以微混練製程開發不同奈米無機層材/聚對苯二甲酸乙二酯奈米複材之製備與性質探討

Study on the Preparation and Characterization of Different Nano Inorganic Layered Materials/Poly(ethylene terephthalate) Nanocomposites through the Microcompounding

廖君儒(Jun-Ru Liao)

指導教授 ： 蔡宗燕

中原大學/理學院/奈米科技碩士學位學程/碩士(2014年)

https://doi.org/10.6840/cycu201400661

摘要

本研究分別選用天然蒙脫土(Clay)與人工合成鋰鋁層狀雙氫氧化物(LiAl LDH)二種無機層狀材料作為補強材，其中天然黏土利用溶膠-凝膠法(Sol-gel)進行改質，於黏土層間形成網狀交聯結構破壞其層狀堆疊達到具脫層結構之型態；鋰鋁層狀雙氫氧化物則藉由共沉澱法(Coprecipitation method)與水熱法(Hydrothermal method)合成，並利用層間陰離子置換法(Ion-exchange method)將有機改質劑1,3苯二甲酸二甲酯-5-磺酸鈉(Dimethyl 5-sulfoisopthalate, DMSI)插層(Intercalated)於層間。透過廣角X-ray 繞射儀(WXRD)、熱重分析儀(TGA)及紅外線光譜儀(FT-IR)了解改質前後無機層材的層間距變化及改質型無機層材之插層量所佔之比例，並以掃描式電子顯微鏡(SEM-EDS)觀測層狀材料之分散形態。分別將有機改質後之無機層狀材料，以微混練製程添加於聚對苯二甲酸乙二酯(PET)中製備奈米級複合材料，對其熱穩定性、結晶性、機械性質、抗紫外線以及阻氣性質相互比較並探討影響之原因。
　　奈米複材則藉由廣角X-ray 繞射儀(WXRD)、穿透式電子顯微鏡(TEM)了解層狀材料於聚對苯二甲酸乙二酯中的分散性，並利用熱重分析儀(TGA)測量其熱裂解溫度(T5d)，添加LDH-DMSI熱穩定性可由原先393.6 ℃提升至403.1 ℃，示差掃描熱卡儀(DSC)測量複材之結晶溫度(Tcc)，則由195.1 ℃提升至200.5 ℃，動態機械分析儀(DMA)測試複材之儲存模數(Storage modulus)，當添加CL120-SiO2提升36.7 %、而添加LDH-DMSI僅提升11.87 %。最後利用氣體滲透分析儀(GPA)、紫外光-可見光光譜儀(UV-Vis)分別測試複材之阻氣性、光學性質，添加脫層化蒙脫土CL120-SiO2對於CO2之Gas barrer可由原先的2.39 barrer降低至1.77 barrer，提升1.34倍；光學性質方面對UVA阻隔可提升28.04 %、UVB提升63.80 %，並仍然保有92.9 %的可見光穿透率。

關鍵字

熔膠-凝膠法 ； 奈米複材 ； 雙螺桿混練 ； 人工層狀雙氫氧化合物 ； 聚對苯二甲酸乙二酯 ； 天然黏土

並列摘要

There are two types of inorganic layered materials ,which are natural montmorillonite (Clay) and synthetic lithium aluminum layered double hydroxides (LiAl LDH).applied as additives which natural clay was treated by sol - gel process (Sol-gel) to delaminate the stacked layers, crosslinked network formed between the clay. lithium aluminum layered double hydroxides synthesized by coprecipitation method and hydrothermal method, followed by intercalating Dimethyl 5-Sulfoisophthalate (DMSI) in to the layers by negative Ion-exchange method. Through a wide-angle X-ray Diffraction (WXRD), Thermal Gravimetric Analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR) could understand the before-and-after changes of the interlayer spacing and modification of modified clay, as the Scanning Electron Microscope (SEM-EDS) observations form the layered material. Added the Inorganic layered materials which were modified into the Poly(ethylene terephthalate) (PET) in the preparation of nanocomposites when Micro compounding, and discuss the reasons and influence of its thermal stability, crystalline, mechanical properties, UV resistance, and gas barrier property .
　From Wide-angle X-ray Diffraction (WXRD), Transmission Electron Microscopy (TEM), nanocomposites would understand the layered material in polyethylene terephthalate in the dispersion, using thermal gravimetric analyzer (TGA) to measure the thermal decomposition temperature (T5d), added LDH-DMSI thermal stability to race the original 393.6 ℃ to 403.1 ℃; the composites temperature (Tcc) measured by Differential Scanning Calorimetry (DSC) , increased from 195.1 ℃ to 200.5 ℃. Composites storage modulus tested by Dynamic Mechanical Analyzer (DMA), upgraded to 36.7 percent when adding CL120-SiO2; upgrade only 11.87% when adding LDH-DMSI. Finally, the Gas Permeation Analyzer (GPA), UV - visible spectrophotometer (UV-Vis) were used testing the composites resistance of the gas, optical properties; Gas barrer of CO2 lower from the original 2.39 barrer to 1.77 barrer by adding delamination of montmorillonite CL120-SiO2, the upgrade is 1.34 times; optical properties can improve barrier against UVA 28.04%, UVB enhance 63.80%, and still has a 92.9% visible light transmittance.

並列關鍵字

Layered double hydroxide ； Nanocomposites ； Sol-Gel ； twin screw ； Poly(ethylene terephthalate) ； Clay

參考文獻

2. 黃坤山; 蔡筱蘄, 抗靜電聚酯之熱性質及其加工性研究. 紡織綜合研究期刊 2013, 23, (4), 1-9.

38. 柯揚船, 聚合物-無機奈米複合材料. 五南: 2004.

46. 葉建麟, 奈米化無機層材以雙螺桿混練製備聚烯烴奈米複材之開發與性質探討. 中原大學化學研究所學位論文 2013, 1-138.

52. 徐偉銓, 聚對苯二甲酸乙二酯/鎂鋁或鋰鋁層狀雙氫氧化合物奈米複材之新觸媒探討與其結晶性質之研究. 中原大學化學研究所學位論文 2014, 280.

4. Chang, J.-H., Comparison of Thermomechanical Properties and Morphologies of Polyester Nanocomposite Fibers: PBT, PET, and PTT. Polymer-Plastics Technology and Engineering 2008, 47, (8), 791-801.