胺基修飾二氧化矽介孔材料之添加對乙二醇殼聚醣自癒性水膠之物性研究

Study on the Physical Properties of Ethylene Glycol Chitosan Self-healing Hydrogel by Addition of Amino Modified Mesoporous Silica Material

楊昀(YUN YANG)

指導教授 ： 葉瑞銘

中原大學/理學院/化學研究所/碩士(2019年)

https://doi.org/10.6840/cycu201900665

摘要

本碩士論文的研究主軸，是利用導入不同型態的二氧化矽粉體(表面官能基、有無孔隙及孔隙的多寡)導入於具亞胺鍵之乙二醇殼聚醣自癒性水膠，以製備一系列的有機-無機複合自癒性水膠，並以流變儀研究導入不同二氧化矽粉體對此複合自癒性水膠之流變行為之影響。
在二氧化矽粉體的製備方面，首先以鹼催化之溶膠-凝膠法對四甲氧基矽氧烷進行水解縮合反應，製備一種表面具單純-OH基之無孔二氧化矽粉體(簡稱HS)。 另一方面，以鹼催化之溶膠-凝膠法對四乙氧基矽氧烷/3-氨基丙基三乙氧基矽烷(莫耳數比為25: 1)進行水解縮合反應，製備一種表面具-OH基及部份胺基(-NH2)之無孔二氧化矽粉體(簡稱AS)。 在有孔的二氧化矽粉體製備方面，調控四乙氧基矽氧烷/3-氨基丙基三乙氧基矽烷的莫耳數比(55:1/25:1/5:1/1:1)共四種，以鹼催化進行溶膠-凝膠反應，同時以果糖為非界面活性劑模板，並在具胺基之二氧化矽粉體合成完畢之後，利用大量的清水將果糖洗出，以製備一系列具介孔的二氧化矽粉體。 所合成的六種粉體藉由紅外光譜儀(FTIR)、核磁共振光譜儀(13C-NMR及29Si-NMR)，利用能量散佈分析儀(ESD)檢測氮元素及矽元素的比例，利用氮氣吸/脫附儀(BET)檢測六種粉體的孔隙大小及表面積大小，利用掃描式電子顯微鏡(SEM)及穿透式電子顯微鏡(TEM)觀察六種不同二氧化矽粉體的表面型態。
在自癒水膠材料的製備上，以自身合成之雙端醛基聚乙二醇(分子量4000)與[中性]的乙二醇聚殼醣商品進行反應，以合成一系列具動態亞胺鍵(-C=N-)的自癒性水膠，進一步以FTIR 確認亞胺鍵已經成功的生成，並以流變儀探討自癒性水膠之流變行為(包含: 應變掃描、應變轉換、儲存模數、極限應變及回復率)。
在自癒水膠複合材料的製備與流變行為檢測上，分為三個不同的部份來討論，(1) 將HS及AS二氧化矽粉體導入自癒水膠材料中，發現具有-OH 官能基的HS二氧化矽粉體的導入會造成自癒合水膠複合材料初始儲存模數的下降、極限應變百分率的微幅上升及回復率的上升。 另一方面，表面具有少量一級胺基的AS二氧化矽粉體導入自癒水膠材料會造成自癒合水膠複合材料初始儲存模數的上升、極限應變百分率的明顯上升及回復率的微幅上升。 (2)在相同的胺基含量修飾的AS二氧化矽粉體，比較無孔洞及有孔洞的二氧化矽粉體的導入對自癒水膠材料的流變行為影響，可以發現: 有孔洞的胺基修飾的二氧化矽粉體相較於會對自癒水膠材料的初始儲存模數、極限應變百分率及回復率都有較大幅的提升。 (3) 在相同的非介面活性劑濃度下，胺基修飾含量越多的二氧化矽粉體在導入自癒水膠材料中時，對自癒水膠材料材料的初始儲存模數、極限應變百分率及回復率也都有較大幅度的性質提升。

關鍵字

自癒性水膠 ； 二氧化矽 ； 複合式水膠 ； 流變

並列摘要

The main research axis of this master's thesis is to introduce different types of silica powders (surface functional groups, presence or absence of pores, and pores) into ethylene glycol chitosan self-healing hydrogel with imine bond. In order to prepare a series of organic-inorganic composite self-healing hydrogels, and rheometer to study the influence of different silica powders on the rheological behavior of the composite self-healing hydrogels.
In the preparation of the silica powder, the base-catalyzed sol-gel method is used to prepare a non-porous silica powder having a simple -OH group by performing hydrolysis/condensation reactions of tetramethyl orthosilicate (TMOS), as denoted as HS. On the other hand, a base-catalyzed sol-gel method is used to carry out a hydrolysis condensation reaction on tetraethyl orthosilicate (TEOS) and (3-aminopropyl)triethoxysilane (APTES) (molar ratio of 25:1) to prepare a non-porous silica powder having -OH group and partial primary amine group (-NH2), as denoted as abbreviated as AS. With fructose as non-surfactant template, controlling the molar ratio of TEOS/APTES in the preparation of porous silica powder (55:1/25:1/5:1/1:1), four mesoporous silica powders with different amount of primary amine modification were obtained. The above six kinds of silica powders synthesized were characterized by Fourier-Transformation infrared (FTIR), nuclear magnetic resonance (13C-NMR and 29Si-NMR) spectroscopy, and the ratio of nitrogen element and silicon element was measured by energy dispersive spectrometer (EDS). The pore size and surface area of six powders was measured by BET. The surface morphology of six different silica powders was observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).
In the preparation of self-healing hydrogels, a self-synthesized double-end aldehyde-based polyethylene glycol (molecular weight 4000) is reacted with a [neutral] ethylene glycol poly-shell sugar commodity to synthesize a series of dynamic imines. The self-healing hydrogels of the imine bond (-C=N-), further confirmed by FTIR that the imine bond has been successfully formed, and the rheological behavior of the self-healing hydrogel is analyzed by rheometer (including: strain scanning, strain conversion, storage modulus, ultimate strain and recovery rate).
In the preparation and rheological behavior detection of self-healing hydrogels, it is divided into three different parts to discuss: (1) Introducing HS and AS silica powder into self-healing hydrogels, and found that the introduction of OH-functionalized HS silica powder results in a decrease in the initial storage modulus of the self-healing hydrogel composite, a slight increase in the ultimate strain percentage, and an increase in the recovery rate. On the other hand, the introduction of AS silica powder with a small amount of primary amino groups on the surface of the self-healing hydrogels results in an increase in the initial storage modulus of the self-healing hydrogel composites, a significant increase in the ultimate strain percentage, and a slight increase in the recovery rate. (2) In the same amine content modified AS silica powder, the effect of the introduction of non-porous and voided silica powder on the rheological behavior of self-healing hydrogels can be found: Compared with the initial storage modulus, ultimate strain percentage and recovery rate of amine-modified silica powder, the amine-modified silica powder has a large increase. (3) At the same concentration of non-surfactant, the more the primary amine content of the silica powder is introduced into the self-healing hydrogels, the initial storage modulus and ultimate strain of the self-healing hydrogels. Both the percentage and the response rate of self-healing hydrogels have also improved significantly.

並列關鍵字

self-healing ； silica ； composite hydrogel ； rheology

參考文獻

第六章 參考文獻

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