超疏水金屬有機骨架的製備與應用

Preparation and application of hydrophobic metal-organic frameworks

許郁翎(Yu-Ling Hsu)

指導教授 ： 林嘉和

中原大學/理學院/化學研究所/碩士(2018年)

https://doi.org/10.6840/cycu201800404

摘要

本研究論文中，透過合成後修飾的方法來製備超疏水有機金屬骨架孔洞材料。首先以長度較長的H2TZDB(4,4'-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic acid)為配位基，合成新穎MOFs，ZrTz-68、HfTz-68，及製備常見的UiO-66-NH2，再透過修飾疏水官能基進而提升水氣穩定性。並將上述MOFs加入環氧樹脂中，經熱交聯反應，應用於低介電、低熱傳材料和防腐蝕塗料。
在性質鑑定上，利用粉末X-射線繞射儀（PXRD）來鑑定MOFs結構及存在，孔隙及表面積分析儀測定其孔洞特性與氮氣等溫吸附，接觸角量測儀（CA）確認其疏水性，掃描式電子顯微鏡（SEM）進行相形態之分析，熱重分析儀（TGA）檢測其熱性質，另一方面則以傅立葉轉換紅外線光譜（FT-IR）鑑定環氧樹脂結構，再藉由精密阻抗分析儀來測定介電值，熱導係數儀（HD）求得熱導係數，循環伏特安培儀（CV）量測材料之防蝕能力。
實驗結果，純環氧樹脂添加MOFs後，低介電常數由4.26下降至3.77，熱傳導係數0.1943 W/mK下降至0.08124 W/mK，腐蝕電位-867.4 mV增加至-523.5 mV，說明孔洞性與疏水性確實對介電常數、熱傳導係數、防腐蝕能力具有影響。

關鍵字

金屬有機骨架；疏水；環氧樹脂

並列摘要

In this study, hydrophobic metal-organic frameworks（MOFs）have been synthesized via postsynthetic modification method. First, we synthesized the novel MOFs of ZrTz-68 and HfTz-68,with organic ligand of longer length and contain the functional group:（4,4'-(1,2,4,5-tetrazine-3,6-diyl)dibenzoic acid, H2TZDB）as the organic linker . Furthermore, we also synthesized a quite common MOF of UiO-66-NH2. By using same strategy to modify MOFs with hydrophobic functional group, we got the optimized result that has the best water stability in the air. These MOFs were incorporated into the backbone of epoxy through heat curing, thus applied to low dielectric material, low thermal conductivity material, and anticorrosive coating.
These MOFs have been characterized by the powder X-ray diffraction （PXRD）and gas adsorption measurements. We can observe the changing of the water stability from the result by using the contact angel detector（CA）. The shape and particle size of the new MOFs were identified by field emission scanning electron microscope（FE-SEM）. Further characterization for all the MOFs were done with thermal gravimetric analysis（TGA）. Moreover, after a series of conditions for its epoxy synthetic, and to confirm the structure were characterized by fourier transform infrared spectroscopy（FT-IR）, Hot Disk（HD）and Cyclic voltammetry（CV）.
After pure epoxy added hydrophobic MOFs, the low dielectric constant dropped from 4.26 to 3.77. The thermal conductivity dropped from 0.1943 W/mK to 0.08124 W/mK. The corrosion potential increased from -867.4 mV to -523.5 mV. It shows that the porosity and hydrophobicity do have an effect on the dielectric constant, heat transfer coefficient and corrosion resistance.

並列關鍵字

MOFs；hydrophobic；epoxy

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