Effect of Various Synthesized Intercalation Agents on Physical Properties of Polymer/Clay Nanocomposites

博士 === 國立交通大學 === 應用化學系所 === 94 === Nanoclay-filled polymeric systems offer the prospect of greatly improving many of the properties of their mother polymers. In the recent literature, there have been reports of nanoclay-filled polymeric systems that display significant improvements in tensile and t...

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Main Authors: Yeh Ting-Ju, 葉定儒
Other Authors: Chang Feng-Chih
Format: Others
Language:en_US
Published: 2005
Online Access:http://ndltd.ncl.edu.tw/handle/80896267477622194294
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spelling ndltd-TW-094NCTU55000042016-06-06T04:10:54Z http://ndltd.ncl.edu.tw/handle/80896267477622194294 Effect of Various Synthesized Intercalation Agents on Physical Properties of Polymer/Clay Nanocomposites 合成不同插層劑對高分子/黏土奈米複合材料物理性質之影響 Yeh Ting-Ju 葉定儒 博士 國立交通大學 應用化學系所 94 Nanoclay-filled polymeric systems offer the prospect of greatly improving many of the properties of their mother polymers. In the recent literature, there have been reports of nanoclay-filled polymeric systems that display significant improvements in tensile and thermal properties, heat distortion temperatures, and resistance to flammability and reduced permeability to small molecules and reduced solvent uptake. A common observation emerging from these studies is that the magnitude of improvement depends strongly on the state of dispersion of the clay layers in the polymer matrix. The experiment work in this dissertation was divided into four areas: 1. We have prepared polystyrene/clay nanocomposites using an emulsion polymerization technique. The nanocomposites were exfoliated at up to a 3 wt % content of pristine clay relative to the amount of polystyrene (PS). We used two different surfactants for the montmorillonite: the aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS) and the ammonium salt of cetylpyridinium chloride (CPC). The nanocomposite prepared from the clay treated with the POSS containing surfactant is exfoliated, while an intercalated clay was obtained from the CPC-treated surfactant. The value of Tg of the PS component in the nanocomposite is 8 °C higher than the virgin PS and its thermal decomposition temperature (21 °C) is also higher significantly. The presence of the POSS unit in the MMT enhances the thermal stability of the polystyrene. 2. We synthesized intercalation agent APB and prepared polystyrene/clay nanocomposites using an emulsion polymerization technique. We used two different intercalation agents to treat clay: the phosphonium salt (APP) and the ammonium salt (APB). We expected that the intercalation agent APB containing rigid adamantine group also has high thermal stability besides phosphonium group. The molecular weights of polystyrene (PS) obtained from the nanocomposite is slightly lower than the virgin PS formed under similar polymerization conditions. The coefficient of thermal expansion (CTE) was obtained from thermomechanical analysis. A 44~55 % decrease of CTE is observed for APB- and APP-intercalated clay nanocomposites relative to the pure PS. 3. We employed two surfactants for the montmorillonite: cetylpyridinium chloride (CPC) and the CPC/α-CD inclusion complex. The inclusion complex was characterized by X-ray diffraction, 13C CP/MAS NMR spectra, and 1H NMR spectroscopy, and TGA. The 1H NMR spectra of the complexes indicate that the stoichiometry of the complexes is 1:2 (i.e.,one CPC molecule and two α-CD units). The CPC/α-CD-treated clay is more effective than is virgin CPC-treated clay at enhancing the thermal stability of polystyrene. 4. We have used the solvent blending method to prepare polybenzoxazine/clay nanocomposites possessing various clay contents. We synthesized a monofunctional benzoxazine monomer (MBM) and then treated the clay with this intercalation agent. To better understand the curing kinetics of the polybenzoxazine/clay nanocomposites, we performed dynamic and isothermal differential scanning calorimetry (DSC) measurements. The Kissinger and Ozawa methods gave fairly close results for the calculated activation energies, which decreased upon increasing the clay content. The Kamal method-based on an autocatalytic model-suggested a total reaction order of between 2.4 and 2.8. Chang Feng-Chih 張豐志 2005 學位論文 ; thesis 148 en_US
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description 博士 === 國立交通大學 === 應用化學系所 === 94 === Nanoclay-filled polymeric systems offer the prospect of greatly improving many of the properties of their mother polymers. In the recent literature, there have been reports of nanoclay-filled polymeric systems that display significant improvements in tensile and thermal properties, heat distortion temperatures, and resistance to flammability and reduced permeability to small molecules and reduced solvent uptake. A common observation emerging from these studies is that the magnitude of improvement depends strongly on the state of dispersion of the clay layers in the polymer matrix. The experiment work in this dissertation was divided into four areas: 1. We have prepared polystyrene/clay nanocomposites using an emulsion polymerization technique. The nanocomposites were exfoliated at up to a 3 wt % content of pristine clay relative to the amount of polystyrene (PS). We used two different surfactants for the montmorillonite: the aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS) and the ammonium salt of cetylpyridinium chloride (CPC). The nanocomposite prepared from the clay treated with the POSS containing surfactant is exfoliated, while an intercalated clay was obtained from the CPC-treated surfactant. The value of Tg of the PS component in the nanocomposite is 8 °C higher than the virgin PS and its thermal decomposition temperature (21 °C) is also higher significantly. The presence of the POSS unit in the MMT enhances the thermal stability of the polystyrene. 2. We synthesized intercalation agent APB and prepared polystyrene/clay nanocomposites using an emulsion polymerization technique. We used two different intercalation agents to treat clay: the phosphonium salt (APP) and the ammonium salt (APB). We expected that the intercalation agent APB containing rigid adamantine group also has high thermal stability besides phosphonium group. The molecular weights of polystyrene (PS) obtained from the nanocomposite is slightly lower than the virgin PS formed under similar polymerization conditions. The coefficient of thermal expansion (CTE) was obtained from thermomechanical analysis. A 44~55 % decrease of CTE is observed for APB- and APP-intercalated clay nanocomposites relative to the pure PS. 3. We employed two surfactants for the montmorillonite: cetylpyridinium chloride (CPC) and the CPC/α-CD inclusion complex. The inclusion complex was characterized by X-ray diffraction, 13C CP/MAS NMR spectra, and 1H NMR spectroscopy, and TGA. The 1H NMR spectra of the complexes indicate that the stoichiometry of the complexes is 1:2 (i.e.,one CPC molecule and two α-CD units). The CPC/α-CD-treated clay is more effective than is virgin CPC-treated clay at enhancing the thermal stability of polystyrene. 4. We have used the solvent blending method to prepare polybenzoxazine/clay nanocomposites possessing various clay contents. We synthesized a monofunctional benzoxazine monomer (MBM) and then treated the clay with this intercalation agent. To better understand the curing kinetics of the polybenzoxazine/clay nanocomposites, we performed dynamic and isothermal differential scanning calorimetry (DSC) measurements. The Kissinger and Ozawa methods gave fairly close results for the calculated activation energies, which decreased upon increasing the clay content. The Kamal method-based on an autocatalytic model-suggested a total reaction order of between 2.4 and 2.8.
author2 Chang Feng-Chih
author_facet Chang Feng-Chih
Yeh Ting-Ju
葉定儒
author Yeh Ting-Ju
葉定儒
spellingShingle Yeh Ting-Ju
葉定儒
Effect of Various Synthesized Intercalation Agents on Physical Properties of Polymer/Clay Nanocomposites
author_sort Yeh Ting-Ju
title Effect of Various Synthesized Intercalation Agents on Physical Properties of Polymer/Clay Nanocomposites
title_short Effect of Various Synthesized Intercalation Agents on Physical Properties of Polymer/Clay Nanocomposites
title_full Effect of Various Synthesized Intercalation Agents on Physical Properties of Polymer/Clay Nanocomposites
title_fullStr Effect of Various Synthesized Intercalation Agents on Physical Properties of Polymer/Clay Nanocomposites
title_full_unstemmed Effect of Various Synthesized Intercalation Agents on Physical Properties of Polymer/Clay Nanocomposites
title_sort effect of various synthesized intercalation agents on physical properties of polymer/clay nanocomposites
publishDate 2005
url http://ndltd.ncl.edu.tw/handle/80896267477622194294
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