文
論文頁數：	94
中文關鍵詞：	聚合、奈米複合材料、黏土
外文關鍵詞：	polyacrylonitrile, MMT, redox polymerization
相關次數：	點閱：61 下載：1
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本研究不同於傳統的製備方法，採用新型的方法來製備奈米複合材料。採用的單體丙烯晴主要用以生產合成纖維、合成橡膠、塑膠、ABS樹脂、碳材等，用途相當廣泛。首先使用二乙醇胺改質蒙脫土，再引入四價鈰鹽與改質後蒙脫土表面上的氫氧基團起始氧化自由基聚合反應，隨著單體丙烯晴加入的量不同而產生不一樣型態的黏土。由最後的鑑定結果得知本實驗的產物是插層 / 脫層型奈米複合材料，並且經由蒙脫土的導入成功提升聚丙烯晴的熱性質

第二部分的研究則提高二乙醇胺的量去改質黏土，希望可以得到完全脫層的複合材料，最後所得到的結果仍然是插層 / 脫層型奈米複合材料，因為所添加的單體量相同但是起始的聚合點卻增加，使得高分子鏈變短以致於不能達到完全脫層的效果，整體而言黏土的排列均一性增加，不會有像第一部分完全沒插層的部分。

本實驗提供一個很簡單的路徑在室溫下就可以得到高產率的插層/脫層混合型態奈米複合材料，相信也可以應用在其他相關複合材料上面，達到很好的效果。

Polymerization of acrylonitrile from surface of Diethanolamine ( DEA )-modified montmorillonite ( MMT ) by Ce( IV )/HNO3 redox system is an efficient way to produce delaminated MMT which got intercalated/exfoliated morphology. This method combines the advantages of redox system and inorganic filler: low reaction temperature, high yield, low activation energy, good physical properties, improvement of mechanical properties… Here we use acrylonitrile ( AN ) as monomer which can be used as a good material of acrylic fiber and ABS plastic; DEA intercalated MMT serves as the initiator of the system, amount of intercalating DEA was analyzed by EA. Nanocomposites made from different molar ratio of AN with respect to hydroxy groups ( OH ) of DEA was investigated by XRD, TGA, IR. Molecular weight of polyacrylonitrile ( PAN ) was accomplished before extraction of polyacrylonitrile from nanocomposites by LiCl/DMF solution. Molecular weight of PAN decreased as the amount of feeding AN decreased. D-spacings of MMT enlarged as the amount of feeding AN increased and basal reflection detected from XRD disappeared when amount of AN was 160 times as more as OH groups of DEA bounded on MMT. After embedded the nanocomposites in epoxy resin and sectioned it with ultramicrotome to 30nm. We can easily observed the nanoscale dispersion of nanocomposites characterized by TEM. PAN/DEA-MMT can be used as a kind of carbon source and a better PAN material to apply in many other aspects such as copolymer, fiber,etc…

Table of Contents

Abstract………………………………………i

Abstract (in chinese)………………………ii  

Acknowledgments………………………………iii 

Table of Contents……………………………v

List of Tables…………………………………viii

List of Figures………………………………ix

Chapter1 Introduction ………………………1 

Chapter2 Literature Review …………………4  

2.1Clays …………………………………………4 

2.1.1 General……………………………………4 

2.1.2 Modification of Clay……………………5 

2.2 Polymer/Clay Nanocomposites…………………7

2.2.1 Nanocomposites…………………………………7

2.2.2 Nanocomposite preparation………………………9

 (a) Exfoliation - adsorption…………………………………9
 
 (b) In situ intercalative polymerization………………10

 (c) Melt intercalation………………………………………10

 (d)Template synthesis………………………………………11 

2.2.3 Nanocomposite(clay) structures………………………11

2.2.4 Techniques used for the characterization           of nanocomposites………………13

 (a) XRD………………………………………………………13

 (b) TEM ……………………………………………………15

2.3 Polyacrylonitrile / Clay Nanocomposites ………………16

2.4 Redox Polymerization…………………………………………20

Chapter3 Experimental………………………………………………23

3.1 Materials………………………………………………………23

3.2 Sample Preparation…………………………………………25

3.2.1 Synthesis of DEA-MMT………………………………25

3.2.2 Syntheses of PAN/DEA-MMT nanocomposites……………27

3.2.3 Polymer recovery from nanocomposites………………29

3.2.4 Bury ……………………………………………………30

3.3 Characterizations…………………………………………31

Chapter4 Results and Discussion……………………………35

4.1 Characterizaion of Organo-Clay (DEA-MMT)……………35

4.1.1 XRD……………………………………………………35

4.1.2 TEM………………………………………………37

4.1.3 EA and ICP …………………………………39

4.2 Characterizaon of Nanocomposites (PAN/DEA-MMT ) prepared by surface-initiated polymerization………42

Part A. DEA-MMT5cec system……………………………42

4.2.1 Nanocomposites prepared with different amount of Ce(IV)……………………………………………………………42

4.2.2 Nanocomposites prepared with different amount of monomer…………………………………………………………45

4.2.2.1 Xrd ……………………………………………………45

4.2.2.2 Tem……………………………………………………48

4.2.2.3 IR…………………………………………………54

4.2.2.4 TGA……………………………………………………55

4.2.2.5 DSC ……………………………………………………58

4.2.2.6 Verification of carbon residue after TGA treatment……………………………61

4.2.2.7 Tacticity of  PAN recovered from nanocomposite…62

Part B. DEA-MMT10cec system……………………………………63

4.2.3 Morphology of Nanocomposite compared with pre-system ………………………………………………………63

4.2.3.1.Xrd…………………………………………………62

4.2.3.2 Tem……………………………………………………65

4.2.3.3 TGA…………………………………………………70

4.2.3.4 DSC……………………………………………………73

Chapter 5 Conclusion ………………………………………76

Referenes……………………………………………………78

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校內：2008-07-26公開
校外：2008-07-26公開

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