Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3590
標題: 藉由新穎方法合成氧代氮代苯并環己烷與其性質之研究
Syntheses and Properties of Benzoxazines by Novel Approach
作者: 曹雅如
Tsao, Ya-Ru
關鍵字: benzoxazine;氧代氮代苯并環己烷;epoxy;azomethine;環氧樹脂
出版社: 化學工程學系所
引用: [1] H. Ishida, Allen, J. D. J. Polym. Sci. Part B: Polym. Phys., 34, 1019(1996) [2] X. Ning, and H. Ishida, J. Polym. Sci. Part A : Polym. Chem., 32, 1121 (1994) [3] H. Ishida, and Y. Rodriguez, Polymer, 36, 3151(1995) [4] Z. Brunovska, J. P. Liu, and H. Ishida, Macromol. Chem. Phys., 200, 1745(1999) [5] T. Agag and T. Takeichi, Macromolecules, 34, 7257-7263(2001) [6] T. Agag and T. Takeichi, Macromolecules, 36, 6010-6017(2003) [7] Wang, Y. X.; Ishida, H. Macromolecules, 33, 2839(2000) [8] Z. Brunovska, R. Lyon, H. Ishida Thermochim Acta, 357, 195(2000) [9] Z. Brunovska, H. Ishida, J. Polym. Sci., 73, 2937(1999) [10] H. Kimura,Y. Murata, A. Matsumoto, K. Hasegawa, K. Ohtsuka, A. Fukuda, J. Polym. Sci., 74, 2266(1999) [11] T. Agag and T. Takeichi, J. Polym. Sci. Part A : Polym. Chem. 44, 1424(2006) [12] Y. L. Liu, J. M. Yu, C. I. Chou, J. Polym. Sci. Part A : Polym. Chem. 42, 5954-5963 (2004) [13] Y. L. Liu, J. M. Yu, J. Polym. Sci. Part A : Polym. Chem. 44, 1890 (2006) [14] C. H. Lin, S. X. Cai, T. S. Leu, T. Y. Hwang, H. H. Lee, J. Polym. Sci. Part A : Polym. Chem. 44, 3454(2006) [15] J. Dunkers, H. Ishida, J. Polym. Sci. Part A : Polym. Chem., 37, 1913(1999) [16] T. Takeichi, Y. Guo, S. Rimdusit, Polymer, 46, 4909(2005) [17] Ishida, U.S. Pat. 5,543,516(1996) [18] Magendie et al., U.S. Pat. US 2004/0054120 A1 [19] Y. L. Liu, C. I. Chou, J. Polym. Sci. Part A : Polym. Chem. 43, 5267 (2005) [20] M. A. ESPINOSA, V. CA' DIZ, M. GALIA, J. Polym. Sci. Part A : Polym. Chem. 42, 279 (2004)
摘要: 
本實驗首先利用2-hydroxybenzaldehyde與三個單官能胺類(4-aminotoluene/4-aminophenol/4-aminobenzoic acid)及三個商業用二胺(BAPP/DDM/DDS)合成一系列含Schiff base linkage之化合物(PT-HB/4-AP-2-HB/4-AA-2-HB/BAPP-HB/DDM-HB/DDS-HB)。再經由親核加成將DOPO與含Schiff base linkage之化合物反應合成一系列同時擁有P和C雙對掌中心之diastereomers單體(P-PTHB/o-DAH/ P-AAHB/P-BAPP-HB/P-DDM-HB/P-DDS-HB)。利用上述這些同時擁有酚基以及二級胺之diastereomers單體與甲醛反應合成一系列新穎含磷之benzoxazine(P-CH3-Bz/P-OH-Bz/P-COOH-Bz/P-BAPP-Bz/ P-DDM-Bz/ P-DDS-Bz)。藉由FTIR、NMR、MASS、EA鑑定其結構正確。
因為benzoxazine為一酸催化開環反應,我們發現單官能benzoxazine P-OH-Bz與P-COOH-Bz擁有與雙官能benzoxazine相似之玻璃轉移溫度,其中P-COOH-Bz之玻璃轉移溫度高達191oC。我們由p(P-COOH-Bz)在不同聚合溫度下之FTIR追蹤可以看出反應在220 oC聚合溫度後,生成芳香族酯基(Ar-COOR)之特徵峰。顯示在P-COOH-Bz的開環反應過程中,p(P-COOH-Bz)的酚基與P-COOH-Bz本身的酸基產生鍵結。此結果也與DSC所測得之玻璃轉移溫度在聚合溫度200oC和220oC間急遽上升40oC可相互驗證。
由於立體障礙的關係,p(P-BAPP-Bz)、p(P-DDM-Bz)和p(P-DDS-Bz)之玻璃轉移溫度及熱裂解溫度不如預期的高。然而,p(P-BAPP-Bz)、p(P-DDM-Bz)和p(P-DDS-Bz)的合成顯示出一個新的benzoxazine合成路徑,將在未來持續探討。

A series of new monomers, P-PTHB, o-DAH, P-AAHB, P-BAPP-HB, P-DDM-HB and P-DDS-HB, were successfully synthesized from the nucleiphilic addition of the Schiff-base compounds (PT-HB, 4-AP-2-HB, 4-AA-2-HB, BAPP-HB, DDM-HB, DDS-HB) and DOPO.
A series of novel benzoxazines, P-CH3-Bz, P-OH-Bz, P-COOH-Bz, P-BAPP-Bz, P-DDM-Bz and P-DDS-Bz, were prepared from the above P-PTHB, o-DAH, P-AAHB, P-BAPP-HB, P-DDM-HB and P-DDS-HB, respectively. And their structures were confirmed by FTIR, NMR, MASS, EA.
The Tg of p(P-OH-Bz) and p(P-COOH-Bz) are almost the same as difunctional polybenzoxazines. Especially, P-COOH-Bz exhibits the highest Tg of 191oC. According to FTIR spectra of p(P-COOH-Bz) after each cure stage, the condensation reaction between the phenolic OH and the carboxylic acid resulted in aromatic ester (Ar-COOR) during the curing reaction.
Due to the steric hindrance, the Tg and Td of p(P-BAPP-Bz), p(P-DDM-Bz) and p(P-DDS-Bz) are not as high as expected. However, the synthesis of p(P-BAPP-Bz), p(P-DDM-Bz) and p(P-DDS-Bz) leads to a new route for the synthesis of new benzoxazine, which will be discussed in the future.
URI: http://hdl.handle.net/11455/3590
其他識別: U0005-2707200621131100
Appears in Collections:化學工程學系所

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