Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3617
標題: 合成以芳香族二胺為基質的Benzoxazines樹脂與其聚合物性質之探討
Synthesis and Characterization of Aromatic Diamine-Based Benzoxazines and thermal properties of resulting thermosets
作者: 謝昭偉
Hsieh, Chao-Wei
關鍵字: Benzoxazine
氧代氮代苯并環己烷
Aromatic diamine
芳香族二胺
出版社: 化學工程學系所
引用: 1.Allen, D. J.;Ishida, H. J Polym Sci Part B: Polym Phys,1996, 34, 1019 2.Reghunadhan Nair, C. P. Prog Polym Sci, 2004, 29, 401 3.Wang, Y. X.;Ishida, H. J Appl Polym Sci, 2002, 86, 2953 4.Brunovska, Z.;Liu, J. P.;Ishida, H. Macromol Chem Phys, 1999, 200, 1745 5.Holly, F. W.;Cope, C. J Am Chem Soc, 1944, 66, 1875 6.Burke, W. J. J Am Chem Soc, 1949, 71, 609 7.Burke, W. J.;Bishop, J. L.;Mortense Glennie, E. L.; Bauer, W. N.;Jr. J. Org.Chem., 1965, 30, 3423 8.Ning, X.;Ishida, H. J Polym Sci Part A: Polym Chem, 1994, 32, 1121 9.Ishida, H.;Rodriguez, Y. Polymer, 1995, 36, 3151 10.Wang, Y. X.;Ishida, H. Macromolecules, 2000, 33, 2839 11.Wirasate, S.;Dhumrongvaraporn, S.;Allen, D.J.;and Ishida, H. J. Appl. Polym. Sci., 1998, 70, 1299 12.Hemvichian, K.;Ishida, H. Polymer, 2002, 43, 4391 13.Low, H. Y.;Ishida, H. J Polym Sci Part B: Polym Phys, 1998, 36, 1935 14.Allen, D. J.;Ishida, H. Polymer, 1996, 37, 4487 15.Rimdusit, S.;Ishida, H. Polymer, 2000, 41, 7941
摘要: 摘 要 本論文的實驗首先是利用四種商業化的芳香族二胺(DDM/DDS /BAPP/ BAB)合成一系列含有Imine linkage的化合物(DDM-HB/ DDS-HB/BAPP-HB/BAB-HB)。再利用NaBH4將HC=N還原成H2C-NH。最後將這些同時含有酚基和二級胺的單體與甲醛反應合成一系列新穎Benzoxazine(DDM-Bz/DDS-Bz/BAPP-Bz/BAB-Bz)。然後藉由NMR、FTIR來鑑定其結構的正確,然後經過高溫開環聚合反應後,利用DSC、TGA檢測它的熱性質。這一系列的Benzoxazine經過高溫硬化後,相較於以雙酚為基質的Benzoxazine,具有高玻璃轉移溫度(Tg)、高熱裂解溫度(Td)和高燃燒後的殘餘量(Char yield),有著較好的熱穩定性。 傳統雙官能的Benzoxazine合成都是利用diphenols、paraformaldehyde和 monoamines來做分子設計,將希望的官能基導入,來改變Polybenzoxazine的性質。本次實驗成功的將Aromatic diamine 導入分子中,而且沒有發生gel的現象,因此使的Benzoxazine的分子設計可以更加多元化。 第二部份的實驗則是將DOPO取代第一部份實驗所使用的還原劑NaBH4來還原imine linkage,藉此將磷原子導入Benzoxazine的分子結構內,以提升耐燃性,但是由於黏度太高不易加工,所以試著將合成的P-Bz和其他功能性高分子(如F-a、DDM-Bz、epoxy)混摻,藉此來提昇高分子的熱性質和機械性質。結果發現加入適量的P-Bz有效的提昇了F-a的熱穩定性。將P-Bz當作CNE的硬化劑,也可以得到熱性質不錯的產物,而且UL-94測試可達V-0等級。
Abstract Four high-purity aromatic diamines-based benzoxazines, which could not easily be synthesized by traditional approaches, were successfully synthesized by a facile, widely useful three-step synthetic method using four typical aromatic diamines – DDM, DDS, BAPP, and BAB, respectively, as starting materials. The structures of the monomers were confirmed by 1H-NMR, 13C-NMR, 1H-1H 2D NMR and 1H-13C 2D NMR spectra. Their high performance thermosets, were obtained by thermal curing of benzoxazines, and their properties were studied and compared with polymer derived from F-a, a typical aromatic biphenol-based benzoxazine. The aromatic-diamines based polybenzoxazines exhibit higher glass transition temperature and thermal stability than most conventional aromatic biphenols-based polybenzoxazines. Among the benzoxazines, DDM-Bz and F-a are constitutional isomers, but the Tg value and 5% decomposition temperature of P(DDM-Bz) are 53 and 111 oC, respectively higher than those of P(F-a), demonstrating the power of the molecule-approach to enhance the thermal properties. Because of the large varieties of aromatic diamines, this approach can increase the molecule-design flexibility of benzoxazines. The second experiment is addition of DOPO on the imine linkage of DDM-HB、DDS-HB and BAPP-HB,result in intermediates with a secondary amine linkage. The last step is the ring closure condensation of P-DDM-HB、P-DDS-HB and P-BAPP-HB, leading to benzoxazine (P-DDM-Bz、P-DDS-Bz and P-BAPP-Bz).To promote thermal stability and Mechanical characterization of copolymers based on P-Bz and Functionized polymers( DDM-Bz、F-a and epoxy).
URI: http://hdl.handle.net/11455/3617
其他識別: U0005-0808200717335000
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-0808200717335000
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