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  • 學位論文

具電活性之自癒性水膠之合成、鑑定與性質研究

Synthesis, Characterization and Properties of Electroactive Self-Healing Hydrogels

指導教授 : 葉瑞銘

摘要


本碩士論文的研究主軸分為兩大部分,(一) 非電活性自癒型水膠最佳條件參數的研究探討 ( 調整反應物的分子量大小 ),先找到最佳條件,後將其應用到第二部分的研究上;(二) 新型電活性自癒型水膠的合成、鑑定及流變行為研究。 找到最佳流變參數的非電活性自癒型水膠合成條件後,以此為基礎,來合成新型的電活性自癒型水膠。本研究自行合成具有電活性的二胺類單體及購買到的具單胺基的幾丁聚醣與具有二醛末端基的聚乙二醇進行化學反應,形成具有電活性的自癒型 (亞胺鍵) 水膠,並進一步探討 (1) 電活性二胺單體導入的有無、(2) 電活性二胺單體導入的種類及 (3) 電活性二胺單體導入的含量三種參數對自癒性水膠的流變行為及自癒性參數所造成的量化影響。 在研究論文的第一部分,使用商品具胺基的幾丁聚醣 (分子量為50,000 ~ 190,000 (LC) 及310,000 ~ 375,000 (HC)) 及自行合成具二醛末端基的聚乙二醇 (分子量為2,000 (DP-2000), 4,000 (DP-4000)及6,000 (DP-6000)),所合成的6個水膠皆具有自癒性,經由凍乾實驗處理樣品後,再以掃描式電子顯微鏡(SEM)觀察材料的表面型態,可發現所使用的反應物若分子量越大則合成之材料的孔洞尺寸越大。 且由流變儀所得到的流變行為結果顯示: 由LC及DP-6000所得的自癒性水膠具有最佳參數 (最短的癒合時間及最佳的回復率),因此,以此條件為基礎,進一步合成接下來的電活性自癒型水膠。 在研究論文的第二部分,合成電活性自癒型水膠首先需要利用氧化偶合法合成具磺酸根 (-SO3H) 及不具磺酸根之苯胺三聚體 (簡稱SACAT及ACAT),接著利用核磁共振光譜儀 (1H-NMR)、傅立葉紅外光譜儀 (FTIR)及質譜儀 (MS) 確認其化學結構。 並利用UV-Visible光譜監測ACAT及SACAT氧化的特性。 在水膠材料的製備方面,將0.07 M 的ACAT水溶液0.9 ml及0.07 M/0.14M 的SACAT水溶液0.9 ml先與0.1 g的DF-6000粉體進行反應,接著加入2 wt-% 的LC水溶液2.5g,繼續均勻攪拌大約10分鐘,即可得到所製備的電活性自癒型水膠。 進一步利用FTIR對所合成的電活性自癒型水膠進行鑑定,確認亞胺鍵在電活性二胺及具二醛末端基的聚乙二醇也有產生。 另一方面,藉由循環伏特安培儀 (Cyclic Voltammetry , CV)量測電活性水膠材料之氧化還原特性,研究數據顯示:(1)電活性二胺單體的導入確實會使原本非電活性水膠材料具備電活性。 (2) SACAT單體導入水膠較ACAT單體導入水膠有較佳的電活性。 (3) 導入較多含量的SACAT(0.14 M) 於水膠中比導入較少含量的SACAT (0.07 M) 於水膠中具較佳的電活性。 電活性單體導入自癒性水膠在流變行為會造成明顯的變化,探討如下:(1) ACAT的導入,會造成原本的自癒性水膠的原始模量提升、極限應變小幅下降、癒合時間大幅延長、回復率不變。 (2) 相較於ACAT, SACAT的導入會造成原本的自癒性水膠的原始模量小幅下降、極限應變小幅提升、癒合時間小幅延長、回復率大幅下降。 (3) 增加導入SACAT含量進水膠,會使電活性自癒性水膠的原始模量大幅下降、極限應變大幅下降、癒合時間小幅縮短、回復率小幅下降。 總而言之,自行合成的電活性苯胺三聚體的二胺類單體導入自癒性水膠,可有效結合電活性與自癒性的功能,產生電活性的自癒型水膠,但電活性的導入明顯的對水膠的自癒/流變行為產生影響,在原始模量、極限應變、癒合時間及回復率皆有一定程度的影響。

並列摘要


In this dissertation, two main subjects associated with the self-healing hydrogels were involved. In the first part, the best rheological parameters were studied for the synthesis of non-electroactive self-healing hydrogels (non-ESHs). Subsequently, the electroactive self-healing hydrogels (ESH) were prepared by incorporating as-synthesis conjugated diamine with/without sulfonated group. In the first part, non-ESH were synthesized by reacting primary amine group of chitosan (Mw = 50,000 ~ 190,000 (LC) and Mw = 310,000 ~ 375,000 (HC)) and aldehyde group of double-sided aldehyde-based polyethylene glycol (DF-PEG) (Mw = 2,000 (DP-2000), 4,000 (DP-4000) and 6,000 (DP-6000)). FTIR spectra of all six non-ESH samples were used to identify the imine bonding formation between amine group of chitosan and aldehyde of DF-PEG. Rheology studies of non-ESH were found to reveal best self-healing behavior in LC-DP-6000 (shortest healing time and best recovery). For the second part, the ESHs were prepared by incorporating the conjugated diamine with/without sulfonated group. First of all, the amine-capped aniline trimer (ACAT) and sulfonated ACAT (SACAT) was synthesized by oxidative coupling reaction, followed by characterized by 1H-NMR, FTIR and Mass spectroscopy. Subsequently, the ESHs were prepared by reacting 0.9 ml of 0.07 M ACAT aqueous solution or 0.9 ml of 0.07 M or 0.14 M SACAT aqueous solution with 0.1 g of DP-6000, followed by introducing 2.5 g of 2 wt-% of LC aqueous solution. The as-prepared mixture was under magnetic stirring for ~ 10 minutes to give the desired ESHs. Redox capability of as-prepared ESHs was identified by electrochemical cyclic voltammetry (CV) studies. It should be noted that the incorporation of ACAT into non-ESH may introduce the redox capability into ESH. Secondly, the incorporation of SACAT into ESHs was found to reveal higher redox capability as compared to that of ACAT. Moreover, higher loading of SACAT in ESHs was found to exhibit higher redox capability as compared to that of lower loading of SACAT in ESHs. For the studies of self-healing behavior of ESHs, a series of experiments were performed by rheometer. First of all, ESH containing ACAT was found to reveal an enhancement in original storage modulus, slightly decrease in G and G from strain amplitude sweep, slightly enhancement in self-healing process after damage and constant in recovery percentage as compared to that of non-ESH. Moreover, the incorporation of SACAT in ESH was found to exhibit slightly decrease in original storage modulus, slightly increase in G and G from strain amplitude sweep, slightly increase the self-healing process after damage and significantly decrease in recovery percentage as compared to that of ESH containing ACAT at same feeding concentration. Moreover, the increase of SACAT in ESH was found to reveal significantly decrease in original storage modulus, significantly decrease in G and G from strain amplitude sweep, slightly decrease in self-healing process after damage and slightly decrease in recovery percentage. To sum up, incorporating of conjugated diamine into self-healing hydrogels may introduce electroactivity into gels and significantly affect the self-healing behavior of original hydrogels.

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