林金福臺灣大學：材料科學與工程學研究所林上強Lin, Shanq-ChyangShanq-ChyangLin2007-11-262018-06-282007-11-262018-06-282005http://ntur.lib.ntu.edu.tw//handle/246246/55364本論文主要分成兩部分，第一部份是採用先前實驗室製備幾丁聚醣/蒙脫石奈米複合材料的技術，並改良一些實驗步驟，製備奈米級矽酸鹽幾丁聚醣溶液，並嘗試將其當作PMMA乳化聚合的乳化劑，以期藉由脫層蒙脫石改善PMMA的性質。 第二部份則為本論文的重點，以過硫酸鉀改質後的蒙脫石當作PMMA乳化聚合的起始劑，藉由聚合反應時產生之大量能量，使蒙脫石脫層，則可以製成PMMA奈米複合材料。另一方面，利用甲苯經由萃取將PMMA乳液移除，可得到奈米級矽酸鹽溶液。藉由TGA、DSC、TMA和MHT的分析，可得知藉由此法所得之PMMA奈米複合材料的熱性質跟機械性質皆有明顯的改善，由此可得知脫層蒙脫石已均勻分散於高分子乳液中。最後藉由TEM和AFM的分析，將脫層後之蒙脫石的大小尺寸確定出來，長與寬皆約為100 nm ~ 3000 nm，而厚度約為6~8 nm。This thesis contains two parts. In the first part, we adopted the previous method to produce the chitosan/montmorillonite nanocomposites. With some modification, we obtained a nanoscale silicate chitosan solution (NSCS) and it can be used as emulsifier for PMMA emulsion polymerization to improve the properties of PMMA. In the second part, we employed KPS-modified montmorillonite as an initiator for PMMA emulsion polymerization. During polymerization, montmorillonites were exfoliated and intermingled with PMMA in polymer particles to form a will-dispersed nanocomposite. On the basis of the analysis of TGA, DSC, TMA, and MHT, the thermal and mechanical properties of such-formed nanocomposite have been significantly improved. On the other hand, nanoscale silicate solution (NSS) can be afforded after removal of PMMA by extraction with toluene. Both length and width of exfoliated montmorillonite are about 100 ~ 3000 nm and the thickness of exfoliated montmorillonite is about 6 ~ 8 nm which are confirmed by TEM and AFM analysis.Table of Contents 中文摘要 ………………………………………………………………Ⅰ Abstract …………………………………………………………………Ⅱ Table of Contents ……………………………………………………….Ⅲ Table Lists ………………………………………………………………Ⅶ Figure Lists ……………………………………………………………..Ⅷ Chapter 1 Introduction …………………………………………………...1 1-1 Preface ……………………………………………………………….1 1-2 Review of Scientific Literatures …………………..…………………1 1-2-1 Brief Introduction of Montmorillonite ………………………...1 1-2-2 Organo-Modification of Montmorillonite ………..……………3 1-2-3 Manufacture of Polymer/Montmorillonite Nanocomposite …...4 1-2-4 Brief Introduction of PMMA ………………………………….6 1-2-5 Polymerization of Methyl Methacrylate ………………………7 1-2-6 Emulsion Polymerization of PMMA ………………………….8 1-2-7 The Literatures of PMMA/Clay nanocomposites ………..……9 1-2-8 Brief Introduction of Chitosan ……...………………………..10 1-2-9 The Properties of Chitosan …………...………………………11 1-2-9-1 The Solubility of Chitosan …………………...……...11 1-2-9-2 Properties of Chitosan Solution ……………...…...…12 1-2-9-3 The Mechanism of Degradation of Chitosan with KPS …………………………………………………12 1-2-10 Motivation …………………………………………………..13 Chapter 2 Experimental Section ………………………………………..15 2-1 Materials ……………………………………………………………15 2-2 Equipments …………………………………………………………16 2-2-1 Extraction of Montmorillonite ……………………………….16 2-2-2 Modification of Montmorillonite …………………………….16 2-2-3 Analysis of Thermal Properties……….………………………17 2-2-4 Analysis of Mechanical Properties …………………………...17 2-2-5 Molecular Properties and Structural Analysis ………………..18 2-3 Preparation of Montmorillonite and Its Modification ……………...19 2-3-1 Modification of Montmorillonite …………………………….19 2-3-1-1 Extraction of Montmorillonite ………………………19 2-3-1-2 Modification of Montmorillonite by KPS …………..20 2-3-2 Preparation of the Nanoscale-Silicate Chitosan Solution (NSCS) with KPS-MMT and Chitosan ……………………………….21 2-3-3 Purification of Methyl Methacrylate Monomer ……………...22 2-3-4 Emulsion Polymerization of MMA in Nanoscale-Silicate Chitosan Solution (NSCS) …………………………………...22 2-3-5 Emulsion Polymerization of MMA with KPS-MMT as an Initiator and Preparation of Nanoscale-Silicate Solution (NSS) …………………………………………………….…23 2-3-6 Analysis of Thermal Properties ………………………………24 2-3-6-1 Thermogravimetric Analyzer (TGA) ………………..24 2-3-6-2 Differential Scanning Calorimeter (DSC) …………..25 2-3-7 Measurements of Mechanical Properties …….……………...25 2-3-7-1 Micro Hardness Tester (MHT) ……………………...25 2-3-8 Investigation of The Morphology …….…………...…………26 2-3-8-1 X-Ray Diffraction (XRD) …………………………...26 2-3-8-2 Fourier Transform Infrared Spectrophotometer (FT-IR) ……...………………………………………27 2-3-8-3 Scanning Electron Microscope (SEM) ……………...27 2-3-8-4 Transmission Electron Microscope (TEM) …………28 2-3-8-5 Atomic Force Microscope (AFM) …………………..28 Chapter 3 Results and Discussions ……………………………………..29 3-1 Characterization of Pristine MMT and KPS-MMT Powders …........29 3-2 Emulsion Polymerization of MMA with Nanoscale-Silicate Chitosan Solution (NSCS) and their Morphology and Properties of Prepared Nanocomposite ……………………………………………………..30 3-2-1 Emulsion Polymerization of MMA with NSCS …………..…30 3-2-2 Morphology of PMMA/Montmorillonite Nanocomposites Prepared from The Nanoscale-Silicate Chitosan Solution (NSCS) ……………………………………………………....32 3-2-3 Thermal Properties of PMMA/Montmorillonite Nanocomposites Prepared from The Nanoscale-Silicate Chitosan Solution (NSCS) …………………………………...32 3-3 Emulsion Polymerization of MMA with KPS-MMT as an Initiator and their Morphology and Properties of PreparedNanocomposite .34 3-3-1 Emulsion Polymerization of MMA with KPS-MMT as an Initiator ………………………………………………………34 3-3-2 Morphology of PMMA/Montmorillonite Nanocomposites Prepared from The Emulsion Polymerization of MMA with KPS-MMT …………………………………………..……….35 3-3-3 Properties of PMMA/Montmorillonite Nanocomposites Prepared from The Emulsion Polymerization of MMA with KPS-MMT ……………………………………………..…….37 Chapter 4 Conclusions ………………………………………………….40 4-1 Properties of MMT and KPS-MMT….…………………………......40 4-2 Emulsion Polymerization of MMA with NSCS and their Morphology and Properties of Prepared Nanocomposites ….……………………40 4-3 Emulsion Polymerization of MMA with KPS-MMT as an Initiator and their Morphology and Properties of Prepared Nanocomposites .41 4-4 Properties of Nanoscale-Silicate Platelets (NSP) …………………..42 4-5 Future Work ………………………………………………………...42 Chapter 5 References …………………………………………………...443578034 bytesapplication/pdfen-US蒙脫石奈米級矽酸鹽幾丁聚醣溶液奈米級矽酸鹽溶液montmorillonitePMMANSCSNSSthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/55364/1/ntu-94-R92527011-1.pdf