乙烯基酯樹脂/無機層狀材料奈米複合材料之製備與性質探討

Synthesis And Characterization of Vinyl Ester Resin／Inorganic Layered Materials Nanocomposites

顏千翔(Chien-Hsiang Yen)

指導教授 ： 蔡宗燕

中原大學/理學院/化學研究所/碩士(2015年)

https://doi.org/10.6840/cycu201500736

摘要

本研究利用無機層狀材料之滲透膨潤(Osmotic Swelling)特性，驅使苯乙烯單體滲透至層板結構之間，再進行自由基聚合反應(radical polymerization)，如同原位聚合法(In-Situ polymerization)之效果，可使無機層狀材料在高分子基材中分散較好，無機層狀材料選用人工合成的層狀雙氧化物與天然黏土，天然黏土以離子交換法將椰油醯兩性基二丙酸二鈉（Disodium cocoamphodipropionate, K2）插層於層板間，並以X-ray繞射儀(X-Ray Diffraction, XRD)、紅外線光譜儀(Fourier Transform Infrared, FT-IR)及熱重分析儀(Thermogravimetry Analyzer, TGA)觀察改質前後天然黏土的層間距變化及改質劑官能基之存在，並利用熱重損失計算改質劑在天然黏土之插層量；層狀雙氫氧化物選用市售之鎂鋁層狀雙氫氧化物(MgAl-LDH)與鋅鋁層狀雙氫氧化物(ZnAl-LDH)，以鍛燒法輔以水熱法進行還原，將十二烷基苯磺酸鈉(Sodium dodecylbenzenesulfonate, SDBS)置換至層間，再以X-ray繞射儀(XRD)觀察還原後之結晶相與層間距離；以熱重分析儀(TGA)與熱重分析/質譜儀(Thermogravimetric Analyzer/Mass Spectrometer, TG-MS)對改質前後熱裂解區段進行分析，並計算出改質劑之插層量；以紅外線光譜儀(FT-IR)鑑定改質劑官能基之存在；以固態核磁共振儀(Solid State Nuclear Magnetic Resonance, SSNMR)鑑定27Al之環境；以掃描式電子顯微鏡(Scanning electron microscope, SEM)觀察表面型態。
奈米複合材料先藉由X-ray繞射儀(XRD)、穿透式顯微鏡(Transmission electron microscopy, TEM)觀察無機層狀材料之分散型態；再以熱重分析儀(TGA)測量其熱裂解溫度(T5d)；以動態機械分析儀(Dynamic Mechanical Analyzer, DMA)測試玻璃轉移溫度(Glass Trassion Temperatue, Tg)，添加CL120-K2的Tg提升20.0 ˚C，但T5d降低2.8 ˚C；添加ZnAl-SDBS-LDH的Tg提升20.6 ˚C，但T5d降低6.6 ˚C；以萬能拉力機測試抗拉強度，以巴氏硬度計測定表面硬度，添加CL120-K2抗拉強度從35.73 MPa提升至51.71 MPa，而表面硬度從65提升至70；添加ZnAl-SDBS-LDH抗拉強度從35.73 MPa提升至56.37 MPa，而表面硬度從65提升至67；以阿基米得原理測量體積收縮率(Volume shrinkage)，添加CL120-K2可降低2.76 %，添加ZnAl-SDBS-LDH可降低1.45 %，並有效降低螺紋印現象(Print-Through Phenomeon, PTP)。

關鍵字

乙烯基酯樹脂；層狀雙氫氧化物；蒙脫土；奈米複合材料

並列摘要

Osmotic swelling is a typical characteristic property of inorganic layered materials. The aim of this work is to permeate styrene monomer into the gallery layers under the phenomenon of osmotic swelling, and subsequently prepared vinyl ester/inorganic layered materials nanocomposite by radical polymerization.
Clay and layered double hydroxides (LDH) are common inorganic layered hydroxides. Two types of synthetic modified layered double hydroxides based on MgAl-LDH or ZnAl-LDH and a natural Montmorillonite, were applied in this study. Sodium dodecylbenzene sulfonate(SDBS) was intercalated into LDH by the rehydration process of calcined LDH in the presence of surfactant, whereas Disodium cocoamphodipropionate(K2) was intercalated into Montmorillonite by cation-exchange reaction method. Characterization of materials was investigated by using X-ray Diffraction (XRD), thermogravimetric analysis (TGA) and fourier transform infrared spectroscopy (FT-IR) to monitor the changes of the interlayer spacing, weight loss and functional groups of modified LDH and Montmorillonite. The morphology and structures of LDH were observed by scanning electron microscope (SEM) and transmission electron microscopy (TEM), while the amount of modifier intercalated into the LDH layers was calculated by TGA and outgassing analysis of TGA/MS.
By XRD and TEM, dispersion mophology of inorganic layered material in vinyl ester would be observed. glass transition temperature (Tg) and thermal decomposed temperature (T5d) at 5 wt% weight lost were observed by dynamic mechanical analyzer (DMA) and TGA. It is found that by additional of CL120-K2 and ZnAl-SDBS-LDH could improve the glass transition temperature up to 20.0 ˚C and 20.6 ˚C and decrease the thermal decomposition temperature around 2.8 ˚C and 6.6 ˚C, respectively. By adding CL120-K2, the tensile strength could be improved from 35.73 MPa to 51.71 MPa, and from 35.73 MPa to 56.37 MPa for ZnAl-SDBS-LDH. Moreover, the Barcol hardness value could be improved from 65 to 70 by additional of CL120-K2, and from 65 to 67 by additional of ZnAl-SDBS-LDH. Volume shrinkage decrease 2.76 % and 1.45 % by additional of CL120-K2 and ZnAl-SDBS-LDH, and than print-through phenomenon (PTP) was improved by additional of 3.0 phr of CL120-K2 or ZnAl-SDBS-LDH.

並列關鍵字

Vinyl ester resin；layered double hydroxides；Montmorillonite；Nanocomposite

參考文獻

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