以有機酸酐進行幾丁聚醣胺基衍生化之研究

Studies on N-derivatization of Chitosan Using Anhydrides of Organic Acids

葉衛鼎(Wei-Ting Yeh)

指導教授 ： 陳齊聖

朝陽科技大學/理工學院/民生化工產業研發碩士專班/碩士(2010年)

摘要

本研究以不同種類之有機酸酐，在乙酸/甲醇溶液系統中，進行幾丁聚醣胺基之衍生化。衍生化反應所使用之有機酸酐為：偏苯三甲酸酐(trimellitic anhydride，衍生化之產物簡稱TMC)，琥珀酸酐(succinic anhydride，衍生化之產物簡稱SC)，順丁烯二酸酐(maleic anhydride，衍生化之產物簡稱MC)，磺酸苯甲酸酐(2-Sulfobenzoic acid cyclic anhydride，衍生化之產物簡SBC)，以及醋酸酐(acetic anhydride)。衍生化反應之取代率，以聚乙烯硫酸鉀溶液( N/400 P.V.S–K )滴定方式，測量反應前後自由胺基之差異計算。衍生化之幾丁聚醣在中性去離子水中溶解度，均顯著增加，依序為: MC（1.93%） > SBC（1.77%）> TMC（0.94）> SC（0.93）（去乙醯度85%之幾丁聚醣為0.21%）。衍生化之幾丁聚醣亦溶於大部份之稀酸溶液中。本研究亦探討以FTIR之光譜特性，定量去乙醯度以及取代率之方法。特徵吸收峰之強度與取代率約成正比，唯此種觀察尚未歸納出定量之關係。

關鍵字

幾丁聚醣 ； 醯化反應 ； 溶解度 ； 有機酸酐

並列摘要

This research studied the N-derivatization, using various organic acid anhydrides, in acetic acid / methanol solvent system, of chitosans. The organic acid anhydrides used included trimellitic anhydride (derivatized chitosan abbreviated as TMC), succinic anhydride (derivatized chitosan abbreviated as SC), maleic anhydride (derivatized chitosan abbreviated as MC), 2-sulfobenzoic acid cyclic anhydride (derivatized chitosan abbreviated as SBC) and acetic anhydride. The degree of substitution was determined by titration, using potassium polyvinyl sulfate (PVSK), and measuring the difference of the number of free amine before and after the reaction. The water solubilities of the derivatized chitosans were found to be significantly increased as compared to underivatized chitoson (degree of deacetylation was 85%): MC (1.93%) > SBC (1.77%) > TMC (0.94) > SC (0.93) (that of underivatized chitosan was 0.21%). The derivatized chitosans obtained in this research were soluble in most diluted acid solutions. This research investigated the quantification of the degrees of deacetylation and substitution by comparing FTIR spectrum. The intensities of the characteristic absorption peaks were found to increase with increasing degree of substitution. However, quantification relationship has yet to be established.

並列關鍵字

Solubility ； Anhydride ； Acylation reaction ； Chitosan

參考文獻

楊清任，「磺酸苯、偏苯三甲基、順丁稀二和琥珀酸酐進行幾丁聚糖胺基衍生化之製備」，碩士論文，朝陽科技大學應用化學系，臺中（2008）。

王嘉薇，「丁醯化幾丁聚醣之研究」，碩士論文，國立成功大學化學工程研究所，臺南（2003）。

degree of acetylation of chitin and chitosan by thermal analysis,” J. Thermal. Anal., Vol. 28, pp.189-193 (1983).

Bough, W. A., Salter, W. L., WU, A. C. M., and Perkins, B. E.” Influence of manufacturing variables on the characteristics and effectiveness of chitosan products. II. Coagulation of activated sludge suspensions,” Biotechnoloy and bioengineerin, Vol. 20, pp.1945-1955 (1978).

Baxter, A., Dillon, M., Taylor, K.D.A., Roberts, G.A.F, “Improved method for IR determination of the degree of N-acetylation of chitosan.” ,International Journal of Biological Macromolecules, Vol. 14, pp.166-169(1992).