含三苯胺之可光致發光聚氨基甲酸乙酯的合成及其性質研究

Studies on Synthesis and Properties of Photoluminescent Polyurethanes Containing Triphenylamine Moiety

張赫任(Ho-Zen Chang)

指導教授 ： 李文福

大同大學/工程學院/化學工程學系所/碩士(2012年)

摘要

本研究是使用aniline和4-fluorobenzonitrile合成出4, 4’-dicyano triphenylamine，並於鹼性條件下水解反應製成4, 4’-dicarboxy triphenylamine，再和isophthalic acid與poly (ethylene glycol) 進行酯化反應，合成尾端為COOH 官能基之含三苯胺polyester。利用FT-IR鑑定其官能基；再利用端末基分析法檢測其acid value和OH value並計算出分子量；再和GPC測出的分子量做對照。本研究以酸價為進料之標準與開環聚合好的polycaprolactone (PCL)行酯化反應，最後再和二異氰酸酯類單體(tolylene-2,4-diisocyanate、isophorone diisocyanate)、鏈延長劑(butanediol)反應製成聚氨基甲酸乙酯(polyurethane, PU) 結構高分子；另使用不具三苯胺結構的聚酯製成PU作為對照組。本研究主要探討以不同結構合成之熱塑性PU對其形狀記憶、光學、熱、物理性質之影響。
實驗結果顯示已成功合成出三苯胺單體(4, 4’-dicarboxy triphenylamine)、聚酯 (polyester) 、polycaprolactone 和polyurethane。另以端末基分析法算出之分子量低於GPC所測得的。在TGA、DSC測試部分，poly(ethylene isophthalate/triphenylamine-co-PCL)- polyurethane有較高之熔點和結晶性，PEG鏈長越長則有較高的分子量所以會有較好的熱安定性；UV、PL測試中可以發現含4, 4’-dicarboxy triphenylamine單體的polymer在353 nm有最大吸收波峰、433 nm有最大螢光放射波峰與PEG的鏈長沒有直接的關係；水接觸角部分，PEG鏈段越長則水接觸角越小；而形狀記憶部分軟鏈段的比例越高則會有較高的回復性，TDI因其結構較剛硬，故其回復速率較快，PEG鏈段越長則回復速度越快、最終回復率越高。

關鍵字

光致發光 ； 聚酯 ； 聚氨基甲酸乙酯 ； 形狀記憶 ； 端末基分析法 ； 三苯胺 ； 水接觸角

並列摘要

In this study, 4, 4’-dicyano triphenylamine was firstly synthesized by nucleophilic substitution of 4-fluorobenzonitrile and aniline, followed by alkaline hydrolysis of the dinitrile intermediate to obtain 4, 4’-dicarboxy triphenylamine. Furthermore, polyester prepolymer was prepared by polycondensation with 4, 4’-dicarboxy triphenylamine, poly (ethylene glycol) and isophthalic acid. Their acid values and hydroxyl values were measured by end-group analysis. The acid value of polyester prepolymer was used as the basis of synthesis of following reaction. Then, polycaprolactone (PCL) was prepared by ring-opening polymerization with caprolactone. Finally, polyurethane polymer was synthesized by diisocyanate compounds [tolylene-2,4-diisocyanate (TDI)、isophorone diisocyanate (IPDI)] and chain-extender. In TGA and DSC analysis, the poly(ethylene isophthalate /triphenylamine)-polyurethanes have higher melting point and higher crystallinity. The Polyurethanes having longer chain lengths of PEG have better thermal stability because the average molecular weight were higher due to longer chain lengths of PEG. The effect of triphenylamine content in the polyurethane polymers on their photoluminescent properties was investigated. The results showed that the more the amount of photoluminescent monomer in polymer structure, the higher the intensity of the maximum wavelength of UV/vis and PL. Water contact angle analysis show that the longer the length of PEG segments, the smaller the water contact angle of the polyurethanes. The results also show that PL intensity of the polyurethanes was not affected by the chain lengths of PEG. The shape memory effect analysis shows the higher the ratio of soft segment length, the faster the shape recovery rate. The recoverable rate for PU having TDI is faster than those having IPDI. The results also show that the longer the chain lengths of PEG in the polyurethanes, the faster the recovery rate and the higher the final recovery ratio.

並列關鍵字

photoluminescence ； polyester ； polyurethane ； shape memory effect ； end-group analysis ； triphenylamine ； water contact angle

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