利用有機小分子鹼催化溶膠凝膠反應製備電活性聚亞醯胺/二氧化鈦奈米複合薄膜及其性質探討

Preparation and Properties of Electroactive Polyimide-Titania Hybrid Sol-Gel Membranes Through Small Basic Molecule-Catalyzed Route

黃貞瑜(Jane-Yu Huang)

指導教授 ： 葉瑞銘

中原大學/理學院/化學研究所/碩士(2010年)

https://doi.org/10.6840/cycu201000519

摘要

本實驗利用氧化偶合法合成之胺基封端之苯胺三聚體以做為合成
聚亞醯胺之反應單體及溶膠凝膠反應之有機小分子鹼催化劑，來首次製備一系列具電活性聚亞醯胺/二氧化鈦(EPI/TiO2, EPTs)奈米複合薄膜材料。 首先，將二氧化鈦前驅物(tetraethyl orthotitanate ,Ti(OEt)4與鏊合劑乙醯基丙酮(acetylacetone)以製備無機溶液，接著導入一系列不同含量的胺基封端苯胺三聚體 (amine-capped aniline trimer, ACAT)做為有機小分子鹼催化劑來催化溶膠凝膠反應的進行，然後導入適當量的4,4´-(4,4´-
isopropylidene- diphenoxy)bis(phthalic anhydride)(BSAA) 以合成一系列具電活性聚亞醯胺/二氧化鈦奈米複合薄膜材料。
研究結果顯示，經由電化學防腐蝕測試結果得知: 電活性聚亞醯胺/二氧化鈦奈米複合材料較電活性聚亞醯胺具較佳之防蝕性。 無機二氧化鈦粒子在聚亞醯胺薄膜基材中的分散均勻，且顆粒粒徑大小約~ 15 nm，此觀察結果可以穿透式電子顯微鏡得知。 複合膜材之機械性質、熱性質及氣體穿透性質及表面疏水性質都較電活性聚亞醯胺要好，可由動態機械分析儀(DMA)、熱失重分析儀(TGA) 、微分掃描分析儀(DSC)、氣體穿透分析儀(GPA)及接觸角分析儀量測等方式。 電活性聚亞醯胺之氧化還原性質由循環伏安儀量測。

關鍵字

二氧化鈦 ； 苯胺三聚體 ； 防腐蝕 ； 聚亞醯胺

並列摘要

In this study, a series of elctroactive polyimide-titania hybrid sol-gel materials were first successfully prepared under the incorporation of small basic molecules-catalyzed route through conventional thermal imidization
reactions. Typically, tetraethyl orthotitanate (Ti(OEt)4) was used as inorganic sol-gel precursor reacting with coupling agent (acetylacetone; ACAC) to give inorganic solution. Subsequently, amine-capped aniline
trimer (ACAT) functioned as small organic base catalyst for sol-gel reaction and diamine monomer for the preparation of electroactive polyimide was incorporated into inorganic solution. Dianhydride (BSAA) was then
introduced into the previous solution to give electroactive poly(amic acid)/titania hybrid solution, followed by thermal imidization to give a series of electroactive polyimide/titania hybrid membranes. Morphology of titania
particles existed in hybrid membranes was investigated by transmission electron microscopy (TEM) and exhibited approximate ~ 15 nm in diameter. It should be noted that the hybrid coatings was found to reveal better corrosion protection as compared to that of neat electroactive polyimide based on a series of electrochemical corrosion measurements in saline conditions. Effects of material composition on the mechanical strength, thermal stability,
gas permeability, surface wettability of as-prepared elctroactive polyimide-titania materials were also investigated by DMA, TGA, DSC, GPA and contact-angle measurements, respectively. Redox behavior of as-prepared hybrid materials was identified by electrochemical CV studies.

並列關鍵字

amine-capped aniline trimer ； polyimide-titania ； corrosion

參考文獻

semiconductivity of the [SN]x polymer, Trans Faraday Soc., 294 (1964).

2. H. Shirakawa, S. Ikeda Polymer, 2, 231 (1971).

3. (a) H. Shirakawa, E. J. Lousi, A.G. MacDiamid, C. K. Chiang, A. J. Heeger

J. C. Soc., C. C., 578 (1977).; (b) C.K. Chiang, C.R. Fincher, Y. W. Park, A.

conductivity in doped polyacetylene, Phys., Rev Lett., 39, 1098 (1977).