以溶液原位聚合法製備改質型層狀材料/壓克力樹脂奈米複材及其性質探討

Preparation and Characterization of Poly(methylmethacrylate) /Clay Nanocomposites by in-situ Solution Polymerization

陳坤義(Kun-Yi Chen)

指導教授 ： 蔡宗燕

中原大學/理學院/化學研究所/碩士(2020年)

https://doi.org/10.6840/cycu202000686

摘要

本研究以溶液原位聚合法合成聚甲基丙烯酸甲酯/改質型無機層材奈米複材並探討其不同改質型無機層材對奈米複材之機械性質、熱性質及光學性質等影響。天然蒙脫土以椰油醯兩性基二丙酸二鈉（DisodiumCocoamphodipropionate, K2）進行有機化改質，人工無機層材以十二烷基苯磺酸鈉( Sodium dodecylbenzenesulfonate, SDBS )
進行有機化改質，有機改質的目的是提升無機層材與高分子基材的相容性，利用 X 光繞射儀（X-ray Diffraction, XRD）觀察無機層材之層間距變化，傅立葉轉換紅外線光譜儀（Fourier Transform Infrared, FT-IR）鑑定改質型無機層材層間之有機與無機的官能基，證明 K2、SDBS的長碳鏈成功插層於無機層材的層間。以熱重分析儀（Thermogravimetry Analyzer, TGA）定量分析改質型無機層材中改質劑的插層量。
以不同的無機層材與改質劑製備有機化無機層材( CL120-K2、CL88-K2、MgAl-SDBS、ZnAl-SDBS )進行溶液原位聚合法製備聚甲基丙烯酸甲酯/無機層狀材料奈米混成複材。以 XRD 及穿透式電子顯微鏡（Transmission electron microscopy, TEM）觀察其分散性，而 CL120-K2、CL88-K2、MgAl-SDBS、ZnAl-SDBS 複材在3 phr的添加量為部份脫層部份插層之分散型態；SP-CL88-K2-5phr其熱裂（Decomposed temperature, Td）提升最高為 83℃，自 222.7℃提高至 305.7℃，而 SP-CL120-K2-5phr和 SP-MgAl-SDBS其玻璃轉移溫度（Glass transition temperature, Tg）提升 14℃，自 110℃提高至 124 ℃； 在光學性質方面，添加5 phr黏土後其複材的穿透度均可在90%以上，而SP-CL88-K2-5phr其紫外光阻抗能力最好，與純的聚甲基丙烯酸甲酯相較，當波長為 320 nm 時，降低約 49.4%，自穿透率從 89.1%降低至 39.7%；在機械性質方面，SP-CL88-K2-5phr其儲存模數提高最多，從 1129 MPa 增加至 1546 Mpa(提升了36.9%)，鉛筆硬度方面，純的聚甲基丙烯酸甲酯鉛筆硬度為 HB-H，而SP-CL120-K2- 3phr和 SP-CL88-K2-3phr 和 MgAl-SDBS-3phr 其鉛筆硬度自 HB 提升達到 3H-4H；在氣體阻隔方面，SP-CL88-K2-5phr在氧氣阻隔方面提升41%，在氮氣阻隔方面提升11%。
因此本實驗中的聚甲基丙烯酸甲酯/黏土奈米級複合材料顯現出可有效改善材料的多重特性。

關鍵字

聚甲基丙烯酸甲酯 ； 黏土 ； 層狀雙氫氧化合物

並列摘要

This study is to improve the mechanical, thermal, and optical properties of poly(methyl methacrylate) (PMMA)/montmorillonite nanocomposites, prepared with clay containing an organic modifier by in-situ solution polymerization. Pristine sodium montmorillonite clay was modified by disodium cocoamphodipropionate (K2) and layered double hydroxides (LDH) was modified by sodium dodecylbenzenesulfonate (SDBS), via ion exchange to enhance the compatibility between the clay platelets and the methyl methacrylate polymer matrix. The characteristics of modified clays were identified by X-ray Diffraction (XRD) for the d-spacing of the modified montmorillonite, Fourier transform infrared (FTIR) for the organic function group of the modified montmorillonite, and thermogravimetric analyzer (TGA) for the theoretical intercalant amount of the modified agent in the modified clays.
Four types of modified inorganic layered materials, CL120-K2, CL88-K2, MgAl-SDBS, and ZnAl-SDBS, were applied to prepare the PMMA/clay nanocomposites via in-situ solution polymerization. The dispersion morphology was characterized by XRD and transmission electron microscopy (TEM). The results show that SP-CL120-K2, SP-CL88-K2, SP-MgAl-SDBS, and SP-ZnAl-SDBS nanocomposites with 3 phr clay loadind displayed partly intercalated and partly exfoliated morphologies. The decomposition temperature (Td) of SP-CL88-K2-5 phr was increased 83℃ from 222℃ to 305℃. The glass transition temperature (Tg) of SP-CL120-K2-5phr and SP-MgAl-SDBS-5phr was increased 14℃ from 110℃ to 124℃. The PMMA/clay nanocomposites show a slight decline in transmissionin of the visible light region as clay content increased but maintain an optical transmission of approximately 90%. The UV resistance of SP-CL88-K2-5phr was decreased 49.4% from 89.1% to 39.4%. The storage modulus of SP-CL88-K2-5phr was increased 29.2% from 1129 MPa to 1546 Mpa. The pencil hardness of the pure PMMA film was found to be HB, but the hardness of SP-CL120-K2-3phr, SP-CL88-K2-3phr, and SP-MgAl-SDBS-3phr nanocomposites was even up to 3H-4H. In terms of gas barrier, SP-CL88-K2-5phr increased 41% in oxygen barrier and 11% in nitrogen barrier. Therefore, the performance of PMMA/clay nanocomposites have shown the great improvement in various properties.

並列關鍵字

poly(methylmethacrylate) ； clay ； layered double hydroxides

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