林金福臺灣大學：高分子科學與工程學研究所簡安廷Chien, An-TingAn-TingChien2007-11-292018-06-292007-11-292018-06-292006http://ntur.lib.ntu.edu.tw//handle/246246/62899A series of partial and fully water-soluble monomers, including methyl methacrylate, methyl acrylate, vinyl acetate, acrylamide, and glycidyl methacrylate, were used to fabricate polymer-Montmorillonite(MMT) nanocomposite through soap-free emulsion polymerization or solution polymerization, while MMT was intercalated by potassium persulfate(KPS) initiator in advance. Due to the confined space of clay interlayer regions, the polymerizing chains were aggregated into a disk-like or irregular domain depending on their intrinsic properties. The growing domains would trigger the exfoliation of MMT, and further polymerization afforded the latex particles of Polymer-MMT nanocomposites. In addition, for fully water soluble monomer, such as acrylamide, the growing chain would also exfoliate MMT. However, they formed a hydrogel system with dispersed exfoliated MMT nanoplatelets. In brief, the exfoliated polymer-MMT nanocomposite could be fabricated from partial or fully water-soluble monomers through polymerization in the interlayer regions of MMT. In order to study the effect of dispersed MMT nanoplatelets on the properties of polymers, exfoliated poly(vinyl acetate)-montmorillonite (PVAc-MMT) nanocomposite films and crosslinked poly(vinyl acetate- Glycidyl methacrylate)-montmorillonite (PVAc-GMA-MMT) crosslinked nanocomposite films were fabricated for further analysis. These transparent smooth films performed many superior properties, such as mechanical properties, vapor barrier properties, chemical resistance and fire retardation. In conclusion, MMT nanoplatelets acted as nano-size scaffolds in the nanocomposite structure to improve physical properties.中文摘要 ………………………………………………………………I Abstract ……………………………………………………………III Table of Contents …………………………………………………V Table Lists …………………………………………………………IX Figure Lists …………………………………………………………X Chapter 1 Introduction ……………………………………………1 1-1 Preface …………………………………………………………1 1-2 Polymer-Silicates(Clay) Nanocomposites ………………3 1-2-1 Nanocomposites and Nanotechnology ………………4 1-2-2 Montmorillonite and Exfoliated Silicates…11 1-2-3 Intercalation and Exfoliation of Polymer-Clay Nanocomposites……………………………………20 1-2-4 Specific Properties of Polymer-Clay Nanocomposites………………22 1-3 Emulsifier-free Emulsion Polymerization…………28 1-3-1 Introduction to Emulsion Polymerization………29 1-3-2 Theory of Emulsifier-free Emulsion Polymerizaiton……30 1-3 Brief Introduction of Some Polymers…………………33 1-5 Literature Reviews………………………………………38 1-6 Motivation and Outline…………………………………42 Chapter 2 Experimental Section …………………………45 2-1 materials…………………………………………………45 2-2 Equipments………………………………………………46 2-2-1 Modification of MMT by KPS and Fabrication of polymer-MMT nanocomposites and MMT nanoplatelets…46 2-2-2 Preparation of Polymer-Clay Nanocomposites Films………46 2-2-3 Molecular Weight Analysis………………………47 2-2-4 Morphology and Structure Analysis……………47 2-2-5 Analysis of Physical Properties………………48 2-3 Fabrication of Polymer-Clay Nanocomposites ……50 2-3-1 Purifacation of Monomers………………………50 2-3-2 Modification of Montmorillonite by KPS……51 2-3-3 Fabrication of Polymer-MMT nanocomposite Latexes and Pure Polymer Latexes with KPS-MMT……………………52 2-3-4 Fabrication of Polymer-MMT nanocomposite Hydrogel and Pure Polymer Hydrogel with KPS-MMT…………………53 2-4 Preparation of Polymer-MMT Nanocomposite Films……55 2-4-1 PVAc-MMT nanocomposite and pure PVAc films……55 2-4-2 PVAc-GMA-MMT nanocomposite and pure PVAc-GMA films…………………………………………55 2-5 Purification of Clay Nanoplatelets……………………56 2-6 Morphology and Structure Analysis……………………57 2-6-1 X-ray Diffraction (XRD)……………………………57 2-6-2 Transmission Electron Microscopy (TEM)………58 2-6-3 Scanning Electron Microscopy (SEM)……………59 2-6-4 Atomic Force Microscopy (AFM) …………………59 2-7 Physical Properties……………………………………59 2-7-1 Optical Properties…………………………………60 2-7-2 Thermal Properties…………………………………60 2-7-3 Mechanical Properties……………………………61 2-7-4 Inflammable Properties…………………………62 2-7-5 Chemical Resistance ………………………………62 2-7-6 Water Vapor Permeability…………………………63 Chapter 3 Results and Discussions ………………………66 3-1 The Study of Exfoliation Process of MMT during Fabricating PMMA-MMT Nanocomposites………………………66 3-1-1 Investigation by TEM ………………………………66 3-1-2 Investigation by XRD ……………………………68 3-1-3 A brief mechanism for the formation of latex particles of PMMA-MMT nanocomposite………………………69 3-2 An Investigation on the Morphology of Polymer-MMT Nanocomposite and Exfoliation Process of MMT for Different Polymer Bases……………………………………71 3-2-1 X-Ray Diffraction…………………………………71 3-2-2 PVAc-MMT and PMA-MMT nanocomposite…………72 3-2-3 PAAm-MMT nanocomposite …………………………73 3-2-4 PVAc-MMA-MMT, PVAc-GMA-MMT, and PAAm-MMA-MMT nanocomposite ……………………74 3-2-5 A Brief Summary for Different Polymer Base Polymer-MMT Nanocomposite …………………………………………75 3-3 An Observation of MMT Nanoplatelets ………………76 3-4 The Physical Properties of PVAc-MMT and PVAc-GMA-MMT Nanocomposite Films………………………………………77 3-4-1 XRD and TEM Investigation………………………78 3-4-2 Molecular weight and Thermal properties of polymer-MMT nanocomposite……………………………………………78 3-4-3 Surface morphology and Optical Properties ……………79 3-4-4 Mechanical Properties (Tensile Test)…………………………80 3-4-5 Water Vapor Permeability ……………………………………81 3-4-6 Chemical Resistance …………………………………………83 3-4-7 Inflammable Properties ………………………………………84 Chapter 4 Conclusions …………………………………85 Chapter 5 References …………………………………87en-US高分子乳液蒙脫石奈米複合材料EmulsionMontmorilloniteNanocompositethesis