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  • 學位論文

聚甲基丙烯酸甲酯/改質型黏土奈米複材的製備與其紫外光阻隔及機械特性之研究

Study on the Synthesis, UV Resistance and Mechanical Properties of Poly(methyl methacrylate)/Organic Modified Montmorillonite Nanocomposites

指導教授 : 蔡宗燕

摘要


本研究以聚甲基丙烯酸甲酯/天然黏土奈米級複合材料之合成探討其不同改質型黏土對機械性質、熱性質及光學性質的影響。天然蒙脫土以有機改質劑椰油醯兩性基二丙酸二鈉(DisodiumCocoamphodipropionate,K2)和椰油醯胺丙基甜菜鹼(Cocamidopropylhydroxysultaine, C50)製備改質型黏土,以離子交換法將天然黏土表面有機化改質,增加其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)鑑定改質蒙脫土層間之有機與無機的官能基,證明K2、C50的長碳鏈改質於蒙脫土層間。以熱重分析儀(Thermogravimetry Analyzer, TGA)定量分析改質蒙脫土中改質劑的插層量。 以不同的天然黏土與改質劑組合而成的改質土(CL42-K2、CL120-K2、CL120-C50、CL88-K2)進行溶液聚合法製備聚甲基丙烯酸甲酯/無機層狀材料奈米級複合材料。以XRD及穿透式電子顯微鏡(Transmission electron microscopy, TEM)觀察其分散性,可知SP-CL120-K2及SP-CL88-K2複材為脫層型分散型態,而SP-CL120-C50及SP-CL42-K2複材為部份脫層部份插層之分散型態;SP-CL120-K2-5%其熱裂解溫度(Decomposed temperature, Td)最高提升56℃,自240℃提高至296℃,而SP-CL88-K2-5%其玻璃轉移溫度(Glass transition temperature, Tg)提升28℃,自96℃提高至124 ℃;在光學性質方面,添加黏土後其複材的穿透度均可在87.4%以上,而SP-CL88-K2-5%其紫外光阻抗能力最好,與純的聚甲基丙烯酸甲酯相比,當波長為320 nm時,降低約31%,自86.3%降低至59.6%;在氣體阻隔方面,SP-CL88-K2在添加量3 wt%時,其氣體阻隔效果最好,與純的聚甲基丙烯酸甲酯相比可改善65%,自0.9429 barrer降低至0.3292 barrer;在機械性質方面,SP-CL88-K2-5%由於其分散性效果最佳,使得其儲存模數提高約29%,從1315 MPa增加至1700 MPa,鉛筆硬度方面,純的聚甲基丙烯酸甲酯鉛筆硬度為HB,而複材的鉛筆硬度提升至少H以上,SP-CL120-K2-3%和SP-CL88-K2-3% 其鉛筆硬度自HB提升達到3H。 另外將三種不同黏土以相同改質劑製成之改質土(CL42-K2、CL120-K2及CL88-K2),利用乳化聚合法製備PMMA/clay奈米複合材料。首先以XRD及TEM的鑑定,可知EP-CL42-K2及EP-CL120-K2其分散型態為脫層型分散,而EP-CL88-K2為部份脫層部分插層之分散型態;熱性質方面,隨著改質土添加量的提高,其EP-CL88-K2-3%的熱裂解溫度Td最高提升12 ℃,自294℃提高至306℃,而EP-CL120-K2-5%其玻璃轉移溫度Tg提升6℃,自121℃提高至127℃;在光學性質方面,添加黏土後穿透度均可在86.0%以上,而EP-CL120-K2-5%其紫外光阻抗能力最好,與純的聚甲基丙烯酸甲酯相比降低約30%,自83.9%降低至58.7%;在氣體阻隔方面,在添加量3 wt%時,其氣體阻隔效果最好,EP-CL120-K2-3%可改善80%,自0.9261 barrer降低至0.1885 barrer;在機械性質方面,EP-CL120-K2由於其分散性效果最佳,使得其儲存模數提高約64.6%,從1637 MPa增加至2695 MPa;鉛筆硬度方面,純的聚甲基丙烯酸甲酯鉛筆硬度為H,EP-CL120-K2-3%和EP-CL88-K2-3%其鉛筆硬度提升達到3H。 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種特性。

並列摘要


The potential to improve the mechanical, thermal, and optical properties of poly(methyl methacrylate) (PMMA)/montmorillonite nanocomposites, prepared with clay containing an organic modifier, were investigated. Pristine sodium montmorillonite clay was modified by using (disodium cocoamphodipropionate, K2) and (cocamidopropylhydroxysultaine, C50), via ion exchange to enhance the compatibility between the clay platelets and the methyl methacrylate polymer matrix. The characteristics of modified clays were exhaustively identified by X-ray Diffraction (XRD) for the d-spacing of the montmorillonite layer, Fourier transform infrared (FTIR) for the organic modifier and function group of montmorillonite, and thermogravimetric analyzer (TGA) for the theoretical intercalation amount of the modified agent in the modified clay. Four types of modified clays of CL42-K2, CL120-K2, CL120-C50, and CL88-K2 were applied to prepare the PMMA/clay nanocomposites via solution polymerization. The dispersion morphology was characterized by XRD and transmission electron microscopy (TEM). The results show that SP-CL120-K2 and SP-CL88-K2 nanocomposites displayed exfoliated morphologies. Conversely, SP-CL120-C50 and SP-CL42-K2 nanocomposites displayed intercalated and partly exfoliated morphologies. The decomposition temperature (Td) of SP-CL120-K2-5% was increased 56℃ from 240℃ to 296℃. The glass transition temperature (Tg) of SP-CL88-K2-5% was increased 28℃ from 96℃ 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 87.4%. The UV resistance of SP-CL88-K2-5% was decreased 31% from 86.3% to 59.6%. The lowest gas permeability of SP-CL88-K2-3% was 0.3292 barrer, which was decreased 65% in permeability incomparison to the pristine polymer sample. The storage modulus of SP-CL88-K2-5% was increased 29% from 1315 MPa to 1700 MPa due to the exfoliated nanostructure. The pencil hardness of the pure PMMA film was found to be HB, but that of all the PMMA/clay nanocomposite films was at least in H standard. The hardness of SP-CL120-K2 and SP-CL88-K2 nanocomposites with 3 wt% clay loading was even up to 3H. There were three types of modified clays of CL42-K2, CL120-K2, and CL88-K2 was used to synthesize the PMMA/clay nanocomposites via emulsion polymerization. The XRD and TEM were employed to study the dispersion morphology of PMMA/clay nanocomposites. The result shows EP-CL42-K2 and EP-CL120-K2 nanocomposites displayed exfoliated morphologies. On the contrary, the EP-CL88-K2 nanocomposites displayed intercalated and partly exfoliated morphologies. The Td of EP-CL88-K2-3% was increased 12℃ from 294℃ to 306℃. The Tg of EP-CL120-K2-5% was increased 6℃ from 121℃ to 127℃. The PMMA/clay nanocomposites show a slight decline in transmissionin of the visible light region as clay content increased but keep an optical transmission of approximately 86.0%. The UV resistance of EP-CL120-K2-5% was decreased 30% from 83.9% to 58.7%. The lowest gas permeability of EP-CL120-K2-3% was 0.1885 barrer, which was 80% decrease in permeability incomparison to the pristine polymer sample. The storage modulus of EP-CL120-K2-5% was increased 64.6% from 1637 MPa to 2695 MPa due to the exfoliated nanostructure. The pencil hardness of the pure PMMA film was found to be H, and the hardness of EP-CL120-K2 and EP-CL88-K2 nanocomposites with 3 wt% clay loading was even up to 3H. Therefore, the performance of PMMA/clay nanocomposites have shown the great improvement in various properties.

參考文獻


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被引用紀錄


陳建誠(2016)。光固型壓克力/無機層狀奈米複材之製備性質研究〔碩士論文,中原大學〕。華藝線上圖書館。https://doi.org/10.6840%2fcycu201600876
吳悌嘉(2015)。具難燃機能聚甲基丙烯酸甲酯/改質型黏土奈米複材之製備與性質研究〔碩士論文,中原大學〕。華藝線上圖書館。https://doi.org/10.6840%2fcycu201500778

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